Benha University Physics department MASS ......ionization mass spectra of some 6-fluoroquinolones molecules, namely: Norfloxacin, Pefloxacin, Ciprofloxacin and Levofloxacin.While the

MASS SPECTROMETRIC STUDY OF SOME FLUOROQUINOLONE

DRUGS USING ELECTRON IONIZATION AND CHEMICAL IONIZATION

TECHNIQUES IN COMBINATION WITH SEMI-EMPIRICAL

CALCULATIONS

BY

MAMOUN SARHAN MAHMOUD ABD EL KAREEM

(MSc PHYSICS)

Atomic Energy Authority Cairo Egypt

THESIS

SUBMITTED FOR THE PhD DEGREE (EXPERIMENTAL PHYSICS)

From

FACULITY OF SCIENCE

BENHA UNIVERSITY

Supervisors

2013

Prof Dr M I El-Zaiki Prof of Nuclear Physics

Physics Department

Faculty of Science (Benha University)

Prof Dr Ezzat TMSelim Atomic amp Molecular Physics Division

Experimental Nuclear Physics Department

Atomic Energy Authority (Egypt)

Prof Dr MARabbih Atomic amp Molecular Physics Division

Experimental Nuclear Physics Department


Prof Dr AMHassan Rezk National Center for Radiation Research

and Technology


Benha University

Faculty of Science

Physics department

Abbreviations and Acronyms

EI Electron Ionization

CI Chemical Ionization

MO Molecular Orbital

MNDO Modified Neglect of Diatomic Overlap

TFCndashMSMS Turbulent Flow ChromatographyTandem Mass

Spectrometry

SPE Solid-Phase Extraction

FQ Fluoroquinolone

SPME Solid-Phase Microextraction

LCMSMS Liquid ChromatographyndashTandem Mass Spectrometry

IE Ionization Energy

ΔHf Heats of Formation

PA Proton Affinity

AE Appearance Energy

IP Ionization Potential

GCMS Gas ChromatographMass Spectrometer

RI Relative Intensity

mz Mass to Charge Ratio

ACKNOWLEDGMENT

This work was performed in the Molecular Physics Division of the Experimental

Nuclear Physics Department in cooperation with Radiation Chemistry Department

National Center for Radiation Research and Technology Atomic Energy Authority

Cairo Egypt

I wish to express my deepest thanks to Head of Experimental Nuclear Physics

Department of the Egyptian Atomic Energy Authority and Head of Physics Department

Faculty of Science Benha University for their encouragement interest

Special thanks to Professor DrME ElndashZeiki Faculty of Science Benha University

for continuous support and for encouragement interest during the course of this work

I would like to express my deepest thanks to Professor Dr Ezzat TMSelim

Experimental Nuclear Physics Department of the Egyptian Atomic Energy Authority for

his great efforts in illuminating the discussion

I would like to express my gratitude and appreciation to Professor Dr MARabbih


his great efforts for suggesting and supervising this work and also for his valuable

guidance and illuminating discussions

I would like to express my gratitude and appreciation to Professor Dr AMHassan

Rezk Radiation Chemistry Department National Center for Radiation Research and

Technology Atomic Energy Authority for his great efforts in the mass spectrometric

measurements and supervising this work

Abstract

A mass spectrometer of the type QMS (SSQ710) is used to record the electron

ionization mass spectra of some 6-fluoroquinolones molecules namely Norfloxacin

Pefloxacin Ciprofloxacin and LevofloxacinWhile the chemical ionization mass spectra

of these compounds are recorded using Thermo Finnigan TRACE DSQ GCMS system

In EI mass spectra the relative intensities for the molecular ions [M]+bull

of the studied

compounds and the prominent fragment ions are reported and discussed Furthermore

fragmentation patterns for the four compounds have been suggested and discussed and

the most important fragmentation processes such as [M-CO2]+bull

[M-C2H4N]+ and [M-

CO2-C2H4N]+are investigated

On the other hand the chemical ionization (CI) mass spectra of the compounds have

been recorded using methane as the reagent gas These spectra are discussed in terms of

the structure of the compounds with particular reference to their conventional electron

ionization mass spectra The protonated molecules [M+H]+ are more relatively intense

than [M]+bull

ions in the recorded EI mass spectra indicating higher stability in the case of

[M+H]+

Also fragmentation patterns for the four compounds have been suggested and discussed

(using chemical ionization technique) and the most important fragmentation processes

such as [MH-CO2]+bull

[MH-C2H4N]+ and [MH-H2O]

+ are investigated

Using MNDO semi-empirical method for computation together with the experimental

results gave valuable information about the heats of formation and ionization energies of

the molecules The effect of substituents on the geometry of the neutral and ionized

molecules are reflected in the values of the ionization energy and heats of formation of

neutral ∆Hf(M) and ionized ∆Hf(M)+∙

molecules The calculated values for ionization

energies of Norfloxacin Pefloxacin Ciprofloxacin and Levofloxacin are 81 8 88 and

83 eV respectively The calculated charge distributions at N1 and O12 in the qinolone

ring of the studied molecules as well as the presence of a lone pair electrons at N1 and O12

atoms indicate that the ionization processes occur at these two atoms The appearance

(AE) and activation energies of the fragment ions [M-CO2]+bull

and [M-C2H4N]+ are also

calculated and discussed It is noteworthy that all the presently calculated values of

ionization appearance and activation energies are not yet published The MNDO method

is also used to probe the protonation of the studied compounds The calculated proton

affinities (PAs) together with ∆Hf [M+H]+ values at nitrogen (N1) and at oxygen (O12)

atoms are calculated These results give interesting features for the protonation sites The

protonation at oxygen (O12) site is more favored than that at nitrogen (N1) site

Furthermore the calculated values of the heats of formation of neutral [M] ionized [M]+bull

protonated molecule [M+H]+ and PAs values are reported for the first time

CONTENTS

Page

ABSTRACT і

CHAPTER 1 INTRODUCTION AND AIM OF THE WORK

11 Introduction 1

12 Aim of the Work 5

CHAPTER 2 THEORETICAL CONSIDERATIONS

21 Processes of Ionization and Dissociation by Electron

Ionization 6

22 Frank - Condon Principle 9

23 Ionization Probability Near Thershold 9

24 Determination of Thermochemical Data 10

25 Stevensons Rule 11

26 Characteristics of Mass Spectra 12

27 Simple Bond Cleavage Processes 12

28 Rearrangements Processes 13

29 Processes of Ionization and Dissociation by Chemical

Ionization 13

210 Proton Affinity 14

211 Semiempirical quantum chemical methods and the

predicting mass spectrometric fragmentations 15

CHAPTER 3 APPARATUS AND EXPERIMENTAL CONDITIONS

31 Apparatus 16

32 Materials 16

33 Experimental Conditions 17

CHAPTER 4 RESULTS AND DISCUSSION

41 Results 18

411 Experimental Measurements 18

412 Computational Results 19

42 Discussion 20

421 Mass spectra of Norfloxacin using EI technique 25

422 Ionization processes of Norfloxacin using EI technique 29

423 Fragmentation of Norfloxacin using EI technique 31

424 Mass spectrum of Norfloxacin using CI technique 37

425 Chemical ionization proton transfer 40

426 Fragmentation of Norfloxacin using CI technique 41

427 The proton affinity (PA) heat of formation(∆Hf) and

the charge distributions of Norfloxacin 43

43 1 Mass spectra of Pefloxacin under EI technique 45

43 2 Ionization Process of Pefloxacin using EI technique 49

43 3 Fragmentation of Pefloxacin using EI technique 51

434 Fragmentation of Pefloxacin using CI technique 55

435 The proton affinity (PA) heat of formation (∆Hf) and

charge distributions of Pefloxacin 58

44 1 Mass spectra of Ciprofloxacin using EI technique 59

44 2 Ionization process of Ciprofloxacin using EI technique 63

443 Fragmentation of Ciprofloxacin using EI technique 65

444 Fragmentation of Ciprofloxacin using CI technique 70

445 The proton affinity (PA)heat of formation (∆Hf) and

charge distributions of Ciprofloxacin 73

45 1 Mass spectra of Levofloxacin using EI technique 74

45 2 Ionization process of Levofloxacin using EI technique 78

453 Fragmentation of Levofloxacin using EI technique 80

454 Fragmentation of Levofloxacin using CI technique 83


charge distributions of Levofloxacin 86

CHAPTER 5 CONCLUSIONS 87

REFRENCES 88

ARABIC SUMMARY

List of Figures and Schemes

figure

Name

Page

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Figure 11

Figure 12

Figure 13

Figure 14

Figure 15

Potential energy curves for a molecule M ionized to either a

nondissociative M+bull

or dissociative state F+ + N

bull Path (a)

represents the adiabatic transition while path (v) represents

the vertical transition

Structure of fluoroquinolones

The structures of Norfloxacin Pefloxacin Ciprofloxacin

and Levofloxacin

The numbering system of the 6-fluoroquinolone compounds

used in this study

The protonation sites at oxygen(O12) and nitrogen(N1) atoms

for 6-fluoroquinolone compounds

The EI mass spectrum of Norfloxacin at 70 eV


The CI mass spectrum of Norfloxacin

The EI mass spectrum of Pefloxacin at 70 eV


The CI mass spectrum of Pefloxacin

The EI mass spectrum of Ciprofloxacin at 70 eV


The CI mass spectrum of Ciprofloxacin

The EI mass spectrum of Levofloxacin at 70 eV

7

20

22

23

24

26

27

38

46

47

57

60

61

72

75

Figure 16

Figure 17

Scheme 1

Scheme 2

Scheme 3

Scheme 4

Scheme 5

Scheme 6

Scheme 7

Scheme 8


The CI mass spectrum of Levofloxacin

Schemes

Main fragmentation pathways of Norfloxacin at 70 eV

Main fragmentation pathways of Norfloxacin under CI

technique

Main fragmentation pathways of Pefloxacin at 70 eV

Main fragmentation pathways of Pefloxacin under CI

technique

Main fragmentation pathways of Ciprofloxacin at 70 eV

Main fragmentation pathways of Ciprofloxacin under CI

technique

Main fragmentation pathways of Levofloxacin at 70 eV

Main fragmentation pathways of Levofloxacin under CI mode

76

85

33

42

52

56

67

71

81

84

List of Tables

Table

Name

Page

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

Table 10

Table 11

The different functional groups of 6-fluoroquinolones

The molecular ion (M)+bull

and the main fragment ions [mz] with their

relative intensities [] at 70 and 15 eV electron energies in the mass

spectra of Norfloxacin

Calculated charge distribution of neutral and charged Norfloxacin

molecule using MNDO method together with the charge difference (∆)

Calculated bond lengths of neutral and charged Norfloxacin using

MNDO method together with the bond length difference (∆ L)

Calculated ∆Hf(M)∆Hf(M)+bull

and IE values for the four 6-

fluoroquinolone molecules using MNDO method

Protonated molecules [M+H]+ and major fragment Ions [mz] with their

relative intensity [] for chemical ionization mass spectra of

Norfloxacin Pefloxacin Ciprofloxacin and Levofloxacin at 70 e V

Calculated heat of formation values for the protonated molecules

∆Hf(M+H)+ and proton affinities (PA) at O12 and N1 sites for 6-

fluoroquinolone drugs using MNDO method




spectra of Pefloxacin

Calculated charge distribution of neutral and charged Pefloxacin


Calculated bond lengths of neutral and ionized Pefloxacin using





20

28

30

34

35

39

44

48

50

53

62

Table 12

Table 13

Table 14

Table 15

Table 16

spectra of Ciprofloxacin

Calculated charge distribution of neutral and ionized Ciprofloxacin


Calculated bond lengths of neutral and ionized Ciprofloxacin using





spectra of Levofloxacin

Calculated charge distribution of neutral and ionized Levofloxacin


Calculated bond lengths of neutral and ionized Levofloxacin using


64

68

77

79

82

CHAPTER (1)

INTRODUCTION AND AIM OF THE WORK

11 Introduction

Mass spectrometer is a microanalytical technique that can be used selectively to detect

and determine the amount of a given analyte Mass spectrometer is also used to determine

the elemental composition and some aspects of the molecular structure of an analyte

These tasks are accomplished through the experimental measurement of the mass of gas-

phase ions produced from molecules of an analyte Unique features of mass spectrometer

include its capacity for direct determination of the nominal mass (and in some cases the

molar mass) of an analyte and to produce and detect fragments of the molecule that

correspond to discrete groups of atoms of different elements that reveal structural

features Mass spectrometer has the capacity to generate more structural information per

unit quantity of an analyte than can be determined by any other analytical

technique(1)

The production of positive ions by electron ionization is a widely employed

technique as it can be utilized for the analysis of nearly all gases volatile compounds

and metallic vapours The ion beam current can be accurately controlled because the

ionizing electron beam is generally change limited The energy of the electron beam can

also be varied precisely Thus ionized species of the complex molecules can be produced

both with or without fragmentation so as to reveal details relating to the molecular

structure(2)

As the energy of the electron beam is further increased the probability of ionization

increases and the parent ion is formed with the excess energy in its vibrational and

electronic degree of freedom When the excess energy possessed by the molecular ion

over the ground state become equal to the dissociation energy in one of the degrees of

freedom fragmentation takes place If the energy supplied to the molecular ion is again

increased more and more fragmentation occurs and the spectrum become complex In

organic mass spectrometry generally the mass spectrum is run at 70 eV to get

reproducible spectra(3)

The electron ionization (EI) method together with other techniques such as chemical

ionization (CI) mass spectrometry has proved to be a valuable tool in structural

characterization of positive ions and for determining fragmentation mechanism(4)

The

mass spectrum of each compound is unique and can be used as a chemical fingerprint

to characterize the compound and the molecular ion peak appears at mz value equal to

the molecular weight of the compound(4)

However one of the problems with the conventional electron ionization mode is that

molecular ions are often produced too excited that no peak representing the molecular

weight of the intact molecule is observed in the spectra In addition the spectra tend to be

complex and therefore difficult to interpret

On the other hand in CI mass spectrometry the characteristic ionization of the

materials in question is produced by ionic reactions than electron ionization CI mass

spectra are generally quite different and often more useful The technique gives ions of

low internal energy and is generally characterized by a lower abundance of the fragment

ions than electron ionization technique This is an important advantage since one can

focus on the molecular weight The technique has also been used to investigate the

relationship between the mass spectra of EI and of CI technique

On the other hand quantum chemical methods for the calculations of thermochemical

data have developed beyond the level of just reproducing experimental data and can now

make accurate predictions where the experimental data are unknown or uncertain(5)

The

semi-emiperical molecular orbital (MO) methods of quantum chemistry (6-17)

are widely

used in computational studies of large molecules particularly in organic chemistry and

biochemistry In their implementation they neglect many of the less important integrals

that occur in the ab initio MO formalism These severe simplifications call for the need to

represent the remaining integrals by suitable parametric reference data This strategy can

only be successful if the semi-empirical model retains the essential physics to describe

the properties of interest(18)

Different semi-empirical methods are available to study different molecular

properties both in the ground state and electronically excited states The present work

will focus on the semi-empirical calculation-using MNDO method- of the

thermochemical properties for ground state charged and protonated molecules in the gas

phase(18)

Inspection of the published works done using electron ionization chemical ionization

techniques and semi-empirical calculations for the structural identification of the present

compounds show that

(1) A fast and sensitive method has been developed for the determination of five

fluoroquinolones namely Enrofloxacin Ciprofloxacin Difloxacin Sarafloxacin and

Ofloxacin in commercial bovine milk after simple extraction method and LC-MS by

Ruiz-Viceo et al(19)

(2) A simple and rapid method for the determination of residues of Enrofloxacin and

Ciprofloxacin in tissues of farm animals using turbulent flow chromatographtandem

mass spectrometer (TFCndashMSMS)is described by Ralph et al (20)

(3) A solid-phase extraction (SPE) and liquid chromatography-tandem mass spectrometry

method was developed by Lee et al(21)

for the determination of selected fluoroquinolone

(FQ) drugs including ofloxacin norfloxacin and ciprofloxacin in wastewater samples

(4) Kurie et al (22)

developed a sensitive and useful method for the determination of five

FQs namely Enoxacin Ofloxacin Ciprofloxacin Norfloxacin and Lomefloxacin in

environmental waters using solid-phase microextraction (SPME) coupled with liquid

chromatographndashtandem mass spectrometer(LCMSMS)

(5) A group of Chinese(23)

investigate the fragmentation mechanism of

fluroquinolonessix compounds of fluroquinolones were analyzed using electrospray ion

trap mass spectrometer by collision induced dissociation in a multi-stage MS full scan

postive mode The mass spectra and structures of the six fluroquinolones were compared

with each other and it was observed that fluroquinolones gave characteristic fragment

ions by the neutral loss of CO2 HF and CO corresponding to the carboxy fluorine and

4-carbonyl group in their structures These characteristics used by the authors for future

structure elucidation in studies of fluroquinolones and analogue compounds

(6) Time of Flight Mass Spectrometer (TOF MS) with different electron energy for EI

and different gas pressure for CI of Levofloxacin lactate (LL) were studied by RQLi

and HYin(24)

The authors found a prominent fragmentation rout of Levofloxacin was an

elimination of CO 2 from molecular ion at mz 361 forming cation A at mz 317

followed by the cleavage of piperizine ring creating caion B at mz 246 and C at mz 71

Further fragmentation pathway was the formation of cation D at mz 231 from B

(7) The ∆Hf(M) ∆Hf [M+H] and local proton affinities (PAs) as well as the charge

distributions for the two highly electronegative hetero atoms (O4 and N1) in six

quinolone derivatives namely Quinolone 1-methyl quinolone 1-ethyl quinolone 1-

cyclopropopyl quinolone 3- carboxylic- quinolone and 6- fluoroquinolone have

been calculated using MNDO method by MARabbih et al(25)

12 Aim of the Work

The aim of the present thesis is to use the electron ionization and chemical ionization

techniques together with semi-empirical calculations (MNDO method) to investigate the

following compounds Norfloxacin Pefloxacin Ciprofloxacin and Levofloxacin from

the following point of view

(1) To record the mass spectra of the studied compounds using electron ionization at

15 as well as 70 eV

(2) To record the mass spectra of the studied compounds using chemical ionization

technique

(3) To correlate the data obtained from the two techniques

(4) To study the structural-reactivity relationship

(5) To suggest the primary fragmentation and subsequent

fragmentation mechanisms for the four compounds

(6) To determine the stability of the product ions using both ionization

techniques

(7) To use semi-emiperical calculations using MNDO method to

calculate the geometries features and the thermochemical

properties for the studied compounds This include

a Ionization energies (IErsquos) of these molecules

b Heats of formation of neutral (ΔHf (M)) and ionized molecules

(ΔHf (M)+bull

)

c Heats of formation of the protonated molecules (ΔHf [M+H]+)

d Proton affinities (PArsquos) of the molecules

f Bond length and charge distribution of the compounds under

investigation

CHAPTER (2)

THEORETICAL CONSIDERATIONS

21 Processes Of Ionization and Dissociation By Electron

Ionization

Electron ionization is a familiar method for creating ions from volatile gas-phase

molecules [M] By using fast moving electrons (or photons) to remove an electron from

the neutral molecule to create the odd-electron molecular ion M+bull

If an electron is removed from the highest occupied orbital of the molecule [M] the

minimum energy necessary for this process in which the molecular ion [M]+bull

is formed

is termed the ionization energy (IE) as in process (1)

e-

[M] [M] +bull

+ 2 e-

(ionization process) (1)

When the electron energy is increased the molecular ion [M]+bull

can dissociate to

form the fragment ion [F]+ and a neutral fragment [N]

bull as a simple bond cleavage process

(2) The minimum energy to do this is called the appearance energy (AE) of the fragment

ion [F] +

[M]+bull

[F]+ + [N]

bull (simple bond cleavage process) (2)

Also [M]+bull

could dissociate to produce a smaller mass fragment [F]+bull

and neutral

molecule N as a rearrangement process (3)

[M]+bull

[F]+bull

+[N] ( rearrangement process) (3)

The ionization process(26)

can be understood as represented in Figure 1 The

vibrational energies of both the molecule [M] and the molecular ion [M]+bull

may

represented by potential energy curves as shown in Figure 1

Io

ni

za

ti

on

E

ne

rg

y

(27)

Th

e

ion

izat

ion

ene

rgy

(IE

)

so

met

ime

s

call

ed

(les

s

cor

rect

ly)

the

ion

izat

ion potential (usually designated by IP or in the older literature I) is the energy

required to remove an electron from a molecule or atom

M rarr M+ + eminus ΔHrxn= IEa

Ionization energies are characterized as adiabatic or vertical values

Appearance Energy (27)

Since IEs are often determined in experiments in which the ionizing electron or

photon energy is varied until the appearance of a fragment ion is observed (threshold

measurements) IEs have been called appearance energies

AB rarr A+ + B + eminus Δ Hrxn = AP

22 Franck-Condon Principle

In electron ionization the impacting electron pass the molecule in a fraction of the

vibrational period no change occur during the course of the electronic transition in the

position and velocities of the nuclei This means that the nuclear configuration of the

system does not change during the transition This is the well known Franck-Condon

principle(28-29)

23 Ionization Probability Near Threshold

In the ionization of atomic system by electron ionization one can explain the

increase in the cross section qualitatively as follows when the energy of the electron

increases above critical energy of ionization an increase in the ionization cross-section

will also occur The theoretical treatment of the ionization probability near the threshold

is difficult but several attempts have been made Wigner(30)

and then Geltman(31)

showed

theoretically that the cross-section behavior in the threshold region is given by a power

law of the form

σ (E) = C (E-Eo)n-1

(4)

Where E is the actual electron energy Eo is the threshold energy C is a constant

and n is the total number of outgoing electrons for the ionization process

24 Determination Of Thermochemical Data

Mass spectrometer technique allows the determination of many thermochemical

quantities Heats of formation of the different molecular species ionization and

appearance energies of the molecular and fragment ions and electron affinities of ions

and radicals can be measured and used to obtain bond dissociation energies

For the molecule [M] the ionization energy of the molecular ion [M]+bull

which is formed

by the reaction

M+e- M

+bull + 2e

- (5)

Can be calculated from the relationship

IE[M]+bull

= ∆Hf[M]+bull

- ∆Hf[M] (6)

Where ∆Hf[M]+bull

and ∆Hf[M] are the heats of formation of the molecular ion and neutral

molecule respectively These values can be calculated using a semi-empirical

methods such as MNDO AM1and PM3

In fragmentation process such as

[M]+bull

[F]+

+ [N]bull (7)

The AE of the fragment ion [F]+

can be calculated from equation (8)

AE[F]+ = IE [F] +D[F-N] + Eexc (8)

Where IE [F]+ is the ionization energy of the fragment FD [F-N] represents the

dissociation energy and Eexc is the excess energy

The (∆Eth) is the calculated thermodynamic threshold value for the formation of an ion by

certain process and calculated from the following equation -

(∆Eth) = ∆Hf[F]+ + ∆Hf[N] - ∆Hf[M] (9)

and Eexc is calculated according to-

Eexc= AE(exp) - ∆Eth (10)

The ∆Hf[F]+ used for ∆Eth calculation must be free from any excess energy and is

obtained from the ionization energy of the free radical [F] by the equation

∆Hf[F]+ = IE[F] +∆Hf[F] (11)

25 Stevensons Rule A useful rule regarding the location of the positive charge was first formulated by

Stevenson(32)

He noted that for hydrocarbons(for example) the positive charge tend to

remain on the fragment with the lower ionization energy Since the idea arose from the

work of Audier(33)

one may call it the Steven-Audier rule

26 Characteristics of Mass Spectra

There are some observations characterizing the mass spectra- (34)

(a) The molecular processes leading to the formation of mass spectra consist of a

series of competing and consecutive unimolecular decomposition reactions of excited

molecular ion

(b) The effects of source temperature are far more pronounced in polyatomic mass

spectra

(c) Metastable transitions are observed ieunimolecular decomposition reactions

occurring with rate of 10-6

sec These transitions corresponding to either molecular or

fragment ions forming other ions by spontaneous decomposition

(d) Some mass spectra particularly of oxygen compounds show the presence of

negative ions they are generally in smaller abundance than the positive ions

27 Simple Bond Cleavage Processes

Simple bond cleavage occurs when the electron pair of a covalent bond is transferred to

two different centers The site of radical within the molecular ion [A-B]+bull

is defined by

the following equations Odd-electron ions dissociate by homolytic bond cleavage to an

even-electron fragment ion and a radical (equations 1213)

[A ndash B] +bull

A+ + B

bull (12)

odd even odd

[A ndash B] +bull

Abull + B

+ (13)

odd odd even

The fragment ion A+

or B+

with the greatest tendency to support an unpaired electron

will have a higher appearance energy

28 Rearrangements Processes Fragment ions can also be formed by processes in which the initial bond connections

in the molecular ion are reordered or rearranged Fortunately many of these

rearrangement processes have been characterized for organic molecules and therefore can

be predicated based on an ionrsquos structure Rearrangement reactions occur with the

movement of two or more sets of electron pairs


Ionization

One of the problems with the conventional electron ionization mode is that

molecular ions are often produced which are so excited that no peak representing the

molecular weight of the compound or the intact molecule is observed in the spectra This

lack of the molecular ion creates a problem in the sample identification because one must

depend on the detection of structure from fragment ions alone In addition the electron

ionization spectra tend to be complex and therefore difficult to interpret(35)

On the other hand in chemical ionization (CI) mass spectrometry the characteristic

ionization of the materials in question is produced by ionic reactions rather than electron

ionization Chemical ionization mass spectra are generally quite different and oftentimes

more useful than electron ionization spectra This technique requires a reaction gas which

can produce a set of ions which are either non reactive or only very slightly reactive with

the reaction gas itself but which can react with other materials The method is certainly

applicable for reaction gases methane isobutane ammonia acetaldehyde di-

methylether and iodomethane

For the methane as the reaction gas one introduces into the source of the mass

spectrometer a mixture of the methane and the added material (analyte) whose spectrum

is to be obtained Under this condition practically all of the electrons passing through the

gas within the source will ionize methane and ionization of the additive (analyte) by

electron ionization will be negligible

All of the primary ions of methane as in equation (14) react rapidly with methane (at

virtually every collision) to give product ions by reactions which are well established

CH4+ e- CH4

+bull CH3

+CH2

+ CH

++ 2e (14)

CH4+bull

+ CH4 CH5+ + CH3

bull (15)

CH3+ + CH4 C2H5

+ + H2 (16)

The major fragment ions of methane produced by 70 eV are CH4+ and CH3

+

consequently the major ions are CH5+ and C2H5

+ The reactions of these ions with the

sample produce the major part of chemical ionization spectrum

210 Proton Affinity

One may define the proton affinity (PA) (36)

of a molecule M as the energy required to

effect the forward reaction in equation (17) or as the negative enthalpy change associated

with the reaction (19)-

[BH]+ + M B+[M+H]

+ (17)

Where [BH]+ is the protonated molecule

The ion CH5+ is an efficient proton donor so that a sample molecule M can be ionized

according to equation (18)-

M + CH5+

[M+H]+ + CH4 (18)

M + H+ MH

+ (19)

∆Hordm = ∆Hf [M+H]+ - ∆Hf [M] - ∆Hf [H

+] = - PA

PA = - ∆Hordm

211 Semi-empirical quantum chemical methods and the

predicting mass spectrometric fragmentations

An impressive number of gas phase chemical studies of ions have emerged during the

last fifty years Most of these studies were experimental and a wide range of

instrumentation methods mostly mass spectrometric ones have been used More

recently these studies have been complemented by high level quantum chemical and

other model calculations providing firm connection between experiment and theory(37)

The semi-empirical molecular orbital (MO) methods of quantum chemistry are widely

used in compoutionaal studies of large molecules particulaary in organic chemistry and

biochemistryDifferent semi-empirical methods are available to study different molecular

properities both in the ground state and electronically excited states(38)

Semi-empirical molecular orbital (MO) methods of quantum chemistry are based on

the HartreendashFock formalism but make many approximations and obtain some parameters

from empirical data They are very important in computational chemistry for treating

large molecules where the full HartreendashFock method without the approximations is too

expensive because the use of empirical parameters appears to allow some inclusion of

electron correlation effects into the methods(39)

Semi-empirical Methods are simplified versions of Hartree-Fock theory using empirical

(= derived from experimental data) corrections in order to improve performance These

methods are usually referred to through acronyms encoding some of the underlying

theoretical assumptions The most frequently used methods (MNDO AM1 PM3) are all

based on the Neglect of Differential Diatomic Overlap (NDDO) integral approximation

while older methods use simpler integral schemes such as CNDO and INDO(40)

The author used the MNDO (Modified Neglected of Diatomic Overlap) is a semi-

empirical method for the present study The method has been developed by Prof

WThiels group at Max-Planck-Institut fuumlr Kohlenforschung in Germany(41)

The basic advantages of the usage of MNDO method can be outlined as (42)

1- The method enables the computation of structural electronic and many physical

properties of large systems

2- The method is suitable for studies in chemicals materials and pharmaceutical industrial

segments

3- The method can be used for its fast candidate structure or transition state identification

and perform high accuracy computations with full quantum treatment methods based

software such as HyperChem

4- MNDO is a well tested semi-emperical molecular orbital (MO) method and its

accuracy for predicting ΔHf (see for example Ref 16) values seems to be sufficient for

the present study(25)

5-The data reported for a large number of compounds prove that the MNDO method

achieves better agreement with experimental than MINDO-3(25)

6- The results of many authors(25)

for positive ions indicate that using MNDO and AM1

methods lead to geometries and energies close to that obtained at high level of ab initio

theory with of course minute faction of the computation effort

CHAPTER (3)

APPARATUS AND EXPERIMENTAL CONDITIONS

The electron ionization (EI) mass spectra of the four compounds investigated in this

work were obtained using the Finnigan Matt SSQ710 Gas ChromatographMass

Spectrometer (GCMS) system This system is controlled by the Dec 5000 Data Handling

System On the other hand the chemical ionization (CI) mass spectra were obtained

using The Thermo Finnigan TRACE DSQ GCMS system with Xcalibur ver 14

software

31 Apparatus

The main features of the the Finnigan Matt SSQ710 mass spectrometer are a high

vacuum system a confined EICI ion source a single quadrupole mass analyzer and a

positive ion negative ion electron multiplier The electron multiplier was operated in the

positive ion mode

The main features of the Thermo Finnigan TRACE DSQ mass spectrometer are almost

the same as the Finnigan Matt SSQ710 mass spectrometer Howeverthe former

spectrometer is provided with a prefilter between the EICI ion source and the single

stage quadrupole analyzer

Samples are introduced into the EICI ion source in both systems using a direct

insertion(solids) probe The solids probe is supplied with a probe holder that contains a

liquid cooling system for the probe The solids probe was operated in the temperature ndash

programmed mode where it is programmed to heat at a specific rate which is selected

according to the nature of the sample being analyzed

32 Materials

The compounds under investigation in the present work ( Norfloxacin Pefloxacin

Ciprofloxacin and Levofloxacin) were obtained from El-Obour Modern Pharmaceutical

Company first industrial zone El-Obour City Cairo Egypt These pure compounds were

used as received without any further purification

Methane (purity 9989 ndash Air products England) was used as the chemical ionization

reagent gas

33 Experimental Conditions

In the EI measurements the ion source temperature was maintained at

150 degC The EI mass spectra were recorded at two electron energies namely 15 and 70

eV

The probe temperature program for the EI measurements was as follows

30 degC for 01 minute

250 degC for 51 minutes


In the CI mode of operation the ion source temperature was maintained at 130 degC The

CI mass spectra were recorded at 70 eV electron energy

The probe temperature program for the CI measurements was as follows

Initial temperature was 70 degC for 60 sec

Ramp rate 50 degCmin

Final temperature 250 degC for 100 sec

CHAPTER (4)

RESULTS AND DISCUSSION

41 Results

411 Experimental measurements

The experimental results are obtained in the form of mass spectra ie relative

intensity (RI) against mass to charge ratio (mz) for all the studied compounds using

electron ionization (EI) and chemical ionization (CI) techniques

In this study the ionization of four members of 6-fluoroquinolones molecules

namely Norfloxacin Pefloxacin Ciprofloxacin and Levofloxacin have been investigated

using EI and CI techniques The measurements include the EI mass spectra of the studied

molecules at two different electron energy values (70 and 15 eV) while the CI mass

spectra have been obtained using methane as a reagent gas at 70 eV only In the study

one can discuss the mass spectral behaviors of these compounds using the two

techniques

Figures 67910121315 and 16 show the directly measured mass spectra of the

studied compounds using EI technique at 70 and 15 eV while Figures 81114 and 17

show the mass spectra of the compounds using CI technique at 70 eV only

The relative intensities (relative to the base peak) of the molecular ions and different

fragment ions at energies 70 and 15 eV of the compounds are listed in Tables 2811 and 14

while the CI mass spectra of the compounds under investigation are listed in Table 6

The fragmentation pathways of the main fragment ions formed from molecular ions at

70 eV are rationalized in schemes 135 and 7 while the fragmentation of the protonated

molecules of the compounds using CI mode are rationalized in schemes 246 and 8

412 Computational Results

Theoretical calculations are used for the physical properties of the molecules and the

gas phase basicity The calculations are performed using semi-emperical molecular

orbital procedure The program used in these computations is namely HyperChemtrade(43)

in

the modified neglect of diatomic overlap (MNDO) method These calculations give

useful information about the structure of the molecules which actually used to support

the experimental evidences The most important parameters calculated using MNDO

calculations include geometries bond lengths charge distribution and heats of formation

of the neutral ∆Hf(M)charged ∆Hf(M)+bull

and protonated molecule ∆Hf[M+H]+ The

ionization energy (IE) and proton affinity (PA) values for the studied molecules are

calculated using equations 6 and 19(chapter 2)The protonation processes at different

sites namely N1 and O12 of the 6- fluoroquinolones in the gas phase are also calculated

The bond lengths of neutral and ionized 6-fluoroquinolones molecules are given in

Tables 41013 and 16 Also the charge distribution of the individual oxygen O12 and

nitrogen N1 atoms for neutral and charged molecules are reported in Tables 3912 and 15

On the other hand the calculated values of IE ∆Hf(M) and ∆Hf(M)+ for all

compounds are given in Table 5 while the values of the heats of formation of the

protonated molecules ∆Hf[M+H]+ together with the proton affinity of the molecules at

oxygen O12 and nitrogen N1 sites are given in Table 7 It is interesting that the calculated

IE energy values for the studied molecules have not been previously reported in the

literature

42 Discussion

6-fluoroquinolones are an essential class of antibacterial compounds widely used in

clinical application(44)

In 1986 the fluoroquinolones were introduced and they were

modified from the class of antibiotics known as quinolones in early 1960 Initially 6-

fluoroquinolones were administrated orally for the treatment of infection caused by gram-

negative organisms and pseudomonas species Several 6-fluoroquinolones play a vital

role for the treatment of community acquired pneumonia and intra-abdominal infections

Quinolones consist mainly of bicyclic ring structure and the different functional groups

are substituted at position N1 (R1) such as ethyl cyclopropyl and at C7 (R2) such as

piperazyinyl as shown in Figure 2 and Table 1

Figure 2 Structure of fluoroquinolones

Table 1 The different functional groups of 6-fluoroquinolones

Molecule

R1

R2

Norfloxacin

Pefloxacin

Ciprofloxacin

Levofloxacin

ethyl

ethyl

cyclopropyl

18 heterocyclic ring

piperazinyl

4-methyl-piprazinyl

piperazinyl

4-methyl-piprazinyl

The presence of different substituent groups is influenced not only the

microbiological and physical properties but also the geometry of the neutral molecule

which effect the thermochemical properties The presence of different functional groups

at N1 or C7 positions influence both microbiological and pharmacokinetic properties(45)

This may lead one to investigate and study the mass spectra the fragmentation pathways

the heats of formation the ionization energies and the appearance energies of some

important fragment ions such as [M-CO2]+ and [M-C2H4N]

+ for the four studied

compounds

The structures of the four compounds are shown in Figure 3 while the numbering

system is shown in Figures 4 Figure 5 shows the possible protonation sites (oxygen O12

and nitrogen N1) of 6-fluoroquinolones

NN

N

F

CH3

O O

OH

PEFLOXACIN

H3C

NN

HN

F

O O

OH

CIPROFLOXACIN

NN

N

F

O O

OH

LEVOFLOXACIN

O

CH3H3C

Figure 3 The structures of Norfloxacin Pefloxacin Ciprofloxacin and Levofloxacin

Figure 4 The numbering system of 6-

fluoroquinolone compounds used in the study

Figure 5 The protonation sites at oxygen atoms and nitrogen (N1) for 6-fluoroquinolone

compounds

421 Mass spectra of Norfloxacin using EI technique

Electron ionization technique is the oldest and best characterized of all the ionization

methods In this technique a beam of electrons passes through the gas-phase of the

sample An electron that collides with a neutral analyte (M) molecule can knock off an

electron resulting in a positively charged ion(46)

The ionization process can produce a

molecular ion (M)+bull

which will has the same molecular weight and elemental

composition of the starting analyte and it can produce a fragment ion(s) which

corresponds to a smaller piece of the analyte molecule as described in equations 1and 3(

chapter 2)

Most mass spectrometers use electrons with energy of 70 electron volts (eV) for

recording mass spectra Decreasing the electron energy can reduce the fragmentation

processes but it also reduces the number of ions formed(46)

In this study 70 and 15 eV

electron energies were used to study the fragmentation processes The mass spectra of

Norfloxacin at these two energies are shown in Figures 6-7 in the range from mz 56 to

mz 320

Norfloxacin C16H18FN3O3 (1-ethyl-6-fluoro-14-dihydro-4-oxo-7(1-piperazinyl)-3-

quinoline carboxylic acid) is a synthetic 6-fluoroquinolone antibiotic which is structurally

related to nalidixic acid(47)

The addition of a fluorine atom at C6 and a piperazine ring at

C7 has increased its potency in contrast to other fluoroquinolones(48)

Table 2 The molecular ion (M)+bull

and the main fragment ions [mz] with their relative

intensities [] at 70 and 15 eV electron energies in the mass spectra of Norfloxacin

15 e V

70 e V

mz

11

60

7

52

14

100

5

9

68

2

4

7

8

7

2

2

2

2

-

-

-

-

-

-

-

-

-

8

12

70

9

59

16

100

9

13

88

5

9

4

11

13

6

6

6

6

7

6

6

7

6

6

8

7

14

15

320

319 [M]+middot

278

277 [M-C2H4N]+

276

275 [M-CO2]+

245

234

233[M-CO2-C2H4N]+

219

218

217

204

203

190

189

176

175

161

95

85

83

81

73

71

69

57

56

422 Ionization processes of Norfloxacin using EI technique

Ionization processes depend on the chemical environment of the atom from which the

electron is removed These have been found to correlate with such chemical parameters

as atomic charge electronegativity reactivity effect of substituent parameters proton

affinities and with the predictions of a wide range of semi-empirical parameters used in

electronic structure calculations(49)

The

removal

of an

electron

from an

organic

molecule

often

leads to

change in

its

relative

thermodynamic stability The energy necessary to produce [M]+bull

depends on the energy

of the electron expelled The process of ionization occurs mainly in molecules which

contain a highly electronegative atoms or groups

Norfloxacin molecule has a highly electronegative atoms O12 (-0298 e) and N1 (-

0309 e) as shown in Table 3 From the calculated charge distributions at N1 and O12 in

the qinolone ring of Norfloxacin and the presence of a lone pair electrons at these atoms

one can suggest that the ionization processes may occur at these atoms The calculated

value of the ionization energy of Norfloxacin is equal to 810 eV (782 kJmol-1

) (using

equation 6 chapter 2)

Table 3 Calculated charge distribution of neutral and charged Norfloxacin molecule

using MNDO method together with the charge difference (∆)

423

Fragm

entatio

n of

Norflo

xacin

using

EI

techniq

ue

Most

previous

research focused on the detection of Norfloxacin in biological samples

(214850-51) where

other research focused on crystal investigation of Norfloxacin(52-56)

However the present

study is interested in the ionization and fragmentation of the compound under electron

ionization Therefore the main fragmentation pathways at 70 eV for Norfloxacin have

been reported in scheme 1 and examined in order to understand the principle of their

electron-induced cleavage

The EI mass spectra of Norfloxacin are recorded at both 15 and 70 eV electron

energies Table 2 contains the relative intensities of the molecular ion and the main

fragment ions from mz 56 up to mz 319 The molecular ion of Norfloxacin at mz 319 is

observed in the spectra at both 70 eV and 15 eV with relative intensities 70 and 60

respectively

The first characteristic fragmentation pathway for Norfloxacin is the formation of the

[M-CO2]+bull

ion at mz 275 (RI =100 ie the base peak in the mass spectrum) This ion is

formed by the elimination of CO2 from the carboxyl group attached to carbon C3 atom of

Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C9

O10

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0309

0199

-0264

0338

-0119

-0015

0102

0082

-0050

0096

0160

13002

0417

-0295

-0367

-0298

-0169

-0395

0127

0095

-0320

0095

0127

-0287

0175

-0202

0314

-0078

0000

0137

0173

-0145

0190

0149

-0004

0399

-0291

-0324

-0230

-0128

-0168

0082

0103

-0339

0105

0078

0022

-0024

0062

-0024

0041

0015

0035

0091

-0095

0094

-0011

-0006

-0018

0004

0043

0068

0041

0227

-0045

0008

-0019

0010

-0049

the molecular ion following the migration of hydrogen atom from the OH group to C3

(Scheme 1) This is confirmed by the calculated bond length for C3C9 in the charged

molecular ion which is greater than that of the neutral molecule by 00078Aring as reported in

Table 4 The relatively high intensity of [M-CO2]+bull

ion indicates the high stability of the

ion The positive charge on the oxygen O12 stabilized the [M-CO2]+bull

fragment (odd-

electron fragment ion) It is worth noting that the fragmentation of the molecular ion to

produce the fragment [M-CO2]+bull

ion is the most favorable process The fragment [M-

CO2]+bull

ion undergoes further fragmentation resulting in the formation of the fragment [M-

CO2- C2H4N]+ ion at mz 233(RI=88) by loss of [C2H4N]

bull radical

The second characteristic fragmentation pathway for Norfloxacin is due to the

formation of the fragment [M-C2H4N]+ ion at mz 277 with RI= 59 by the loss of

C2H4Nbull radical from piperazinyl group This is confirmed by the calculated bond length for

C15C16 and C18C19 in charged molecular ion which are greater than that of the neutral

molecule by 00098Aring and 00044Aring respectively (Table 4)The fragment [M-C2H4N]+ ion

undergoes further fragmentation resulting in the formation of the fragment [M- C2H4N-

CO2]+ ion at mz 233 with RI=88 by the loss of CO2 from [M-C2H4N]

+ ion through

simple cleavage of C3-C9 bond and rearrangement of hydrogen atom from O10-H to C3

(Scheme 1)

The peak observed at mz 218 (RI= 9) in the mass spectrum of Norfloxacin might be

due to the loss of CH3 radical from the fragment [M-CO2- C2H4N]+ ion Also the fragment

ion at mz 218 can be formed directly from [M-CO2] + by loss of the neutral fragment

C3H7N (Scheme 1)

It is interesting to calculate thermochemical quantities such as ∆Hf(M) and ∆Hf(M)+bull

for

Norfloxacin using the MNDO method Hence one can calculate the IE value for

Norfloxacin (using equation 6 chapter 2) as the difference between ∆Hf(M)+bull

and ∆Hf(M)

leading to calculated value of IE (Norfloxacin) equal to 810 eV (782 kJmol-1

) (Table

5) The ionization of Norfloxacin probably occurs as a result of a removal of one of the

lone pair electrons of N1or O12 which may be confirmed by the calculated values for

charge difference (∆) at N1and O12 (0022e and 0068 e respectively) as listed in Table

3To the best of knowledge no experimental or theoretical values for ∆Hf(M)+bull

and

∆Hf(M) for Norfloxacin were reported in the literature

Scheme 1 Main fragmentation pathways of Norfloxacin at 70 eV

N

O O

O HF

NN

M

= 319

- CO2

N

O

F

NN

= 275

C2 H

4 N

= 277

N

O O

O HF

RI = 70 RI = 100

RI = 59

H

N

O

HF

RI = 88

C2H

4N

- CO2

= 233

NN

+ +

- C3 H

7 N

N

O

HF

N

mz mz

mz

mz = 218

RI = 9

mz

HH rearrangement

rearrangement

+

si m

pl e

cl e

av

ag

e

Table 4 Calculated bond lengths of neutral and charged Norfloxacin using MNDO

method together with the bond length difference (∆ L)

Table

5

Calcul

ated

∆Hf(M

)∆Hf(

M)+bull

an

d IE

values

for the

four

6-

fluoro

quinol

one

molec

ules

using

MND

O method

Neutral molecule

Bond Bond Length(Aring)

Charged molecular ion


∆ L

N1-C2 14007

C2-C3 13700

C3-C4 14881

C4-C4a 15012

C4a-C5 14185

C5-C6 14294

C6-C7 14433

C7-C8 14203

C8-C8a 14304

C8a-N1 14204

N1-C20 14830

C20-C21 15379

C3-C9 14950

C9-O10 13571

C9-O11 12304

C4-O12 12275

C6-F13 13223

C7-N14 14306

N14-C15 14706

C15-C16 15517

C16-N17 14676

N17-C18 14677

C18-C19 15514 C19-N14 14706

N1-C2 14167

C2-C3 13650

C3-C4 14863

C4-C4a 15080

C4a-C5 14118

C5-C6 14299

C6-C7 14807

C7-C8 14391

C8-C8a 14142

C8a-N1 13980

N1-C20 14934

C20-C21 15374

C3-C9 15028

C9-O10 13527

C9-O11 12268

C4-O12 12237

C6-F13 13126

C7-N14 13740

N14-C15 14962

C15-C16 15615

C16-N17 14567

N17-C18 14571

C18-C19 15558 C19-N14 14935

00160

-00050

-00018

00068

-00067

00005

00374

00188

-00162

-00224

00104

-00005

00078

-00044

-00036

-00038

-00097

-00566

00256

00098

-00109

-00106

00044

00229

IE

eV k J mol-1

∆Hf(M)+bull

k J mol-1

∆Hf(M)

k J mol-1

Molecule

The appearance energy (AE) of the fragment [M-CO2]+bull

ion at mz= 275 is calculated

(using the heats of formation of ∆Hf (M) molecule ∆Hf (CO2) and ∆Hf [M-CO2]+bull

) and

is found to be equal 830 eV(801 kJmol-1

) The difference between the value for AE [M-

CO2]+bull

and IENorfloxacin=810 eV (782 kJmol-1

) gives the activation energy to produce the

fragment [M-CO2]+bull

ion as equal to 19 kJmol-1

(020eV) This indicates that the process

forming the fragment [M-CO2]+bull

ion is the first fragmentation process as discussed in

section 423 and illustrated in scheme 1 by the author

81 782 305 -485

Norfloxacin

8 772 314 -464

Pefloxacin

88 849 485 -368

Ciprofloxacin

83 801 142 -631

Levofloxacin

Similarly the appearance energy of the [M-C2H4N]+ ion at mz=277 is calculated

(using the heats of formation of the neutral molecule ∆Hf (M) neutral fragment ∆Hf

(C2H4N) and ∆Hf (M-C2H4N)+) and is found to be equal to 94 eV (907 kJmol

-1) The

difference between the value for AE [M-C2H4N]+ and IENorfloxacin=810 eV (782 kJmol

-1)

gives the activation energy to produce the fragment [M-C2H4N]+ ion as equal to 125

kJmol-1

(130 eV) which is larger than the activation energy for forming [M-CO2]+

ion

by 106 kJmol-1

(110 eV) This indicates that the process forming the fragment [M-

C2H4N]+ ion is the second fragmentation process as discussed in section 423 and

illustrated in scheme 1 by the author

424 Mass spectrum of Norfloxacin using CI technique

The chemical ionization technique was introduced as ionization method by Munson

and Field in 1966(57)

by allowing a reagent gas into an EI source The pressure in this

technique is typically 1 torr The chemical ionization technique is usually defined as a

soft-ionization method This means that the energy deposition into the molecule is

thought to be less than that present in the electron ionization mode This is reflected on

the occurrence and or on the yield of ions formed by fragmentation processes which

will be less than the fragments in EI method Hence the mass spectra of CI are much less

complex than the EI spectra and few fragmentations are observed An ion at mz [M+H]+

is the base peak in more spectra of these studied molecules This is an important

advantage since this allows one to focus on the molecular ion In the case of the chemical

ionization mass spectrum of Norfloxacin (Figure 8) methane was used as the reagent gas

in the ionization chamber

Table 6 Protonated molecules [M+H]+ and major fragment Ions [mz] with their relative

intensity [] for chemical ionization mass spectra of Norfloxacin Pefloxacin

Ciprofloxacin and Levofloxacin at 70 e V

Norfloxacin Pefloxacin

Ciprofloxacin Levofloxacin

mz RI[] mz RI[]

mz RI[] mz RI[]

97 17 163 8 218 15 236 32 237 6 250 6 252 5 258 7 264 9 270 8 272 5 274 6 275 9 276 60 277 23 278 55 279 13 290 10 292 9 302 8 304 20 306 12 316 5 318 10 320[M+H]

+ 100 321 18 334[M+CH3]

+ 14 348[M+C2H5]

+ 20

289 6 290 31 291 9 292 12 316 10 317 5 318 27 319 6 332 6 333 6 334[M+H]

+ 100 335 19 346 6 348[M+CH3]

+ 5 362[M+C2H5]

+ 21

276 10 287 8 288 52 289 14 290 17 302 5 304 5 314 6 316 18 317 9 318 38 319 9 320 14 330 5 332[M+H]

+ 100 333 18 334 6 346[M+CH3]

+ 17 360[M+C2H5]

+ 23 361 6

130 7 318 14 319 9 320 31 321 7 344 5 346 6 348 7 360 9 361 9 362[M+H]

+ 100 363 20 376[M+CH3]

+ 5 390[M+C2H5]

+ 19

425 Chemical ionization proton transfer

Gas-phase proton transfer reactions have been the subject of quantitative studies for

more than twenty years and the two fundamental aspects (their thermochemistry and

kinetics) are still under active investigation(58)

Among the wide variety of possible ionization reactions the most common is proton

transfer Indeed when analyte molecules M are introduced in the ionization plasma the

product CH5+ ions of the methane reagent gas can transfer a proton to the molecules M

producing the protonated molecular ions [M+H]+ This chemical ionization reaction can

be described as an acidndashbase reaction The tendency for a reagent ion to protonate a

particular analyte molecule M may be assessed from its proton affinity values The

observation of protonated molecular ions[M+H]+ implies that the analyte molecule M

has a proton affinity much higher than that of the reagent gas (PA(M)gtPA(CH4)) If the

reagent gas has a proton affinity much higher than that of an analyte (PA(CH4)gtPA(M))

proton transfer from CH5+ to M will be energetically unfavorable

(59)

426 Fragmentation of Norfloxacin using CI technique

The fragmentation processes in CI spectrum of Norfloxacin are easily distinguished

The protonated molecule [M+H]+ at mz 320 of Norfloxacin is formed under CI

condition with a strong molecular cationic species (RI=100) (Figure 8) A number of

authors( 214860)

have detected Norfloxacin in biological samples using different mass

spectrometric techniques and detected the protonated molecule at mz = 320 by CI

technique

The protonated molecule [M+H]+ of Norfloxacin undergoes fragmentation along two

different fragmentation pathways The first fragmentation pathway is the formation of the

fragment [MH- CO2]+ ion at mz 276 (RI=60) which is formed by loss of CO2 as shown

in scheme 2

The second fragmentation pathway in the CI mass spectrum of Norfloxacin is the

formation of the fragment ion at mz 278 (RI=55) which probably formed by loss of

neutral radical C2H4Nbull from the protonated molecule to form the fragment [MH- C2H4N]

+

ion

Two peaks observed at mz 334 and 348 are probably formed due to the methyl (CH3)+

and the ethyl (C2H5+) cations transfer processes to form methylated [M+CH3]

+ and

ethylated [M+C2H5]+ molecules with relative intensities 14 and 20 respectively

Further the peak observed at mz 302(RI=8) is formed by elimination of H2O from the

protonated molecule At the same time the protonation process may occurs at O11 or O10

but the distance between the attached proton and ndash OH of the carboxylic group is larger

than 18 Aring indicating that the probability of the loss of H2O is low(61)

N

O O

O HF

NHN

[M+H]+ = 320

- CO2

N

O

F

NHN

mz = 276

mz = 278

N

O O

O HF

RI = 100 RI = 60

RI = 55

H

C2 H

4 N

N

H+ H+

H+

N

O O

F

NHN

H+

- H2 O

mz = 302RI = 8

rearrangment

Scheme 2 Main fragmentation pathways of Norfloxacin using CI technique

427 The proton affinity (PA) heat of formation(∆Hf) and the

charge distributions of Norfloxacin

Proton affinities and heats of formation are important thermodynamic quantities that

can be derived from a variety of experimental measurements Modern computational

methods provide the means to estimate reliably the same quantities with an accuracy that

often rivals that of experiment(62)

In addition these methods can provide information to

complement results obtained experimentally and to examine problems that are not easily

approached directly such as site-specific proton affinities(62)

A case in point is the

protonation of the molecules which often can take place at more than one position

Computational studies can provide a reliable estimate of the proton affinity of molecules

as well as a measure of the thermodynamic difference between the various possible

points of attachment of the proton(62)

One of the computational studies is the calculated charge distributions of the

quinolone ring (pyridinyl) in neutral and charged Norfloxacin molecule (Table 3)The

charges on the atoms N1and O12 (-0309e and -0298e respectively) indicate high

electronegativity values So these atoms (sites) have a higher affinity to attach the proton

than the other atoms in the ring The calculated values of proton affinities (using equation

19 chapter 2 ) for O12 and N1 ( 904 and 749 kJmol-1

respectively) together with the heats

of formation of the protonated Norfloxacin molecule ∆Hf [M+H]+ at the site N1-H (297

kJmol-1

) and at the site O12-H (142 kJmol-1

) indicate that the protonated Norfloxacin

molecule at O12 is more stable than at N1by 155 kJmol-1

One may suggest that the

electrostatic interaction between the proton and oxygen O12 stabilized the protonated

species

Table 7 Calculated heat of formation values for the protonated molecules ∆Hf(M+H)+

and proton affinities (PA) at O12 and N1 sites for 6-fluoroquinolone drugs using MNDO

method

431

Mass

spectr

a of

Peflox

acin

under

EI technique

PA (M) kJmol

-1

∆Hf(M+H)+

kJmol-1

Protonated Site

∆Hf(M) kcalmol

-1

Molecule

904

749

142

297

O12H

N1H

-116

Norfloxacin

916

753

151

314

O12H

N1H

-111

Pefloxacin

904

745

255

418

O12H

N1H

-88

Ciprofloxacin

908

715

2

192

O12H

N1H

-149

Levofloxacin

Pefloxacin C17H20FN3O3 (1-ethyl-6-fluoro-1-4-dihydro-4-oxo-7(4-methyl-1-

piperazinyl) quinolone-3-carboxylic acid) is a second-generation 6-fluoroquinolone

antibacterial agent(63)

Most previous research is focused on the detection of Pefloxacin in

environmental samples(53)

However this work is interested in the structure

thermodynamic properties and fragmentation processes of Pefloxacin compound under

electron ionization (EI) at two electron energies The EI mass spectra of Pefloxacin are

reported at 70 and 15 eV electron energies and are shown in Figures 9-10 while the

relative intensities of the molecular ion and different fragment ions in the mass spectrum

relative to the base peak (mz 289) in the range from mz 56 up to mz 333 are listed in

Table 8



intensities [] at 70 and 15 eV electron energies in the mass spectra of Pefloxacin

15 eV

70 eV

mz

10

55

3

21

100

4

6

16

10

10

6

10

30

26

7

4

12

61

3

18

100

4

6

14

11

7

4

6

20

15

6

4

334

333 [M]+middot

291

290

289 [M-CO2]+

245

219

218 [M-CO2-C4H9N]+

203 [M-CO2-C4H9N-CH3]+

96

81

79

71 [C4H9N]+bull

70

57

56

432Ionization Process of Pefloxacin using EI technique

Pefloxacin molecule has a highly electronegative atoms O12 (-0300 e) and N1(-

0307e) as listed in Table 9 From these charge distributions at N1 and O12 in the

qinolone ring (pyridinyl) of Pefloxacin and the presence of a lone pair electrons at N1 and

O12 one can suggest that the ionization process occur at these atoms

On the other hand the calculated ionization energy of Pefloxacin is found to be equal to

800 eV (772 kJ mole-1

) (using equation 6 chapter 2) This value is nearly within

experimental error equal to the ionization energy (810 eV) of Norfloxacin (Table 5)

Table 9 Calculated charge distribution of neutral and charged Pefloxacin molecule using

MNDO method together with the charge difference (∆)

Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

-0307

0198

-0262

-0297

0178

-0206

0010

-0020

0056

C4

C4a

C5

C6

C7

C8

C8a

C21

C22

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

0337

-0119

-0016

0103

0081

-0050

0095

0162

-0002

04135

-0301

-0357

-0300

-0169

-0391

0128

0143

-0428

0144

0128

0193

0318

-0082

0000

0124

0218

-0171

0190

0151

-0003

0401

-0293

-0328

-0228

-0124

-0164

0114

0124

-0418

0126

0114

0183

-0019

0037

0016

0021

0137

-0121

0095

-0011

-0001

-0014

0008

0029

0072

0045

0227

-0014

-0019

0010

-0018

-0014

-0010

433 Fragmentation of Pefloxacin using EI technique

The molecular ion of Pefloxacin at mz 333 is observed in the EI mass spectrum with

relative intensities 61 and 55 at 70 and 15 eV respectively

The first characteristic fragmentation pathway for Pefloxacin is the formation of the

fragment ion at mz 289 (RI = 100) which represents the base peak in the mass

spectrum and is certainly due to the formation of the fragment [M-CO2]+bull

ion by the

loss of CO2 from the carboxyl group attached to carbon C3 atom of the molecular ion as

shown in scheme 3This is confirmed by the calculated bond length for C3C9 in

charged Pefloxacin molecular ion which is greater than that of neutral molecule by

00055Aring (Table 10)The fragment [M-CO2]+

ion undergoes further fragmentation

resulting in the formation of the fragment [M-CO2- C4H9N]+bull

ion at mz 218 with

relative intensities 14 and 16 at 70 and 15 eV respectively The latter fragment [M-

CO2- C4H9N]+bull

ion fragments to produce the ion at mz 203 (by loss of CH3bull radical)

with relative intensities 11 and 10 at 70 and 15 eV respectively

The second characteristic fragmentation process is due to the cleavage of the

piperiazinyl group at C15-C16 and C20-N14 bonds to produce the fragment ion at mz 71

[C4H9N]+bull

ion directly from the molecular ion with relative intensities 20 at 70 e V and

30 at 15 eV together with neutral fragment [M-C4H9N]bull (Scheme 3)

On the other

hand the presence of ndashCH3 group at N17 lead to produce the fragment [M-C2H4N]+ ion at

mz = 291 RI=3 and also to produce the fragment C4H9N+bull

at mz=71 RI=20 in

compariso

n with

Norfloxaci

n the

absence of

ndashCH3

group lead

to produce

the

fragment

[M-

C2H4N]+

ion at mz

= 277

RI=59

Scheme 3 Main

fragmentat

ion

pathways

of

Pefloxacin

at 70 eV

N

O O

O HF

NN

M

=333

- CO2

N

O

F

NN

mz =289

C4 H

9 N

RI = 61 RI = 100

H

N

O

HF

NH2C

RI = 14

mz = 218

H3C

N

O

H

CH2

F

NH2C

mz =203RI = 11

+ +

+

+

mz = 71RI=20 at 70 eVRI=30 at 15 eV

mz

- CH

3

H2C

N

CH2

CH2H3C

N

H2CCH2

CH2

H2C

H

r ea r

ang

men

t

C4H9N +

N

O

F

NH2C

O

O H

Table 10 Calculated bond lengths of neutral and ionized Pefloxacin using MNDO


The

appearance

energy (AE)

of the

fragment

[M-CO2]+bull

ion at

mz=289 is

calculated

(using the

heats of

formation of

∆Hf(M)

molecule

∆Hf (CO2)

and ∆Hf [M-

CO2]+bull

)and

is found to

be equal to

830 eV(801

kJmol-1

)

The

difference

between the

value for

AE [M-CO2]+bull

and IEPefloxacin= 800 eV (772 kJmol-1

) gives the activation energy to



(030 eV) This indicates that

the process forming the fragment [M-CO2]+bull

ion is the first fragmentation process as

discussed in section 433 and illustrated in scheme 3 by the author

The appearance energy of the [M-C2H4N]+ ion is calculated (using the heats of

formation of the neutral ∆Hf (M) molecule neutral fragment ∆Hf (C2H4N) and ∆Hf (M-

C2H4N)+) and is found to equal 870 eV(840 kJmol

-1)

Neutral molecule


Molecular ion


∆ L

N1-C2 14016

C2-C3 13689

C3-C4 14885

C4-C4a 15009

C4a-C5 14182

C5-C6 14295

C6-C7 14435

C7-C8 14208

C8-C8a 14299

C8a-N1 14220

N1-C21 14819

C21-C22 15379

C3-C9 14953

C9-O10 13581

C9-O11 12293

C4-O12 12274

C6-F13 13223

C7-N14 14312

N14-C15 14704

C15-C16 15521

C16-N17 14676

N17-C19 14677

C19-C20 15526

C20-N14 14699

N17-C18 14640

N1-C2 14180

C2-C3 13665

C3-C4 14877

C4-C4a 15072

C4a-C5 14101

C5-C6 14324

C6-C7 14928

C7-C8 14547

C8-C8a 14088

C8a-N1 13994

N1-C21 14922

C21-C22 15372

C3-C9 15008

C9-O10 13534

C9-O11 12273

C4-O12 12226

C6-F13 13114

C7-N14 13624

N14-C15 15031

C15-C16 15508

C16-N17 14609

N17-C19 14600

C19-C20 15504

C20-N14 15020

N17-C18 14739

00164

-00024

-00008

00063

-00081

00029

00493

00339

-00211

-00226

00103

-00007

00055

-00047

-00020

-00048

-00109

-00688

00327

-00013

-00067

-00077

-00022

00321

00099

The difference between the value for AE [M-C2H4N]+ and IEPefloxacin= 800 eV (772

kJmol-1

) gives the activation energy to produce the fragment [M-C2H4N]+ ion as equal

to 68 kJmol-1

(07 eV This indicates that the formation process of the fragment [M-



434 Fragmentation of Pefloxacin using CI technique

The CI mass spectrum of Pefloaxcin is recorded (Figure 11) and the protonated

molecule [M+H]+ at mz 334 is observed in the spectrum (represents the base peak RI

100)

The protonated molecule of Pefloxacin undergoes fragmentation along two different

characteristic pathways The first fragmentation process formed by the loss of CO2

yielding the fragment [MH-CO2]+ ion at mz 290 (RI=31) while the second

fragmentation process is the formation of the fragment [MH- C2H4N]+ mz 292 (RI =

12) by loss of C2H4Nbull radical Two peaks observed at mz 348 and 362 in the CI

spectrum of Pefloxacin are probably formed due to methyl (CH3)+ and ethyl (C2H5)

+

cations transfer processes to form methylated [M+ CH3]+ and ethylated [M+ C2H5]

+

molecules with relative intensities 5 and 21 respectively Furthermore the peak

observed at mz 316 (RI=10) is formed by elimination of H2O from the protonated

molecule

The peak observed at mz 318 (RI=27) may be formed by loss of CO2 molecule from

ethylated molecule after migration of hydrogen atom to C3 atom forming the fragment

[M+C2H5- CO2]+bull

ion

N

O O

O HF

NN

=334

- CO2

N

O

F

NN

mz =290

RI = 100 RI = 31

HH+

[M+H]+

N

O

CF

NN

H+

O

mz = 316

RI = 10

- H2 O

- C2 H

4 N

N

O O

O HF

H+

N

mz = 292

RI = 12

H+

H3C

mz

Scheme 4 Main fragmentation pathways of Pefloxacin using CI technique


charge distributions of Pefloxacin

The study of the behavior of molecules in the gas phase has always been a relatively

important area of research in mass spectrometry since it produces information about the

properties of molecules such as PAs and heats of formation(64)

The calculated charge

distribution of the quinolone ring of the neutral and charged Pefloxacin are calculated and

listed in Table 9 The charges on the atoms N1 O12 in the qinolone ring (pyridinyl) of

Pefloxacin are -0307 e and -0300 e respectively indicating high electronegativity

values Consequently these atoms have higher affinity to attach the proton than the other

atoms in the qinolone ring (pyridinyl) of Pefloxacin molecule

From the thermochemical calculated data (Table 7) of Pefloxacin one can note that the

calculated values of proton affinities at the site N1-H and at the site O12-H (753 and 916

kJmol-1

respectively) together with the calculated heats of formation of the protonated

Pefloxacin molecule ΔHf[M+H]+ at these two atoms (sites) (314 and 151 kJmol

-

1respectively ) indicate that the protonated Pefloxacin molecule at O12 is more stable

than at N1 by value 163 kJmol-1

441 Mass spectra of Ciprofloxacin using EI technique

Ciprofloxacin C17H18FN3O3 (4-oxo-7-(1-piperazinyl)-6-fluor-1-cyclopropyl-14

dihydroquinolin-3-carbonic acid) is one of fluoroquinolone medications and is applied as

an effective synthetic antibiotic for treating a wide range of infectious diseases(65)

It is

one of nine fluoroquinolones approved in the Russian Federation(65)

The EI mass spectra of Ciprofloxacin are reported at 70 and 15 eV electron energies

and are shown in Figures 12-13 While the relative intensities of the molecular ion and

different fragment ions in the mass spectrum relative to the base peak (mz 287) in the

range from mz 56 up to mz 332 are listed in Table 11



intensities [] at 70 and 15 eV electron energies in the mass spectra of Ciprofloxacin

15 eV

70 eV

mz

11

62

11

67

18

100

11

68

5

7

9

4

4

5

6

6

8

19

14

74

13

71

19

100

11

69

5

8

9

4

5

5

5

6

9

20

332

331 [M]+

290

289 [M-C2H4N]+

288

287 [M-CO2]+

246

245 [M-CO2-C2H4N]+

231

230

229

218

215

204

202

201

57

56

442Ionization process of Ciprofloxacin using EI technique

Ciprofloxacin molecule has a highly electronegative atoms s O12(-0295 e) and N1 (-

0277 e) as listed in Table 12 From the calculated charge distributions at N1 and O12 in

the qinolone ring (pyridinyl) of Ciprofloxacin and the presence of a lone pair electrons at

these two atoms one can suggest that the ionization process may occur at these atoms


for Ciprofloxacin using the MNDO method and consequently one can calculate the IE

value for Ciprofloxacin (using equation 6 chapter 2) as the difference between ∆Hf(M)+bull

and ∆Hf(M) The calculated value for IE of Ciprofloxacin is found to be equal to 880

eV(849 kJmol-1

) (Table 5)To the best of knowledge no experimental or theoretical

values for ∆Hf[M]+bull

and ∆Hf[M] for Ciprofloxacin were reported in the literature

Table 12 Calculated charge distribution of neutral and ionized Ciprofloxacin molecule


Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

(e)

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C22

O10

C9

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0277 0206

-0266 0339

-0117 -0021 0133 0076

-0075 0100 0035

-0053 -0057 -0295 0418

-0370 -0295 -0159 -0387 0128 0098

-0312 0096 0127

-0125 0233

-0179 0206

-0085 -0029 0147 0157

-0059 0116

-0042 -0026 -0034 -0285 0380

-0297 0064

-0137 -0419 0133 0099

-0324 0100 0138

0152 0027 0087

-0133 0032

-0008 0014 0081 0016 0016

-0077 0027 0023 0010

-0038 0073 0359 0022

-0032 0005 0001

-0012 0004 0011

443 Fragmentation of Ciprofloxacin using EI technique

Ciprofloxacin is a broad spectrum antibiotic belonging to the second generation

quinolones It is distributed widely and absorbed very well in different body tissues and

fluids It is widely used in various types of infections urinary track respiratory track

gastrointestinal track and also for skin and soft tissues infections as recommended by the

Food and Drug Administration (FDA)(66)

The EI mass spectrum of Ciprofloxacin has three major fragment ions at mz 289287

and 245 beside the molecular ion at mz 331The main fragment ions and its relative

intensities at 15 and 70 eV are listed in Table 11 while the mass spectra are shown in

Figures 12-13 The molecular ion observed at mz 331with RI= 74 It is worth noting

that Nakata et al(67) had recorded the molecular ion peak of Ciprofloxacin with

reasonable intensity

The molecular ion [M]+bull

undergoes fragmentation by two different pathways The first

fragmentation pathway is the formation of the fragment [M-CO2]+bull

at mz 287 with

RI=100 which represents the base peak in the mass spectra at both 70 and 15 eV by the

loss of CO2 through a C3-C9 simple bond cleavage and hydrogen migration from the

carboxylic group to C3 atom as shown in scheme 5This is confirmed by the calculated

bond length for C3C9 in charged molecular ion which are greater than that of neutral

molecule by 0013Aring (Table 13) The relatively high intensity of [M-CO2]+bull

ion indicates

the high stability of the ion The fragment [M-CO2]+bull

ion undergoes further

fragmentation by the cleavage of C15-C16 and C18-C19 bonds to produce the fragment ion

[M-CO2-C2H4N]+ at mz 245 ( Scheme 5) with relative intensities 69 and 68 at 70

and 15 eV respectively

The second fragmentation pathway in the mass spectrum of Ciprofloxacin is the

formation of the fragment [M-C2H4N]+ ion at mz 289 with relative intensities 71 and 67

at 70 and 15 e V respectively This fragment ion is due to the loss of C2H4Nbull radical from

the molecular ion [M]+bull

by C15-C16 and C18-C19 bond cleavage and hydrogen migration

from piperazinyl group to C8 as shown in scheme 5 This is confirmed by the calculated

bond lengths for C15C16 and C18C19 bonds in the charged molecular ion which are

greater than that of neutral molecule by 00004Aring and 00005Aring respectively (Table 13)

The fragment [M-C2H4N]+ ion undergoes fragmentation by loss of CO2 to produce the

fragment ion [M-C2H4N-CO2]+ at mz 245 (Scheme 5) with relative intensities 69 and

68 at 70 and 15 eV respectively

An ion at mz 56 (C3H6N)+

with RI= 20 19 at 70 and 15 eV respectively is also

reported in the spectrum of Ciprofloxacin and is formed by the cleavage of C15-C16 and

C18-N17 bonds and hydrogen migration to N14 in piperazinyl group

N

O O

O HF

NN

M

= 331

- CO2

N

O

F

NN

= 287

C2 H

4 N

N

O O

O HF

N

RI = 74

RI = 100

RI = 71

H

N

O

HF

RI = 69

C2 H

4 N

- CO2

+ +

H H

H rearengment

N

H rearengm

ent

mz 56RI = 20

mz

mz

mz = 245

mz = 289

H2C

NCH2

CH2

Scheme 5 Main fragmentation pathways of Ciprofloxacin at 70 eV

Table 13 Calculated bond lengths of neutral and ionized Ciprofloxacin using MNDO


Neutral molecule


Molecular ion


∆ L

The appearance energy of [M-CO2]+bull

ion( mz = 287) is calculated (using the heats of

formation of the neutral ∆Hf (M) molecule neutral fragment ∆Hf (CO2) and ∆Hf (M-

CO2)+bull

) and is found to be equal to 930eV(897 kJmol-1

)The difference between the

value for AE [M-CO2]+bull

and IECiprofloxacin= 880 eV (849 kJmol-1

) gives the activation

energy to produce the fragment [M-CO2]+bull


(050 eV)This

indicates that the process forming the fragment [M-CO2]+bull

ion is the first fragmentation

process as discussed in section 443 and illustrated in scheme 5 by the author

The appearance energy of [M-C2H4N]+ ion is calculated (using the heats of formation

of the neutral ∆Hf (M) molecule neutral fragment ∆Hf (C2H4N) and ∆Hf [M- C2H4N]+)

and is found to be equal to 10 eV(965 kJmol-1

)The difference between the value for AE

[M-C2H4N]+ and IECiproflxacin= 880 eV (849 kJmol

-1) gives the activation energy to

produce the fragment [M-C2H4N]+ ion as equal to 115 kJmol

-1(120 eV) This indicates

that the process of forming the fragment [M-C2H4N]+ ion is the second fragmentation


N1-C2 14017

C2-C3 1371

C3-C4 14908

C4-C4a 15019

C4a-C5 14169

C5-C6 1431

C6-C7 14441

C7-C8 14194

C8-C8a 14281

N1-C20 14534

C20-C21 15421

C21-C22 15186

C22-C20 15420

C3-C9 14939

C9-O10 13571

C9-O11 12308

C4-O12 12269

C6-F13 13203

C7-N14 14310

N14-C15 14700

C15-C16 15530

C16-N17 14670

N17-C18 14661

C18-C19 15528

C19-N14 14701

N1-C2 13703

C2-C3 14123

C3-C4 14229

C4-C4a 14585

C4a-C5 14303

C5-C6 14214

C6-C7 14567

C7-C8 14189

C8-C8a 14311

N1-C20 14762

C20-C21 15436

C21-C22 15157

C22-C20 15449

C3-C9 15069

C9-O10 13502

C9-O11 12250

C4-O12 13096

C6-F13 13167

C7-N14 14102

N14-C15 14754

C15-C16 15534

C16-N17 14645

N17-C18 14636

C18-C19 15533

C19-N14 14746

-00314

00413

-00679

-00434

00134

-00096

00126

-00005

00030

00228

00015

-00029

00029

00130

-00069

-00058

00827

-00036

-00208

00054

00004

-00025

-00025

00005

00045

444 Fragmentation of Ciprofloxacin using CI technique

As mentioned before the molecular ion of Ciprofloxacin using EI technique was

observed at mz 331Similarythe protonated molecule[M+H]+ was formed at mz 332

using CI technique with RI= 100 which represents the base peak in the CI mass

spectrum of Ciprofloxacin (Figure 14)

The protonated molecule [M+H]+ of Ciprofloxacin undergoes fragmentation along two

different fragmentation pathways The first fragmentation pathway is formed by the loss

of CO2 to form the fragment [MH-CO2]+ ion mz 288 (RI=52) The second

fragmentation pathway is the formation of the fragment [MH-C2H4N ]+ mz

290(RI=17) by the loss of C2H4Nbull radical as shown in scheme 6 On the other hand a

peak observed at m z 314 (RI=6) is formed by elimination of H2O from the protonated

molecule to form the fragment [MH-H2O]+ ion

Two peaks observed at mz 346 and 360 in the CI mass spectrum of Ciprofloxacin are

probably formed due to the methyl (CH3)+ and the ethyl (C2H5

+) cations transfer

processes to form methylated [M+CH3]+ and ethylated [M+C2H5]

+ molecules with

relative intensities 17 and 23 respectively

Scheme 6 Main fragmentation pathways of Ciprofloxacin using CI technique

N

O O

O HF

NN

- CO2

N

O

F

NN

N

O O

O HF

N

H

C2 H

4 N

H H

H+

[M+H]+ = 332

RI = 100

H+

mz = 288RI = 52

H+

mz= 290RI = 17

- H2 O

N

O O

F

NN

H

H+

mz = 314RI = 6

445

The

proton

affinity (PA)heat of formation (∆Hf) and charge distributions of

Ciprofloxacin

The proton affinity of a molecule is one of its fundamental properties as its heats of

formation and ionization energy(68)

The calculated charge distributions of the quinolone ring of neutral and charged

Ciprofloxacin are listed in Table 12 The charge on the atoms N1 and O12 are -0277 e

and -0295 e respectively indicating high electronegativity values So these atoms (sites)

have higher affinity to attach the proton than the other atoms in the quinolone ring

(pyridinyl) of Ciprofloxacin molecule

From the thermochemical calculated data (Table 7) of Ciprofloxacin one can observe

that the calculated values of proton affinities of the sites N1-H and O12-H are

745kJmol-1

and 904 kJmol-1

respectively together with the calculated heats of

formation of protonated molecule ∆Hf(M+H)+ at the sites N1-H and O12-H (418 and 255

kJmol-1

respectively) indicating that the protonted molecule of Ciprofloxacin at O12 site

is more stable than that at N1 site by 163 kJmol-1

451 Mass spectra of Levofloxacin using EI technique

Levofloxacin C18H20FN3O4 (6-fluoro-2-methyl-6-(4-methylpiperazin-1-yl)-10-oxo-4

oxa-1-azatricyclo-7-trideca-5711-tetraene11-carboxylic acid) is a synthetic

fluoroquinolone antibacterial agent(69)

Levofloxacin is the active levo-isomer of

ofloxacin and has a wide spectrum of antibacterial activity against both Gram-positive

and Gram-negative bacteria as well as a typical pathogens such as Mycoplasma

Chlamydia and Legionella(70)

The EI mass spectra of Levofloxacin are recorded at both 70 and 15 eV electron

energies as shown in Figures15-16 while the relative intensities of the molecular ion and

the main fragment ions in the mass spectrum (relative to the base peak at mz 361) in the

range from mz 56 up to mz 362 are listed in Table14



intensities [] at 70 and 15 eV electron energies in the mass spectra of Levofloxacin

15 e V

70 e V

mz

16

100

14

5

5

5

9

19

8

7

34

-

17

100

17

5

7

6

12

22

11

10

29

4

362

361[M]+bull

317[M-CO2]+bull

276

273

254

247

246[M-CO2-C4H9N]+bull

232

231

71(C4H9N)+bull

56

452Ionization process of Levofloxacin using EI technique

Levofloxacin molecule has a highly electronegative atoms O12(-0297 e) and N1(-

0299 e) as listed in Table 15 From the charge distributions at N1 and O12 in the

quinolone ring (pyridinyl) of Levofloxacin and the presence of a lone pair electrons at

these two atoms one suggest that the ionization processes occur at these atoms


for Levofloxacin using the MNDO method and consequently one can calculate the IE

value for Levofloxacin (using equation 6 chapter 2) as the difference between ∆Hf(M)+bull

and ∆Hf(M) The calculated value for IE of Levofloxacin is found to be equal to 830

eV(801 kJmol-1



and ∆Hf[M] for Levofloxacin were reported in the literature

Table 15 Calculated charge distribution of neutral and ionized Levofloxacin molecule


Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

O21

-0299

0201

-0261

0338

-0099

-0028

0112

0092

0079

0051

-0227

-0292

0181

-0209

0322

-0062

-0005

014

0081

0104

0057

-0252

0007

-002

0052

-0016

0037

0023

0028

-0011

0025

0006

-0025

C22

C24

C23

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

015

0091

0016

0416

-0295

-0366

-0297

-0167

-0395

0142

0144

-0429

0143

0142

0194

0155

0088

0011

0402

-0291

-0332

-0244

-0141

-0081

01

0133

-0434

0135

0108

0188

0005

-0003

-0005

-0014

0004

0034

0053

0026

0314

-0042

-0011

-0005

-0008

-0034

-0006

453 Fragmentation of Levofloxacin using EI technique

The molecular ion peak of Levofloxacin at mz 361 (represent the base peak RI=100

) is observed in the mass spectra at 70 and 15 eV indicating the stability of the

molecular ion of Levofloxacin due to the presence of heterocyclic substituent at N1 and

C8 atoms The molecular ion undergoes fragmentation by the loss of CO2 from the

carboxyl group to form the fragment [M-CO2]+ ion

at mz 317(RI=17) This is

confirmed by the calculated bond length for C3C9 in the molecular ion which is greater

than that of neutral molecule by 00057Aring The fragment ion [M-CO2]+ undergoes further

fragmentation resulting in the formation of the fragment [M-CO2-C4H9N]+ ion at mz 246

( RI=20 ) by loss of the neutral (C4H9N)bull (Scheme 7)

An ion at mz 71 (C4H9N)+ is also found in the mass spectrum of Levofloxacin (RI=29

and 34) at 70 and 15 eV respectively This ion is formed by the cleavage of C15-C16

and C20-N14 bonds in 4-methyl piperizinyl with consecutive rearrangement process

The appearance energy of the [M-CO2]+bull

ion mz (317) is calculated (using the heats

of formation of the neutral ∆Hf (M) molecule neutral molecule ∆Hf (CO2) and fragment

ion ∆Hf (M-CO2)+bull

) and is found to be equal = 850eV(820 kJmol-1

) The difference

between the value for AE [M-CO2]+bull

and IELevofloxacin= 830 eV (801 kJmol-1

) gives the

activation energy to produce the fragment [M-CO2]+bull


(020

eV)

Scheme 7 Main

fragmentation pathways of

Levofloxacin at 70 eV

N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

M

= 361mz = 317

C4H9N

N

O

N

O

HF

CH3

mz = 246

RI= 100 RI= 17

RI = 20

++

H-Rearangment

+

mz = 71RI = 29

+

mz

CH2

N

H2C

CH2

CH3

NH2C

H2C

CH2

CH2

H

Table 16 Calculated bond lengths of neutral and ionized Levofloxacin using MNDO


454 Fragmentation of Levofloxacin using CI technique

Neutral molecule

Bond Bond Le ngth(Aring)

Molecular ion


∆ L

N1-C2 13975

C2-C3 13719

C3-C4 14898

C4-C4a 15017

C4a-C5 14187

C5-C6 14314

C6-C7 14450

C7-C8 14368

C8-C8a 14446

C8a-N1 14153

C8-O21 13588

O21-C22 14028

C22-C24 15634

C24-N1 14823

C24-C23 15475

C3-C9 14961

C9-O10 13569

C9-O11 12301

C4-O12 12276

C6-F13 13223

C7-N14 14236

N14-C15 14675

C15-C16 15526

C16-N17 14676

N17-C19 14678

C19-C20 15524

C19-N14 14680

N17-C18 14632

N1-C2 14088

C2-C3 13706

C3-C4 14890

C4-C4a 15094

C4a-C5 14207

C5-C6 14253

C6-C7 14713

C7-C8 14520

C8-C8a 14459

C8a-N1 14031

C8-O21 13472

O21-C22 14140

C22-C24 15611

C24-N1 14852

C24-C23 15482

C3-C9 15018

C9-O10 13532

C9-O11 12275

C4-O12 12239

C6-F13 13164

C7-N14 13877

N14-C15 14978

C15-C16 15561

C16-N17 14620

N17-C19 14630

C19-C20 15521

C19-N14 14955

N17-C18 14730

00113

-00013

-00008

00077

00020

-00061

00263

00152

00013

-00122

-00116

00112

-00023

00029

00007

00057

-00037

-00026

-00037

-00059

-00359

00303

00035

-00056

-00048

-00003

00275

00098

The CI mass spectrum of Levofloxacin is recorded and investigated The resulting

protonated molecule [M+H]+ at mz 362 (RI= 100 ) represents the base peak (Figure

17)This protonated molecule [M+H]+ undergoes fragmentation along two different

fragmentation pathways The first fragmentation process is the formation of the fragment

[MH-CO2]+ ion with mz 318 (RI= 14) by loss of CO2 The second fragmentation

pathway leads to the formation of the fragment ion [MH-C2H4N]+ with mz 320 (RI=

31) by loss of C2H4Nbull from the protonated molecule Another peak has been observed

at mz 344 (RI=5) is formed by elimination of H2O from the protonated molecule to

form the fragment [MH-H2O]+ ion

Two peaks observed at mz 376 and 390 in the CI mass spectrum of Levofloxacin are

formed due to the methyl (CH3)+ and the ethyl (C2H5

+) cations transfer processes to form

methylated [M+CH3]+ and ethylated [M+C2H5]

+ molecules with relative intensities 5

and 19 respectively

One can note that the relative intensities of the [M+CH3]+bull

ions which are produced

in all mass spectra of the studied molecules have low intensities in comparison with the

relative intensities of the [M+C2H5]+bull

ions indicating the presence of C2H5+ ion with

large intensity than that of CH3+ in the source of chemical ionization

N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

mz = 318

RI= 14

H+

[M+H]+

mz = 362

RI = 100

N

O

N

NH3C

O

O

OH

F

CH3

H+

- H2 O

mz = 344RI = 5

- C2 H

4 N

N

O

O

O

OH

F

CH3

H+

N

CH3

mz= 320RI = 31

H+

Scheme 8 Main fragmentation pathways of Levofloxacin using CI technique


charge distributions of Levofloxacin

The calculated charge distributions of the quinolone ring(pyridinyl) of neutral and

charged Levofloxacin molecule are calculated and listed in Table 7 The charges on the

atoms N1 and O12 are -0299e and -0297 e respectively indicating high electronegativity

values So these atoms (sites) have higher affinity to attach the proton than the other

atoms of the ring

Using the thermochemical calculated data (Table 7) of Levoloxacin one observes

that the calculated values of the proton affinities at the sites N1-H and O12-H are 715 and

908 kJmol-1

respectively together with the calculated heat of formation of the

protonated Levofloxacin molecule at these two atoms (sites ) N1 and O12 ( 192 and 2

kJmol-1

respectively) indicate that the protonated Levofloxacin molecule at the site O12

is more stable than that at the site N1

CHAPTER (5)

CONCLUSIONS

The present EI mass spectra of four 6- fluoroquinolones shows that the molecular ions

[M]+bull

of Norfloxacin PefloxacinCiprofloxacin and Levofloxacin have relative intensities

706174 and 100 respectively The relatively high intensity of [M]+bull

for Levofloxacin

indicates its higher stability due to the presence of heterocyclic substituent at N1 and C8

atoms In comparison the CI mass spectra of the four compounds show that the

protonated molecules [M+H]+ are more relatively intense than [M]

+bull ions in the EI mode

indicating higher stability in the case of [M+H]+

The important primary fragmentation pathways of the studied compounds in the EI mass

spectra indicated

(a) The fragment [M-CO2]+bull

ions produced from Norfloxacin Pefloxacin and

Ciprofloxacin have relative intensity 100 (representing the base peak) while

Levofloxacin have only 17 relative intensity

(b) The fragment [M-C2H4N]+ ions produced from Norfloxacin and Pefloxacin have

relative intensities 59 and 71 respectively while not appeared in the mass

spectra of Pefloxacin and Levofloxacin

On the other hand semi-empirical MNDO calculations gave useful information which

help in explaining the experimental events The appearance and activation energies for

the fragment ions in EI mass spectra are calculated for the first time Of most important

the calculated results show that the protonation at O12 site is more favored than that at N1

site for the compounds under investigation

REFERNCES

(1) JJT Watson and OD Sparkman ldquoIntroduction to Mass Spectrometry

Instrumentation Applications and Strategies for Data Interpretationrdquo 4th Edition John

Wiley amp Sons Ltd (2007)

(2) KAFWhite and MGWood ldquoMass SpectrometryApplication in Science and

Engineeringrdquo Wiley ampSonsInc (1986)

(3) KGDas and E PJames ldquoOrganic Mass Spectrometryrdquo Oxford amp IBH

Publishing Co New Delhi Bombay Calcutta (1976)

(4) JTWatson ldquoIntoduction to Mass Spectrometryrdquo3th EditionOxford amp IBH


(5) ACLarry and RKrishnan ldquoComputational Thermochemistry Prediction and

Estimation of Molecular Thermodynamicsrdquo(Eds KIKarl and DJFrurip) American

Chemical Society pp 176(1998)

(6) MJS Dewar ldquoThe molecular Orbital Theory of Organic Chemistryrdquo McGrawHill

New York NY (1969)

(7) DLPople and JABeveridge ldquoApproximate Molecular Orbital Theoryrdquo Mc Graw-

Hill New YorkNY(1970)

(8) JNMurrell and AJHarget ldquoSemiempirical Self-Consistent-Field Molecular Orbital

Theory of Moleculesrdquo WileyNew YorkNY(1972)

(9) GASegal ldquoModern Theoritcal Chemistryrdquo Plenum New YorkNY 7-8(1977)

(10) MJSDewarScience1871037(1975)

(11) KJug Theor Chim Acta 54263(1980)

(12) MJSDewar JPhysChem892145(1985)

(13) WThielTetrahedron447393(1988)

(14) JJPStewart JComp-Aided Mol Design41(1990)

(15) JJPStewart ldquoReviews in Computational Chemistryrdquo(Eds KBLipkowitz and

DBBoyd)VCH Publishers New YorkNY1 pp45(1991)

(16) MCZamer ldquoReviews in Computational Chemistryrdquo(Eds KBLipkowitz and

DBBoyd) VCH Publishers New YorkNY 2 pp313(1990)

(17) WThiel ldquoAdvances in Chemical Physics New Methods in Computational

Quntum Mechanicsrdquo(Eds IPrigogine and ARStuart)93703(1996)

(18) WThiel ldquoComputational Thermochemistry Prediction and Estimation of Molecular

Thermodynamicsrdquo(Eds KIKarl and DJFrurip) American Chemical Society

pp142(1998)

(19) JARuiz-Vico NRConrado VGCasla LVPerezMELeon-Gonzalez and

LMPolo-Diez Jof Food Compos Analy28 99(2012)

(20) KRalph JHFranz and RFrank Analyt Chim Acta637 208(2009)

(21) HB Lee TE Peart and MLSavoboda Jof Chroma A 1139 45(2007)

(22) MKurie and KHiroyuki Analyt Chim Acta 56216 (2006)

(23) MBin YMSun XYChen and DFZhong J of Chinese Mass Spectrom

Soc3(2006)

(24) RQLi and HYin J of Chinese Mass Spectrom Soc 4 (2003)

(25) M A Rabbih S M A Mamoun and Ezzat T M Selim J of Computer Science

amp Comput Math2 8(2012)

(26) JFranck and EGDymond Transfaraday Soc 21 536(1926)

(27) GLSharon and JE Bartmess ldquoGas-Phase Ion Thermochemistryrdquo http

wwwwebbooknistgovchemistryionEAEA

(28) EUCondon PhysRev 28 1182(1926)

(29) EUCondon and J E Mack PhysRev 35 579(1930)

(30)EP Wigner PhysRev 73 1002(1948)

(31)S Geltman PhysRev 102 171(1956)

(32) DP Stevenson DiscussFaradaySoc 10 35(1951)

(33) HE Audier OrgMass Spectrom 2 283(1969)

(34) HM Rosenstock and MKrauss ldquo Mass Spectrometry of Organic Ionsrdquo (Ed

FWMcLafferty) Academic Press New York (1963)

(35) EMChait Charles Blanchared and Victor H Adams ldquoAdvanced Mass

spectrometryrdquo 6 Applied Science Publisher LTDBarking Essex(1974)

(36) KDownard ldquo Mass Spectrometry rdquo A Foundation Course Royal Society of

Chemistry (2004)

(37) UEinar Top Curr Chem 225 3(2003)

(38) KIKarl and DJFruriprdquoComputional Thermochemistry prediction and estimation

of molecular thermodynamicsrdquo American Chemical Scoiety Pulications Division1155

16thstreetNWWashingtonDC pp143(2003)

(39) httpenwikipediaorgwikiSemi-empirical_quantum_chemistry_method

(40) httpwwwcupuni-muenchendechcompchemenergysemi1html

(41) WThiel and M J S Dewar J Am Chem Soc99 4899(1977)

(42)aWThiel Adv Chem Phys 93 703(1996)

b WThiel in Handbook of molecular physics and quantum

chemistry(EdSWilson)Bd 2 Wiley Chicesterpp 487(2003)

c WThiel and AAVoityuk J Phys Chem 100 616(1996)

d SPatchkovskii and WThiel J Comput Chem 201220(1999)

f WWeber and WThiel Theor ChemAcc103495(2000)

g A Koslowski MEBeck and WThiel Theor Comput Chem

24714(2003)

(43) HyperChemTM Release 75 Pro for Windows ldquoMolecular Modeling Systemrdquo

Hypercube User Evaluation copy Organization Evaluation copy

DealerCopyrightcopy2002 HypercubeInc Serial No99-999-9999999999

(44) VTAndriole Drugs 58 1(1999)

(45) NV Rosenstiel and DAdam Drugs 47872(1994)

(46) Ionization Methods in Organic Mass Spectrometry

wwwresearchukyeducoremassspecjeolioniz

(47) M Coacuterdoba-Borrego M C rdoba-D az and D C rdoba-D az Jof Pharma and

Biomed Analy 18 919(1999)

(48) BGCDanilo GMTalita BLLeila MSECarlos APRLuis OJEduardo and

SPDavi Braz J of Pharmac Scie 43 2(2007)

(49) SRudy and T Darrah Thoma J of Elect Spectro and Related Pheno 98ndash99105

(1999)

(50) ARDana GPCamille WWKeith and JW Proksch Jof ChromatogB

867105(2008)

(51) O Ballesteros I Torob V Sanz-Nebot A Naval n JL Vacute lchez and J Barbosa

J of Chromatogr B 798 137(2003)

(52) S K Upadhyay1 P Kumar and V Arora Jof Struc Chem 47 1078 (2006)

(53) XYang CHong JAi HJianying J of ChromatogrA 1214100(2008)

(54) Y Wang LSun WLiWWang and HLYan Chinese J Struct Chem

241359(2005)

(55) RSaikat GN Rajesh BN Jagadeesh IJaved A K Kruthiventi and N Ashwini

Crystal Growth amp Design 8 4343 (2008)

(56) BSrinivas BDan and VP Sitaram Crystal Growth amp Design 6 2699 (2006)

(57) M S B Munson and F H Field J Am ChemSoc 882621 (1966)

(58) G Bouchoux JY Salpin and D Leblanc Inter J of Mass Spectrom and Ion Proc

153 37(1996)

(59) Ede Hoffmann and SVincent ldquoMass Spectrometry Principles and Applicationsrdquo

Third Edition John Wiley amp Sons Ltd The Atrium Southern Gate Chichester West

Sussex PO19 8SQ England pp 19 (2007)

(60) BSara DGiuseppe DC Antonio LAldo and TGiovanna Jof Chromatogr A

1216 794(2009)

(61) D Carl and L Tokes J Am ChemSoc88536(1966)

(62) KSamira BESEric ISteen HLars and H Steen Inter J of Mass Spectrom 249ndash

250 370(2006)

(63) NYongnian W Yong and KSerge Spectrochimica Acta A701049(2008)

(64) CMAnaMGASflvia MFBCristina A J Ferrer-Correia and N M M

Nibbering Inter J of Mass Spectrom and Ion Proc 172123(1998)

(65) A D Vasil N N Golovnev M S Molokeev and T D Churilov J of Struc

Chem46 363( 2005)

(66) KNaora Y Katagiri NIchikawa M Hayashibara and KIwamoto J Chromatogr

B 530186(1990)

(67) HNakata KKurunthachalam PDJones and JP Giesy Chemosphere 58

759(2005)

(68) LDRoger and JP Craig Inorganic Chem 223839(1983)

(69) httpwwwdrugbankcadrugsDB01137

(70) GM Eliopoulos and CT Eliopoulos ldquoQuinolone Antibacterial (Eds DC Hoope

JS Wolfson ) Agents American Society for MicrobiologyrdquoWashington pp 161

(1993)

دراسة الطيف الكتلى لمركبات الفلوروكينولين

باس تخدام طريقتى التأأين الألكترونى والكيميائى

مصحوبة بالحسابات الش به وضعية

هقدهت هي

هأهىى سسحبى هحوىد عبد الكسينقسن الطبيعت النىويت التجسيبيت ndash هدزض هسبعد

هصس-هيئت الطبقت الرزيت

للحصىل على

فيصيبء تجسيبيت-دكتىزاة فى فلسفت العلىمدزجت ال

2213

الأستبذ الدكتىز عصث طه هحود سلينقسن الطبيعت النىويت ndashأستبذ الفيصيبءالرزيت والجصيئيت

هسكص البحىث النىويت التجسيبيت


عبد الىهبة حسي بذ الدكتىز الأست

زشق السبع

القىهى لبحىث وتكنىلىجيب الاشعبعالوسكص ndash أستبذ الفيصيبء


بساهين إالأستبذ الدكتىز هصطفى

الصعيقىكليت العلىم ndashقسن الفيصيبء ndashأستبذ الفيصيبء النىويت

جبهعت بنهب الأستبذ الدكتىز هحود عبد الفتبح زبيع

قسن الطبيعت النىويت التجسيبيتndashأستبذ الفيصيبءالرزيت والجصيئيت

هسكص البحىث النىويت


جبهعخ ثب

كليخ العلم

قسن النيزيبء

الملخص العربى

الزممريي خبع الاقاممبة ف مممخ للزممريي ثا ي ممد ثوحلممر ثممالوممز SSQ 710سممزامام هايممبك ال زلممخ هممي مم ا إرممن

ال ملكسبسممميي الجينلكسبسممميي ممم ل ز ممم لزسمممطير الايمممل ال زلممم لمممجعو ه كجمممبد النل كيمممليي الإ

الزمريي ز أهب الايل ال زل لذح الو كجمبد مم حبلمخ السج ملكسبسيي الينملكسبسيي م حبلخ الزريي الال

Thermo Finnigan TRACE DSQ GCMSثبسزامام هايبك ال زلخ هي ا رسطيلخ م م رن ال يويبئ

ل زم ى إ 1572عمم مبقزيي هازلنزميي ومب ثعخير الايل ال زل للو كجبد الأل ز رن رسطثبلسج للزريي الإ

ثعخ لز سي الوازلنخ للو كجبد الأعوليبد ا قز اح هبقشخٳرن كذلك للطزيئبدسبسيخ الأيبد الأ( رن رسطير ملذ

[M-CO2] جم أى أحم عوليمبد الز سمي رشمور الايمبد اسخم الم الوسزامهخ+bull

[M-C2H4N]+ and [M-

CO2-C2H4N]+

الايل م لعوليخ الزريي م رسطيريثبى اللاريي ال يويبئ الوزدح ثغب الوسزامام ي خ الزإرن ثبلسجخ للزريي ال يويبئ

عزومبدا علم إ ثعخ البرطخ عي ي خ الزمريي ال يويمبئ زل للو كجبد الأهبقشخ الايل ال ثعخال زل للو كجبد الأ

جممل لممب جممم أى الأيممبد ل ز مم كو يي الإر كيممت ممذ الو كجممبد الممبري عممي الايممل ال زلمم لممب ممم حبلممخ الزممر

[M+H]سبسيخ الزم جمذثذ ه اليمم جييالأ+ثبلو ب مخ 100 ثعمخ هاد بجمبد امماد عبليمخمم الو كجمبد الأ

[M]يبد الاسبسيخثثجبد اماد الأ+bull

ل ز م حبلخ الزريي الإ

سزامهخ م الم اسخ م حبلخ الزريي ال يويمبئ قز اح هبقشخ عوليبد الز سي الوازلنخ للو كجبد الأ ثعخ الوٳ ايضب رن

الايبد جم أى أحم عوليبد الز سي أدد ال ر يي

[MH-CO2]+bull


+

ز ي خملال الايمل ال زلم لمب مم حمبل ثعخ رحمذ الم اسمخ همثي هي الوعلهبد عي الو كجبد الأرن الحصل عل ال

ال يويبئ هي ذ الوعلهبد الإل ز الزريي

ثعخللو كجبد الأ ه الز سي الوازلن -1

يبد الوز خبجبد الأ -2

بقمبد سماء الو كمت أ أيمى الو كمت حم ا ح الز ميي عمي ل ثيم همي الوعلهمبدالحصل عل ا ه ي أيضب ل م أ

-MNDO(semiوي بي ب ال ن ال يويبئيخ الوزوثلخ م ي مخ السزامام الزاجي بد الوازلنخ لخ ثإ ثعالزريي للو كجبد الأ

emiprical method) ه ز خ ثبلزبئي الوعوليخ

لاك خمزإظم همي خملال المذ ثعخل الو كجبد الأالزجميلاد المسيخ م اا ب ضل الزربي البري هيروذ هبقشخ

ييمخ كمذلكلمخ ا الحبلمخ الأيي لمب سماء مم الحبلمخ الوزعبدحم ا ح الز ميي بقمبد الزمر ال ين البرطخ مم حسمبثبد

لال ال اثط هي بي يخ الز سي لجعو ال اثط ال يويبئيخ هي خلال ال ين الوازلنخ

ال ملكسبسممميي الجينلكسبسممميي للو كجمممبد الا ثعمممخ بقمممبد الزمممريي حسمممبة ممممMNDOرمممن اسمممزامام ي مممخ

8 81 الز رسمب ال مين( بسييالسج ملكسبسيي الينملكس

لز ريمت قمم ل زم ى ملمذ علم اإ 83 88

O12ا ه ح الاكسمطيي N1قر روبس ب م ه ر اليز جييي رنسي عوليخ الزريي زيطخ لزع أحم الإل ز بد الأه أ

لمن رشم لأل ه ح مم مذ الم اسمخ بلابقبد الزريي الز رن حسبث جويل ال ين السبث خ م حل خ ال يليي الوجدح

هي قجر

ييخ الحبلخ الأ ثعخ م الحبلخ الوزعبدلخ ح الز يي الوازلنخ للو كجبد الأح ا أيضب رن حسبة

ضمبمخ اليمم جيي للو كجمبد الأ ثعمخ أيضمب رمن حسمبة قبثليمخ إسمز جبل يمخ إمم حسمبة عول نس الا ي خ هذاسزام

O12 عمم هضمل ه ح الاكسمطيي N1 عمم هضمل ه رم الزيزم جيي (PAs) ثعمخ د الأاليم جيي للو كجب

ز جبل سمم ممي رنسممي الزممبئي علمم اى عوليممبد إهأقممم هلممك ل جمم الشممحخ السممبلجخ لممذ الممذ اد ممم الو كجممبد الأ ثعممخ

ه ح هضملاليمم جيي عمم سمز جبل أمضر همي إO12 كسطييالأ عم هضل ه ح ثعخ اليم جيي م الو كجبد الأ

ثعمممممخ الوسمممممز جلخ حممممم ا ح الز ممممميي لايمممممبد الأسبسممممميخ للو كجمممممبد الأ أيضمممممب رمممممن حسمممممبة N1 اليزممممم جيي

[M+H]لليم جيي+

الحبلمخ الوزعبدلمخ ا ح الز ميي حمل جويمل ال مين السمبث خ الزم رمن حسمبثب N1 O12 عم الواقل

∆Hf [M] ييمخ مم الحبلمخ الأ∆Hf [M]+bull

Hf [M+H]∆أيضمب مم حبلمخ الو كجمبد الوسمز جلخ لليمم جيي +

ضبمخ هوخ م الميبهي ب الح ا يخ إحيث رعزج سبث بل ه ح لن رش لأ رن حسبثب (PAs) قبثليخ جذة اليم جيي

لزلك الو كجبد

Abbreviations and Acronyms

EI Electron Ionization

CI Chemical Ionization

MO Molecular Orbital

MNDO Modified Neglect of Diatomic Overlap

TFCndashMSMS Turbulent Flow ChromatographyTandem Mass

Spectrometry

SPE Solid-Phase Extraction

FQ Fluoroquinolone

SPME Solid-Phase Microextraction

LCMSMS Liquid ChromatographyndashTandem Mass Spectrometry

IE Ionization Energy

ΔHf Heats of Formation

PA Proton Affinity

AE Appearance Energy

IP Ionization Potential

GCMS Gas ChromatographMass Spectrometer

RI Relative Intensity

mz Mass to Charge Ratio

ACKNOWLEDGMENT




Cairo Egypt

















Abstract






of the studied




[M-C2H4N]+ and [M-






than [M]+bull


[M+H]+





+ are investigated





















CONTENTS

Page

ABSTRACT і


11 Introduction 1




Ionization 6









Ionization 13





31 Apparatus 16

32 Materials 16



41 Results 18



42 Discussion 20




























REFRENCES 88

ARABIC SUMMARY


figure

Name

Page

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Figure 11

Figure 12

Figure 13

Figure 14

Figure 15




bull Path (a)





and Levofloxacin


used in this study













7

20

22

23

24

26

27

38

46

47

57

60

61

72

75

Figure 16

Figure 17

Scheme 1

Scheme 2

Scheme 3

Scheme 4

Scheme 5

Scheme 6

Scheme 7

Scheme 8



Schemes



technique



technique



technique



76

85

33

42

52

56

67

71

81

84

List of Tables

Table

Name

Page

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

Table 10

Table 11






























20

28

30

34

35

39

44

48

50

53

62

Table 12

Table 13

Table 14

Table 15

Table 16














64

68

77

79

82

CHAPTER (1)


11 Introduction











technique(1)







structure(2)












The


















The


are widely











phase(18)



compounds show that




























and HYin(24)










12 Aim of the Work






15 as well as 70 eV


technique






techniques






(ΔHf (M)+bull

)




investigation

CHAPTER (2)



Ionization






is formed


e-

[M] [M] +bull

+ 2 e-



can dissociate to




ion [F] +

[M]+bull

[F]+ + [N]


Also [M]+bull


and neutral


[M]+bull

[F]+bull





may


Io

ni

za

ti

on

E

ne

rg

y

(27)

Th

e

ion

izat

ion

ene

rgy

(IE

)

so

met

ime

s

call

ed

(les

s

cor

rect

ly)

the

ion

izat















principle(28-29)








showed


law of the form

σ (E) = C (E-Eo)n-1

(4)









which is formed

by the reaction

M+e- M

+bull + 2e

- (5)


IE[M]+bull

= ∆Hf[M]+bull

- ∆Hf[M] (6)

Where ∆Hf[M]+bull





[M]+bull

[F]+

+ [N]bull (7)



AE[F]+ = IE [F] +D[F-N] + Eexc (8)





(∆Eth) = ∆Hf[F]+ + ∆Hf[N] - ∆Hf[M] (9)





∆Hf[F]+ = IE[F] +∆Hf[F] (11)


Stevenson(32)



work of Audier(33)






molecular ion


spectra










is defined by



[A ndash B] +bull

A+ + B

bull (12)

odd even odd

[A ndash B] +bull

Abull + B

+ (13)

odd odd even

The fragment ion A+

or B+









Ionization






















CH4+ e- CH4

+bull CH3

+CH2

+ CH

++ 2e (14)

CH4+bull

+ CH4 CH5+ + CH3

bull (15)

CH3+ + CH4 C2H5

+ + H2 (16)


+




210 Proton Affinity





[BH]+ + M B+[M+H]

+ (17)




M + CH5+

[M+H]+ + CH4 (18)

M + H+ MH

+ (19)


+] = - PA

PA = - ∆Hordm































segments













CHAPTER (3)







software

31 Apparatus




positive ion mode










32 Materials






reagent gas




eV











CHAPTER (4)


41 Results











techniques














in


















literature

42 Discussion













Molecule

R1

R2

Norfloxacin

Pefloxacin

Ciprofloxacin

Levofloxacin

ethyl

ethyl

cyclopropyl


piperazinyl

4-methyl-piprazinyl

piperazinyl

4-methyl-piprazinyl









compounds




NN

N

F

CH3

O O

OH

PEFLOXACIN

H3C

NN

HN

F

O O

OH

CIPROFLOXACIN

NN

N

F

O O

OH

LEVOFLOXACIN

O

CH3H3C





compounds











chapter 2)







mz 320









15 e V

70 e V

mz

11

60

7

52

14

100

5

9

68

2

4

7

8

7

2

2

2

2

-

-

-

-

-

-

-

-

-

8

12

70

9

59

16

100

9

13

88

5

9

4

11

13

6

6

6

6

7

6

6

7

6

6

8

7

14

15

320

319 [M]+middot

278

277 [M-C2H4N]+

276

275 [M-CO2]+

245

234

233[M-CO2-C2H4N]+

219

218

217

204

203

190

189

176

175

161

95

85

83

81

73

71

69

57

56







The

removal

of an

electron

from an

organic

molecule

often

leads to

change in

its

relative










) (using




423

Fragm

entatio

n of

Norflo

xacin

using

EI

techniq

ue

Most

previous


(214850-51) where


However the present









respectively


[M-CO2]+bull



Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C9

O10

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0309

0199

-0264

0338

-0119

-0015

0102

0082

-0050

0096

0160

13002

0417

-0295

-0367

-0298

-0169

-0395

0127

0095

-0320

0095

0127

-0287

0175

-0202

0314

-0078

0000

0137

0173

-0145

0190

0149

-0004

0399

-0291

-0324

-0230

-0128

-0168

0082

0103

-0339

0105

0078

0022

-0024

0062

-0024

0041

0015

0035

0091

-0095

0094

-0011

-0006

-0018

0004

0043

0068

0041

0227

-0045

0008

-0019

0010

-0049







fragment (odd-




CO2]+bull



bull radical








+ ion through


(Scheme 1)




C3H7N (Scheme 1)


for



and ∆Hf(M)


) (Table





and



N

O O

O HF

NN

M

= 319

- CO2

N

O

F

NN

= 275

C2 H

4 N

= 277

N

O O

O HF

RI = 70 RI = 100

RI = 59

H

N

O

HF

RI = 88

C2H

4N

- CO2

= 233

NN

+ +

- C3 H

7 N

N

O

HF

N

mz mz

mz

mz = 218

RI = 9

mz

HH rearrangement

rearrangement

+

si m

pl e

cl e

av

ag

e



Table

5

Calcul

ated

∆Hf(M

)∆Hf(

M)+bull

an

d IE

values

for the

four

6-

fluoro

quinol

one

molec

ules

using

MND

O method

Neutral molecule




∆ L

N1-C2 14007

C2-C3 13700

C3-C4 14881

C4-C4a 15012

C4a-C5 14185

C5-C6 14294

C6-C7 14433

C7-C8 14203

C8-C8a 14304

C8a-N1 14204

N1-C20 14830

C20-C21 15379

C3-C9 14950

C9-O10 13571

C9-O11 12304

C4-O12 12275

C6-F13 13223

C7-N14 14306

N14-C15 14706

C15-C16 15517

C16-N17 14676

N17-C18 14677

C18-C19 15514 C19-N14 14706

N1-C2 14167

C2-C3 13650

C3-C4 14863

C4-C4a 15080

C4a-C5 14118

C5-C6 14299

C6-C7 14807

C7-C8 14391

C8-C8a 14142

C8a-N1 13980

N1-C20 14934

C20-C21 15374

C3-C9 15028

C9-O10 13527

C9-O11 12268

C4-O12 12237

C6-F13 13126

C7-N14 13740

N14-C15 14962

C15-C16 15615

C16-N17 14567

N17-C18 14571

C18-C19 15558 C19-N14 14935

00160

-00050

-00018

00068

-00067

00005

00374

00188

-00162

-00224

00104

-00005

00078

-00044

-00036

-00038

-00097

-00566

00256

00098

-00109

-00106

00044

00229

IE

eV k J mol-1

∆Hf(M)+bull

k J mol-1

∆Hf(M)

k J mol-1

Molecule




) and



CO2]+bull









81 782 305 -485

Norfloxacin

8 772 314 -464

Pefloxacin

88 849 485 -368

Ciprofloxacin

83 801 142 -631

Levofloxacin




-1) The


-1)


kJmol-1


ion

by 106 kJmol-1























mz RI[] mz RI[]

mz RI[] mz RI[]

97 17 163 8 218 15 236 32 237 6 250 6 252 5 258 7 264 9 270 8 272 5 274 6 275 9 276 60 277 23 278 55 279 13 290 10 292 9 302 8 304 20 306 12 316 5 318 10 320[M+H]

+ 100 321 18 334[M+CH3]

+ 14 348[M+C2H5]

+ 20

289 6 290 31 291 9 292 12 316 10 317 5 318 27 319 6 332 6 333 6 334[M+H]

+ 100 335 19 346 6 348[M+CH3]

+ 5 362[M+C2H5]

+ 21

276 10 287 8 288 52 289 14 290 17 302 5 304 5 314 6 316 18 317 9 318 38 319 9 320 14 330 5 332[M+H]

+ 100 333 18 334 6 346[M+CH3]

+ 17 360[M+C2H5]

+ 23 361 6

130 7 318 14 319 9 320 31 321 7 344 5 346 6 348 7 360 9 361 9 362[M+H]

+ 100 363 20 376[M+CH3]

+ 5 390[M+C2H5]

+ 19















(59)





authors( 214860)



technique




in scheme 2




+

ion



+ and






N

O O

O HF

NHN

[M+H]+ = 320

- CO2

N

O

F

NHN

mz = 276

mz = 278

N

O O

O HF

RI = 100 RI = 60

RI = 55

H

C2 H

4 N

N

H+ H+

H+

N

O O

F

NHN

H+

- H2 O

mz = 302RI = 8

rearrangment
























kJmol-1






species



method

431

Mass

spectr

a of

Peflox

acin

under

EI technique

PA (M) kJmol

-1

∆Hf(M+H)+

kJmol-1

Protonated Site

∆Hf(M) kcalmol

-1

Molecule

904

749

142

297

O12H

N1H

-116

Norfloxacin

916

753

151

314

O12H

N1H

-111

Pefloxacin

904

745

255

418

O12H

N1H

-88

Ciprofloxacin

908

715

2

192

O12H

N1H

-149

Levofloxacin












Table 8




15 eV

70 eV

mz

10

55

3

21

100

4

6

16

10

10

6

10

30

26

7

4

12

61

3

18

100

4

6

14

11

7

4

6

20

15

6

4

334

333 [M]+middot

291

290

289 [M-CO2]+

245

219

218 [M-CO2-C4H9N]+

203 [M-CO2-C4H9N-CH3]+

96

81

79

71 [C4H9N]+bull

70

57

56







800 eV (772 kJ mole-1





Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

-0307

0198

-0262

-0297

0178

-0206

0010

-0020

0056

C4

C4a

C5

C6

C7

C8

C8a

C21

C22

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

0337

-0119

-0016

0103

0081

-0050

0095

0162

-0002

04135

-0301

-0357

-0300

-0169

-0391

0128

0143

-0428

0144

0128

0193

0318

-0082

0000

0124

0218

-0171

0190

0151

-0003

0401

-0293

-0328

-0228

-0124

-0164

0114

0124

-0418

0126

0114

0183

-0019

0037

0016

0021

0137

-0121

0095

-0011

-0001

-0014

0008

0029

0072

0045

0227

-0014

-0019

0010

-0018

-0014

-0010







ion by the







ion at mz 218 with


CO2- C4H9N]+bull





[C4H9N]+bull



On the other



at mz=71 RI=20 in

compariso

n with

Norfloxaci

n the

absence of

ndashCH3

group lead

to produce

the

fragment

[M-

C2H4N]+

ion at mz

= 277

RI=59

Scheme 3 Main

fragmentat

ion

pathways

of

Pefloxacin

at 70 eV

N

O O

O HF

NN

M

=333

- CO2

N

O

F

NN

mz =289

C4 H

9 N

RI = 61 RI = 100

H

N

O

HF

NH2C

RI = 14

mz = 218

H3C

N

O

H

CH2

F

NH2C

mz =203RI = 11

+ +

+

+


mz

- CH

3

H2C

N

CH2

CH2H3C

N

H2CCH2

CH2

H2C

H

r ea r

ang

men

t

C4H9N +

N

O

F

NH2C

O

O H



The

appearance

energy (AE)

of the

fragment

[M-CO2]+bull

ion at

mz=289 is

calculated

(using the

heats of

formation of

∆Hf(M)

molecule

∆Hf (CO2)

and ∆Hf [M-

CO2]+bull

)and

is found to

be equal to

830 eV(801

kJmol-1

)

The

difference

between the

value for

AE [M-CO2]+bull












-1)

Neutral molecule


Molecular ion


∆ L

N1-C2 14016

C2-C3 13689

C3-C4 14885

C4-C4a 15009

C4a-C5 14182

C5-C6 14295

C6-C7 14435

C7-C8 14208

C8-C8a 14299

C8a-N1 14220

N1-C21 14819

C21-C22 15379

C3-C9 14953

C9-O10 13581

C9-O11 12293

C4-O12 12274

C6-F13 13223

C7-N14 14312

N14-C15 14704

C15-C16 15521

C16-N17 14676

N17-C19 14677

C19-C20 15526

C20-N14 14699

N17-C18 14640

N1-C2 14180

C2-C3 13665

C3-C4 14877

C4-C4a 15072

C4a-C5 14101

C5-C6 14324

C6-C7 14928

C7-C8 14547

C8-C8a 14088

C8a-N1 13994

N1-C21 14922

C21-C22 15372

C3-C9 15008

C9-O10 13534

C9-O11 12273

C4-O12 12226

C6-F13 13114

C7-N14 13624

N14-C15 15031

C15-C16 15508

C16-N17 14609

N17-C19 14600

C19-C20 15504

C20-N14 15020

N17-C18 14739

00164

-00024

-00008

00063

-00081

00029

00493

00339

-00211

-00226

00103

-00007

00055

-00047

-00020

-00048

-00109

-00688

00327

-00013

-00067

-00077

-00022

00321

00099


kJmol-1


to 68 kJmol-1







100)







+


+



molecule



[M+C2H5- CO2]+bull

ion

N

O O

O HF

NN

=334

- CO2

N

O

F

NN

mz =290

RI = 100 RI = 31

HH+

[M+H]+

N

O

CF

NN

H+

O

mz = 316

RI = 10

- H2 O

- C2 H

4 N

N

O O

O HF

H+

N

mz = 292

RI = 12

H+

H3C

mz















kJmol-1



-







It is









15 eV

70 eV

mz

11

62

11

67

18

100

11

68

5

7

9

4

4

5

6

6

8

19

14

74

13

71

19

100

11

69

5

8

9

4

5

5

5

6

9

20

332

331 [M]+

290

289 [M-C2H4N]+

288

287 [M-CO2]+

246

245 [M-CO2-C2H4N]+

231

230

229

218

215

204

202

201

57

56










eV(849 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

(e)

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C22

O10

C9

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0277 0206

-0266 0339

-0117 -0021 0133 0076

-0075 0100 0035

-0053 -0057 -0295 0418

-0370 -0295 -0159 -0387 0128 0098

-0312 0096 0127

-0125 0233

-0179 0206

-0085 -0029 0147 0157

-0059 0116

-0042 -0026 -0034 -0285 0380

-0297 0064

-0137 -0419 0133 0099

-0324 0100 0138

0152 0027 0087

-0133 0032

-0008 0014 0081 0016 0016

-0077 0027 0023 0010

-0038 0073 0359 0022

-0032 0005 0001

-0012 0004 0011
















at mz 287 with






ion indicates





















N

O O

O HF

NN

M

= 331

- CO2

N

O

F

NN

= 287

C2 H

4 N

N

O O

O HF

N

RI = 74

RI = 100

RI = 71

H

N

O

HF

RI = 69

C2 H

4 N

- CO2

+ +

H H

H rearengment

N

H rearengm

ent

mz 56RI = 20

mz

mz

mz = 245

mz = 289

H2C

NCH2

CH2




Neutral molecule


Molecular ion


∆ L




CO2)+bull








(050 eV)This














N1-C2 14017

C2-C3 1371

C3-C4 14908

C4-C4a 15019

C4a-C5 14169

C5-C6 1431

C6-C7 14441

C7-C8 14194

C8-C8a 14281

N1-C20 14534

C20-C21 15421

C21-C22 15186

C22-C20 15420

C3-C9 14939

C9-O10 13571

C9-O11 12308

C4-O12 12269

C6-F13 13203

C7-N14 14310

N14-C15 14700

C15-C16 15530

C16-N17 14670

N17-C18 14661

C18-C19 15528

C19-N14 14701

N1-C2 13703

C2-C3 14123

C3-C4 14229

C4-C4a 14585

C4a-C5 14303

C5-C6 14214

C6-C7 14567

C7-C8 14189

C8-C8a 14311

N1-C20 14762

C20-C21 15436

C21-C22 15157

C22-C20 15449

C3-C9 15069

C9-O10 13502

C9-O11 12250

C4-O12 13096

C6-F13 13167

C7-N14 14102

N14-C15 14754

C15-C16 15534

C16-N17 14645

N17-C18 14636

C18-C19 15533

C19-N14 14746

-00314

00413

-00679

-00434

00134

-00096

00126

-00005

00030

00228

00015

-00029

00029

00130

-00069

-00058

00827

-00036

-00208

00054

00004

-00025

-00025

00005

00045















+) cations transfer


+ molecules with



N

O O

O HF

NN

- CO2

N

O

F

NN

N

O O

O HF

N

H

C2 H

4 N

H H

H+

[M+H]+ = 332

RI = 100

H+

mz = 288RI = 52

H+

mz= 290RI = 17

- H2 O

N

O O

F

NN

H

H+

mz = 314RI = 6

445

The

proton


Ciprofloxacin










745kJmol-1

and 904 kJmol-1



kJmol-1


















15 e V

70 e V

mz

16

100

14

5

5

5

9

19

8

7

34

-

17

100

17

5

7

6

12

22

11

10

29

4

362

361[M]+bull

317[M-CO2]+bull

276

273

254

247


232

231

71(C4H9N)+bull

56










eV(801 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

O21

-0299

0201

-0261

0338

-0099

-0028

0112

0092

0079

0051

-0227

-0292

0181

-0209

0322

-0062

-0005

014

0081

0104

0057

-0252

0007

-002

0052

-0016

0037

0023

0028

-0011

0025

0006

-0025

C22

C24

C23

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

015

0091

0016

0416

-0295

-0366

-0297

-0167

-0395

0142

0144

-0429

0143

0142

0194

0155

0088

0011

0402

-0291

-0332

-0244

-0141

-0081

01

0133

-0434

0135

0108

0188

0005

-0003

-0005

-0014

0004

0034

0053

0026

0314

-0042

-0011

-0005

-0008

-0034

-0006




















) The difference



) gives the



(020

eV)

Scheme 7 Main



N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

M

= 361mz = 317

C4H9N

N

O

N

O

HF

CH3

mz = 246

RI= 100 RI= 17

RI = 20

++

H-Rearangment

+

mz = 71RI = 29

+

mz

CH2

N

H2C

CH2

CH3

NH2C

H2C

CH2

CH2

H




Neutral molecule


Molecular ion


∆ L

N1-C2 13975

C2-C3 13719

C3-C4 14898

C4-C4a 15017

C4a-C5 14187

C5-C6 14314

C6-C7 14450

C7-C8 14368

C8-C8a 14446

C8a-N1 14153

C8-O21 13588

O21-C22 14028

C22-C24 15634

C24-N1 14823

C24-C23 15475

C3-C9 14961

C9-O10 13569

C9-O11 12301

C4-O12 12276

C6-F13 13223

C7-N14 14236

N14-C15 14675

C15-C16 15526

C16-N17 14676

N17-C19 14678

C19-C20 15524

C19-N14 14680

N17-C18 14632

N1-C2 14088

C2-C3 13706

C3-C4 14890

C4-C4a 15094

C4a-C5 14207

C5-C6 14253

C6-C7 14713

C7-C8 14520

C8-C8a 14459

C8a-N1 14031

C8-O21 13472

O21-C22 14140

C22-C24 15611

C24-N1 14852

C24-C23 15482

C3-C9 15018

C9-O10 13532

C9-O11 12275

C4-O12 12239

C6-F13 13164

C7-N14 13877

N14-C15 14978

C15-C16 15561

C16-N17 14620

N17-C19 14630

C19-C20 15521

C19-N14 14955

N17-C18 14730

00113

-00013

-00008

00077

00020

-00061

00263

00152

00013

-00122

-00116

00112

-00023

00029

00007

00057

-00037

-00026

-00037

-00059

-00359

00303

00035

-00056

-00048

-00003

00275

00098















and 19 respectively







N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

mz = 318

RI= 14

H+

[M+H]+

mz = 362

RI = 100

N

O

N

NH3C

O

O

OH

F

CH3

H+

- H2 O

mz = 344RI = 5

- C2 H

4 N

N

O

O

O

OH

F

CH3

H+

N

CH3

mz= 320RI = 31

H+








atoms of the ring



908 kJmol-1



kJmol-1



CHAPTER (5)

CONCLUSIONS


[M]+bull



for Levofloxacin







spectra indicated













REFERNCES














New York NY (1969)



















pp142(1998)







Soc3(2006)


















Chemistry (2004)















24714(2003)













(1999)


867105(2008)






241359(2005)






153 37(1996)





1216 794(2009)



250 370(2006)





Chem46 363( 2005)


B 530186(1990)


759(2005)





(1993)




هقدهت هي



للحصىل على


2213





زشق السبع









جبهعخ ثب

كليخ العلم










[M-C2H4N]+ and [M-

CO2-C2H4N]+









[MH-CO2]+bull


+
















هي قجر













ACKNOWLEDGMENT




Cairo Egypt

















Abstract






of the studied




[M-C2H4N]+ and [M-






than [M]+bull


[M+H]+





+ are investigated





















CONTENTS

Page

ABSTRACT і


11 Introduction 1




Ionization 6









Ionization 13





31 Apparatus 16

32 Materials 16



41 Results 18



42 Discussion 20




























REFRENCES 88

ARABIC SUMMARY


figure

Name

Page

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Figure 11

Figure 12

Figure 13

Figure 14

Figure 15




bull Path (a)





and Levofloxacin


used in this study













7

20

22

23

24

26

27

38

46

47

57

60

61

72

75

Figure 16

Figure 17

Scheme 1

Scheme 2

Scheme 3

Scheme 4

Scheme 5

Scheme 6

Scheme 7

Scheme 8



Schemes



technique



technique



technique



76

85

33

42

52

56

67

71

81

84

List of Tables

Table

Name

Page

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

Table 10

Table 11






























20

28

30

34

35

39

44

48

50

53

62

Table 12

Table 13

Table 14

Table 15

Table 16














64

68

77

79

82

CHAPTER (1)


11 Introduction











technique(1)







structure(2)












The


















The


are widely











phase(18)



compounds show that




























and HYin(24)










12 Aim of the Work






15 as well as 70 eV


technique






techniques






(ΔHf (M)+bull

)




investigation

CHAPTER (2)



Ionization






is formed


e-

[M] [M] +bull

+ 2 e-



can dissociate to




ion [F] +

[M]+bull

[F]+ + [N]


Also [M]+bull


and neutral


[M]+bull

[F]+bull





may


Io

ni

za

ti

on

E

ne

rg

y

(27)

Th

e

ion

izat

ion

ene

rgy

(IE

)

so

met

ime

s

call

ed

(les

s

cor

rect

ly)

the

ion

izat















principle(28-29)








showed


law of the form

σ (E) = C (E-Eo)n-1

(4)









which is formed

by the reaction

M+e- M

+bull + 2e

- (5)


IE[M]+bull

= ∆Hf[M]+bull

- ∆Hf[M] (6)

Where ∆Hf[M]+bull





[M]+bull

[F]+

+ [N]bull (7)



AE[F]+ = IE [F] +D[F-N] + Eexc (8)





(∆Eth) = ∆Hf[F]+ + ∆Hf[N] - ∆Hf[M] (9)





∆Hf[F]+ = IE[F] +∆Hf[F] (11)


Stevenson(32)



work of Audier(33)






molecular ion


spectra










is defined by



[A ndash B] +bull

A+ + B

bull (12)

odd even odd

[A ndash B] +bull

Abull + B

+ (13)

odd odd even

The fragment ion A+

or B+









Ionization






















CH4+ e- CH4

+bull CH3

+CH2

+ CH

++ 2e (14)

CH4+bull

+ CH4 CH5+ + CH3

bull (15)

CH3+ + CH4 C2H5

+ + H2 (16)


+




210 Proton Affinity





[BH]+ + M B+[M+H]

+ (17)




M + CH5+

[M+H]+ + CH4 (18)

M + H+ MH

+ (19)


+] = - PA

PA = - ∆Hordm































segments













CHAPTER (3)







software

31 Apparatus




positive ion mode










32 Materials






reagent gas




eV











CHAPTER (4)


41 Results











techniques














in


















literature

42 Discussion













Molecule

R1

R2

Norfloxacin

Pefloxacin

Ciprofloxacin

Levofloxacin

ethyl

ethyl

cyclopropyl


piperazinyl

4-methyl-piprazinyl

piperazinyl

4-methyl-piprazinyl









compounds




NN

N

F

CH3

O O

OH

PEFLOXACIN

H3C

NN

HN

F

O O

OH

CIPROFLOXACIN

NN

N

F

O O

OH

LEVOFLOXACIN

O

CH3H3C





compounds











chapter 2)







mz 320









15 e V

70 e V

mz

11

60

7

52

14

100

5

9

68

2

4

7

8

7

2

2

2

2

-

-

-

-

-

-

-

-

-

8

12

70

9

59

16

100

9

13

88

5

9

4

11

13

6

6

6

6

7

6

6

7

6

6

8

7

14

15

320

319 [M]+middot

278

277 [M-C2H4N]+

276

275 [M-CO2]+

245

234

233[M-CO2-C2H4N]+

219

218

217

204

203

190

189

176

175

161

95

85

83

81

73

71

69

57

56







The

removal

of an

electron

from an

organic

molecule

often

leads to

change in

its

relative










) (using




423

Fragm

entatio

n of

Norflo

xacin

using

EI

techniq

ue

Most

previous


(214850-51) where


However the present









respectively


[M-CO2]+bull



Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C9

O10

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0309

0199

-0264

0338

-0119

-0015

0102

0082

-0050

0096

0160

13002

0417

-0295

-0367

-0298

-0169

-0395

0127

0095

-0320

0095

0127

-0287

0175

-0202

0314

-0078

0000

0137

0173

-0145

0190

0149

-0004

0399

-0291

-0324

-0230

-0128

-0168

0082

0103

-0339

0105

0078

0022

-0024

0062

-0024

0041

0015

0035

0091

-0095

0094

-0011

-0006

-0018

0004

0043

0068

0041

0227

-0045

0008

-0019

0010

-0049







fragment (odd-




CO2]+bull



bull radical








+ ion through


(Scheme 1)




C3H7N (Scheme 1)


for



and ∆Hf(M)


) (Table





and



N

O O

O HF

NN

M

= 319

- CO2

N

O

F

NN

= 275

C2 H

4 N

= 277

N

O O

O HF

RI = 70 RI = 100

RI = 59

H

N

O

HF

RI = 88

C2H

4N

- CO2

= 233

NN

+ +

- C3 H

7 N

N

O

HF

N

mz mz

mz

mz = 218

RI = 9

mz

HH rearrangement

rearrangement

+

si m

pl e

cl e

av

ag

e



Table

5

Calcul

ated

∆Hf(M

)∆Hf(

M)+bull

an

d IE

values

for the

four

6-

fluoro

quinol

one

molec

ules

using

MND

O method

Neutral molecule




∆ L

N1-C2 14007

C2-C3 13700

C3-C4 14881

C4-C4a 15012

C4a-C5 14185

C5-C6 14294

C6-C7 14433

C7-C8 14203

C8-C8a 14304

C8a-N1 14204

N1-C20 14830

C20-C21 15379

C3-C9 14950

C9-O10 13571

C9-O11 12304

C4-O12 12275

C6-F13 13223

C7-N14 14306

N14-C15 14706

C15-C16 15517

C16-N17 14676

N17-C18 14677

C18-C19 15514 C19-N14 14706

N1-C2 14167

C2-C3 13650

C3-C4 14863

C4-C4a 15080

C4a-C5 14118

C5-C6 14299

C6-C7 14807

C7-C8 14391

C8-C8a 14142

C8a-N1 13980

N1-C20 14934

C20-C21 15374

C3-C9 15028

C9-O10 13527

C9-O11 12268

C4-O12 12237

C6-F13 13126

C7-N14 13740

N14-C15 14962

C15-C16 15615

C16-N17 14567

N17-C18 14571

C18-C19 15558 C19-N14 14935

00160

-00050

-00018

00068

-00067

00005

00374

00188

-00162

-00224

00104

-00005

00078

-00044

-00036

-00038

-00097

-00566

00256

00098

-00109

-00106

00044

00229

IE

eV k J mol-1

∆Hf(M)+bull

k J mol-1

∆Hf(M)

k J mol-1

Molecule




) and



CO2]+bull









81 782 305 -485

Norfloxacin

8 772 314 -464

Pefloxacin

88 849 485 -368

Ciprofloxacin

83 801 142 -631

Levofloxacin




-1) The


-1)


kJmol-1


ion

by 106 kJmol-1























mz RI[] mz RI[]

mz RI[] mz RI[]

97 17 163 8 218 15 236 32 237 6 250 6 252 5 258 7 264 9 270 8 272 5 274 6 275 9 276 60 277 23 278 55 279 13 290 10 292 9 302 8 304 20 306 12 316 5 318 10 320[M+H]

+ 100 321 18 334[M+CH3]

+ 14 348[M+C2H5]

+ 20

289 6 290 31 291 9 292 12 316 10 317 5 318 27 319 6 332 6 333 6 334[M+H]

+ 100 335 19 346 6 348[M+CH3]

+ 5 362[M+C2H5]

+ 21

276 10 287 8 288 52 289 14 290 17 302 5 304 5 314 6 316 18 317 9 318 38 319 9 320 14 330 5 332[M+H]

+ 100 333 18 334 6 346[M+CH3]

+ 17 360[M+C2H5]

+ 23 361 6

130 7 318 14 319 9 320 31 321 7 344 5 346 6 348 7 360 9 361 9 362[M+H]

+ 100 363 20 376[M+CH3]

+ 5 390[M+C2H5]

+ 19















(59)





authors( 214860)



technique




in scheme 2




+

ion



+ and






N

O O

O HF

NHN

[M+H]+ = 320

- CO2

N

O

F

NHN

mz = 276

mz = 278

N

O O

O HF

RI = 100 RI = 60

RI = 55

H

C2 H

4 N

N

H+ H+

H+

N

O O

F

NHN

H+

- H2 O

mz = 302RI = 8

rearrangment
























kJmol-1






species



method

431

Mass

spectr

a of

Peflox

acin

under

EI technique

PA (M) kJmol

-1

∆Hf(M+H)+

kJmol-1

Protonated Site

∆Hf(M) kcalmol

-1

Molecule

904

749

142

297

O12H

N1H

-116

Norfloxacin

916

753

151

314

O12H

N1H

-111

Pefloxacin

904

745

255

418

O12H

N1H

-88

Ciprofloxacin

908

715

2

192

O12H

N1H

-149

Levofloxacin












Table 8




15 eV

70 eV

mz

10

55

3

21

100

4

6

16

10

10

6

10

30

26

7

4

12

61

3

18

100

4

6

14

11

7

4

6

20

15

6

4

334

333 [M]+middot

291

290

289 [M-CO2]+

245

219

218 [M-CO2-C4H9N]+

203 [M-CO2-C4H9N-CH3]+

96

81

79

71 [C4H9N]+bull

70

57

56







800 eV (772 kJ mole-1





Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

-0307

0198

-0262

-0297

0178

-0206

0010

-0020

0056

C4

C4a

C5

C6

C7

C8

C8a

C21

C22

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

0337

-0119

-0016

0103

0081

-0050

0095

0162

-0002

04135

-0301

-0357

-0300

-0169

-0391

0128

0143

-0428

0144

0128

0193

0318

-0082

0000

0124

0218

-0171

0190

0151

-0003

0401

-0293

-0328

-0228

-0124

-0164

0114

0124

-0418

0126

0114

0183

-0019

0037

0016

0021

0137

-0121

0095

-0011

-0001

-0014

0008

0029

0072

0045

0227

-0014

-0019

0010

-0018

-0014

-0010







ion by the







ion at mz 218 with


CO2- C4H9N]+bull





[C4H9N]+bull



On the other



at mz=71 RI=20 in

compariso

n with

Norfloxaci

n the

absence of

ndashCH3

group lead

to produce

the

fragment

[M-

C2H4N]+

ion at mz

= 277

RI=59

Scheme 3 Main

fragmentat

ion

pathways

of

Pefloxacin

at 70 eV

N

O O

O HF

NN

M

=333

- CO2

N

O

F

NN

mz =289

C4 H

9 N

RI = 61 RI = 100

H

N

O

HF

NH2C

RI = 14

mz = 218

H3C

N

O

H

CH2

F

NH2C

mz =203RI = 11

+ +

+

+


mz

- CH

3

H2C

N

CH2

CH2H3C

N

H2CCH2

CH2

H2C

H

r ea r

ang

men

t

C4H9N +

N

O

F

NH2C

O

O H



The

appearance

energy (AE)

of the

fragment

[M-CO2]+bull

ion at

mz=289 is

calculated

(using the

heats of

formation of

∆Hf(M)

molecule

∆Hf (CO2)

and ∆Hf [M-

CO2]+bull

)and

is found to

be equal to

830 eV(801

kJmol-1

)

The

difference

between the

value for

AE [M-CO2]+bull












-1)

Neutral molecule


Molecular ion


∆ L

N1-C2 14016

C2-C3 13689

C3-C4 14885

C4-C4a 15009

C4a-C5 14182

C5-C6 14295

C6-C7 14435

C7-C8 14208

C8-C8a 14299

C8a-N1 14220

N1-C21 14819

C21-C22 15379

C3-C9 14953

C9-O10 13581

C9-O11 12293

C4-O12 12274

C6-F13 13223

C7-N14 14312

N14-C15 14704

C15-C16 15521

C16-N17 14676

N17-C19 14677

C19-C20 15526

C20-N14 14699

N17-C18 14640

N1-C2 14180

C2-C3 13665

C3-C4 14877

C4-C4a 15072

C4a-C5 14101

C5-C6 14324

C6-C7 14928

C7-C8 14547

C8-C8a 14088

C8a-N1 13994

N1-C21 14922

C21-C22 15372

C3-C9 15008

C9-O10 13534

C9-O11 12273

C4-O12 12226

C6-F13 13114

C7-N14 13624

N14-C15 15031

C15-C16 15508

C16-N17 14609

N17-C19 14600

C19-C20 15504

C20-N14 15020

N17-C18 14739

00164

-00024

-00008

00063

-00081

00029

00493

00339

-00211

-00226

00103

-00007

00055

-00047

-00020

-00048

-00109

-00688

00327

-00013

-00067

-00077

-00022

00321

00099


kJmol-1


to 68 kJmol-1







100)







+


+



molecule



[M+C2H5- CO2]+bull

ion

N

O O

O HF

NN

=334

- CO2

N

O

F

NN

mz =290

RI = 100 RI = 31

HH+

[M+H]+

N

O

CF

NN

H+

O

mz = 316

RI = 10

- H2 O

- C2 H

4 N

N

O O

O HF

H+

N

mz = 292

RI = 12

H+

H3C

mz















kJmol-1



-







It is









15 eV

70 eV

mz

11

62

11

67

18

100

11

68

5

7

9

4

4

5

6

6

8

19

14

74

13

71

19

100

11

69

5

8

9

4

5

5

5

6

9

20

332

331 [M]+

290

289 [M-C2H4N]+

288

287 [M-CO2]+

246

245 [M-CO2-C2H4N]+

231

230

229

218

215

204

202

201

57

56










eV(849 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

(e)

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C22

O10

C9

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0277 0206

-0266 0339

-0117 -0021 0133 0076

-0075 0100 0035

-0053 -0057 -0295 0418

-0370 -0295 -0159 -0387 0128 0098

-0312 0096 0127

-0125 0233

-0179 0206

-0085 -0029 0147 0157

-0059 0116

-0042 -0026 -0034 -0285 0380

-0297 0064

-0137 -0419 0133 0099

-0324 0100 0138

0152 0027 0087

-0133 0032

-0008 0014 0081 0016 0016

-0077 0027 0023 0010

-0038 0073 0359 0022

-0032 0005 0001

-0012 0004 0011
















at mz 287 with






ion indicates





















N

O O

O HF

NN

M

= 331

- CO2

N

O

F

NN

= 287

C2 H

4 N

N

O O

O HF

N

RI = 74

RI = 100

RI = 71

H

N

O

HF

RI = 69

C2 H

4 N

- CO2

+ +

H H

H rearengment

N

H rearengm

ent

mz 56RI = 20

mz

mz

mz = 245

mz = 289

H2C

NCH2

CH2




Neutral molecule


Molecular ion


∆ L




CO2)+bull








(050 eV)This














N1-C2 14017

C2-C3 1371

C3-C4 14908

C4-C4a 15019

C4a-C5 14169

C5-C6 1431

C6-C7 14441

C7-C8 14194

C8-C8a 14281

N1-C20 14534

C20-C21 15421

C21-C22 15186

C22-C20 15420

C3-C9 14939

C9-O10 13571

C9-O11 12308

C4-O12 12269

C6-F13 13203

C7-N14 14310

N14-C15 14700

C15-C16 15530

C16-N17 14670

N17-C18 14661

C18-C19 15528

C19-N14 14701

N1-C2 13703

C2-C3 14123

C3-C4 14229

C4-C4a 14585

C4a-C5 14303

C5-C6 14214

C6-C7 14567

C7-C8 14189

C8-C8a 14311

N1-C20 14762

C20-C21 15436

C21-C22 15157

C22-C20 15449

C3-C9 15069

C9-O10 13502

C9-O11 12250

C4-O12 13096

C6-F13 13167

C7-N14 14102

N14-C15 14754

C15-C16 15534

C16-N17 14645

N17-C18 14636

C18-C19 15533

C19-N14 14746

-00314

00413

-00679

-00434

00134

-00096

00126

-00005

00030

00228

00015

-00029

00029

00130

-00069

-00058

00827

-00036

-00208

00054

00004

-00025

-00025

00005

00045















+) cations transfer


+ molecules with



N

O O

O HF

NN

- CO2

N

O

F

NN

N

O O

O HF

N

H

C2 H

4 N

H H

H+

[M+H]+ = 332

RI = 100

H+

mz = 288RI = 52

H+

mz= 290RI = 17

- H2 O

N

O O

F

NN

H

H+

mz = 314RI = 6

445

The

proton


Ciprofloxacin










745kJmol-1

and 904 kJmol-1



kJmol-1


















15 e V

70 e V

mz

16

100

14

5

5

5

9

19

8

7

34

-

17

100

17

5

7

6

12

22

11

10

29

4

362

361[M]+bull

317[M-CO2]+bull

276

273

254

247


232

231

71(C4H9N)+bull

56










eV(801 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

O21

-0299

0201

-0261

0338

-0099

-0028

0112

0092

0079

0051

-0227

-0292

0181

-0209

0322

-0062

-0005

014

0081

0104

0057

-0252

0007

-002

0052

-0016

0037

0023

0028

-0011

0025

0006

-0025

C22

C24

C23

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

015

0091

0016

0416

-0295

-0366

-0297

-0167

-0395

0142

0144

-0429

0143

0142

0194

0155

0088

0011

0402

-0291

-0332

-0244

-0141

-0081

01

0133

-0434

0135

0108

0188

0005

-0003

-0005

-0014

0004

0034

0053

0026

0314

-0042

-0011

-0005

-0008

-0034

-0006




















) The difference



) gives the



(020

eV)

Scheme 7 Main



N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

M

= 361mz = 317

C4H9N

N

O

N

O

HF

CH3

mz = 246

RI= 100 RI= 17

RI = 20

++

H-Rearangment

+

mz = 71RI = 29

+

mz

CH2

N

H2C

CH2

CH3

NH2C

H2C

CH2

CH2

H




Neutral molecule


Molecular ion


∆ L

N1-C2 13975

C2-C3 13719

C3-C4 14898

C4-C4a 15017

C4a-C5 14187

C5-C6 14314

C6-C7 14450

C7-C8 14368

C8-C8a 14446

C8a-N1 14153

C8-O21 13588

O21-C22 14028

C22-C24 15634

C24-N1 14823

C24-C23 15475

C3-C9 14961

C9-O10 13569

C9-O11 12301

C4-O12 12276

C6-F13 13223

C7-N14 14236

N14-C15 14675

C15-C16 15526

C16-N17 14676

N17-C19 14678

C19-C20 15524

C19-N14 14680

N17-C18 14632

N1-C2 14088

C2-C3 13706

C3-C4 14890

C4-C4a 15094

C4a-C5 14207

C5-C6 14253

C6-C7 14713

C7-C8 14520

C8-C8a 14459

C8a-N1 14031

C8-O21 13472

O21-C22 14140

C22-C24 15611

C24-N1 14852

C24-C23 15482

C3-C9 15018

C9-O10 13532

C9-O11 12275

C4-O12 12239

C6-F13 13164

C7-N14 13877

N14-C15 14978

C15-C16 15561

C16-N17 14620

N17-C19 14630

C19-C20 15521

C19-N14 14955

N17-C18 14730

00113

-00013

-00008

00077

00020

-00061

00263

00152

00013

-00122

-00116

00112

-00023

00029

00007

00057

-00037

-00026

-00037

-00059

-00359

00303

00035

-00056

-00048

-00003

00275

00098















and 19 respectively







N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

mz = 318

RI= 14

H+

[M+H]+

mz = 362

RI = 100

N

O

N

NH3C

O

O

OH

F

CH3

H+

- H2 O

mz = 344RI = 5

- C2 H

4 N

N

O

O

O

OH

F

CH3

H+

N

CH3

mz= 320RI = 31

H+








atoms of the ring



908 kJmol-1



kJmol-1



CHAPTER (5)

CONCLUSIONS


[M]+bull



for Levofloxacin







spectra indicated













REFERNCES














New York NY (1969)



















pp142(1998)







Soc3(2006)


















Chemistry (2004)















24714(2003)













(1999)


867105(2008)






241359(2005)






153 37(1996)





1216 794(2009)



250 370(2006)





Chem46 363( 2005)


B 530186(1990)


759(2005)





(1993)




هقدهت هي



للحصىل على


2213





زشق السبع









جبهعخ ثب

كليخ العلم










[M-C2H4N]+ and [M-

CO2-C2H4N]+









[MH-CO2]+bull


+
















هي قجر













Abstract






of the studied




[M-C2H4N]+ and [M-






than [M]+bull


[M+H]+





+ are investigated





















CONTENTS

Page

ABSTRACT і


11 Introduction 1




Ionization 6









Ionization 13





31 Apparatus 16

32 Materials 16



41 Results 18



42 Discussion 20




























REFRENCES 88

ARABIC SUMMARY


figure

Name

Page

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Figure 11

Figure 12

Figure 13

Figure 14

Figure 15




bull Path (a)





and Levofloxacin


used in this study













7

20

22

23

24

26

27

38

46

47

57

60

61

72

75

Figure 16

Figure 17

Scheme 1

Scheme 2

Scheme 3

Scheme 4

Scheme 5

Scheme 6

Scheme 7

Scheme 8



Schemes



technique



technique



technique



76

85

33

42

52

56

67

71

81

84

List of Tables

Table

Name

Page

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

Table 10

Table 11






























20

28

30

34

35

39

44

48

50

53

62

Table 12

Table 13

Table 14

Table 15

Table 16














64

68

77

79

82

CHAPTER (1)


11 Introduction











technique(1)







structure(2)












The


















The


are widely











phase(18)



compounds show that




























and HYin(24)










12 Aim of the Work






15 as well as 70 eV


technique






techniques






(ΔHf (M)+bull

)




investigation

CHAPTER (2)



Ionization






is formed


e-

[M] [M] +bull

+ 2 e-



can dissociate to




ion [F] +

[M]+bull

[F]+ + [N]


Also [M]+bull


and neutral


[M]+bull

[F]+bull





may


Io

ni

za

ti

on

E

ne

rg

y

(27)

Th

e

ion

izat

ion

ene

rgy

(IE

)

so

met

ime

s

call

ed

(les

s

cor

rect

ly)

the

ion

izat















principle(28-29)








showed


law of the form

σ (E) = C (E-Eo)n-1

(4)









which is formed

by the reaction

M+e- M

+bull + 2e

- (5)


IE[M]+bull

= ∆Hf[M]+bull

- ∆Hf[M] (6)

Where ∆Hf[M]+bull





[M]+bull

[F]+

+ [N]bull (7)



AE[F]+ = IE [F] +D[F-N] + Eexc (8)





(∆Eth) = ∆Hf[F]+ + ∆Hf[N] - ∆Hf[M] (9)





∆Hf[F]+ = IE[F] +∆Hf[F] (11)


Stevenson(32)



work of Audier(33)






molecular ion


spectra










is defined by



[A ndash B] +bull

A+ + B

bull (12)

odd even odd

[A ndash B] +bull

Abull + B

+ (13)

odd odd even

The fragment ion A+

or B+









Ionization






















CH4+ e- CH4

+bull CH3

+CH2

+ CH

++ 2e (14)

CH4+bull

+ CH4 CH5+ + CH3

bull (15)

CH3+ + CH4 C2H5

+ + H2 (16)


+




210 Proton Affinity





[BH]+ + M B+[M+H]

+ (17)




M + CH5+

[M+H]+ + CH4 (18)

M + H+ MH

+ (19)


+] = - PA

PA = - ∆Hordm































segments













CHAPTER (3)







software

31 Apparatus




positive ion mode










32 Materials






reagent gas




eV











CHAPTER (4)


41 Results











techniques














in


















literature

42 Discussion













Molecule

R1

R2

Norfloxacin

Pefloxacin

Ciprofloxacin

Levofloxacin

ethyl

ethyl

cyclopropyl


piperazinyl

4-methyl-piprazinyl

piperazinyl

4-methyl-piprazinyl









compounds




NN

N

F

CH3

O O

OH

PEFLOXACIN

H3C

NN

HN

F

O O

OH

CIPROFLOXACIN

NN

N

F

O O

OH

LEVOFLOXACIN

O

CH3H3C





compounds











chapter 2)







mz 320









15 e V

70 e V

mz

11

60

7

52

14

100

5

9

68

2

4

7

8

7

2

2

2

2

-

-

-

-

-

-

-

-

-

8

12

70

9

59

16

100

9

13

88

5

9

4

11

13

6

6

6

6

7

6

6

7

6

6

8

7

14

15

320

319 [M]+middot

278

277 [M-C2H4N]+

276

275 [M-CO2]+

245

234

233[M-CO2-C2H4N]+

219

218

217

204

203

190

189

176

175

161

95

85

83

81

73

71

69

57

56







The

removal

of an

electron

from an

organic

molecule

often

leads to

change in

its

relative










) (using




423

Fragm

entatio

n of

Norflo

xacin

using

EI

techniq

ue

Most

previous


(214850-51) where


However the present









respectively


[M-CO2]+bull



Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C9

O10

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0309

0199

-0264

0338

-0119

-0015

0102

0082

-0050

0096

0160

13002

0417

-0295

-0367

-0298

-0169

-0395

0127

0095

-0320

0095

0127

-0287

0175

-0202

0314

-0078

0000

0137

0173

-0145

0190

0149

-0004

0399

-0291

-0324

-0230

-0128

-0168

0082

0103

-0339

0105

0078

0022

-0024

0062

-0024

0041

0015

0035

0091

-0095

0094

-0011

-0006

-0018

0004

0043

0068

0041

0227

-0045

0008

-0019

0010

-0049







fragment (odd-




CO2]+bull



bull radical








+ ion through


(Scheme 1)




C3H7N (Scheme 1)


for



and ∆Hf(M)


) (Table





and



N

O O

O HF

NN

M

= 319

- CO2

N

O

F

NN

= 275

C2 H

4 N

= 277

N

O O

O HF

RI = 70 RI = 100

RI = 59

H

N

O

HF

RI = 88

C2H

4N

- CO2

= 233

NN

+ +

- C3 H

7 N

N

O

HF

N

mz mz

mz

mz = 218

RI = 9

mz

HH rearrangement

rearrangement

+

si m

pl e

cl e

av

ag

e



Table

5

Calcul

ated

∆Hf(M

)∆Hf(

M)+bull

an

d IE

values

for the

four

6-

fluoro

quinol

one

molec

ules

using

MND

O method

Neutral molecule




∆ L

N1-C2 14007

C2-C3 13700

C3-C4 14881

C4-C4a 15012

C4a-C5 14185

C5-C6 14294

C6-C7 14433

C7-C8 14203

C8-C8a 14304

C8a-N1 14204

N1-C20 14830

C20-C21 15379

C3-C9 14950

C9-O10 13571

C9-O11 12304

C4-O12 12275

C6-F13 13223

C7-N14 14306

N14-C15 14706

C15-C16 15517

C16-N17 14676

N17-C18 14677

C18-C19 15514 C19-N14 14706

N1-C2 14167

C2-C3 13650

C3-C4 14863

C4-C4a 15080

C4a-C5 14118

C5-C6 14299

C6-C7 14807

C7-C8 14391

C8-C8a 14142

C8a-N1 13980

N1-C20 14934

C20-C21 15374

C3-C9 15028

C9-O10 13527

C9-O11 12268

C4-O12 12237

C6-F13 13126

C7-N14 13740

N14-C15 14962

C15-C16 15615

C16-N17 14567

N17-C18 14571

C18-C19 15558 C19-N14 14935

00160

-00050

-00018

00068

-00067

00005

00374

00188

-00162

-00224

00104

-00005

00078

-00044

-00036

-00038

-00097

-00566

00256

00098

-00109

-00106

00044

00229

IE

eV k J mol-1

∆Hf(M)+bull

k J mol-1

∆Hf(M)

k J mol-1

Molecule




) and



CO2]+bull









81 782 305 -485

Norfloxacin

8 772 314 -464

Pefloxacin

88 849 485 -368

Ciprofloxacin

83 801 142 -631

Levofloxacin




-1) The


-1)


kJmol-1


ion

by 106 kJmol-1























mz RI[] mz RI[]

mz RI[] mz RI[]

97 17 163 8 218 15 236 32 237 6 250 6 252 5 258 7 264 9 270 8 272 5 274 6 275 9 276 60 277 23 278 55 279 13 290 10 292 9 302 8 304 20 306 12 316 5 318 10 320[M+H]

+ 100 321 18 334[M+CH3]

+ 14 348[M+C2H5]

+ 20

289 6 290 31 291 9 292 12 316 10 317 5 318 27 319 6 332 6 333 6 334[M+H]

+ 100 335 19 346 6 348[M+CH3]

+ 5 362[M+C2H5]

+ 21

276 10 287 8 288 52 289 14 290 17 302 5 304 5 314 6 316 18 317 9 318 38 319 9 320 14 330 5 332[M+H]

+ 100 333 18 334 6 346[M+CH3]

+ 17 360[M+C2H5]

+ 23 361 6

130 7 318 14 319 9 320 31 321 7 344 5 346 6 348 7 360 9 361 9 362[M+H]

+ 100 363 20 376[M+CH3]

+ 5 390[M+C2H5]

+ 19















(59)





authors( 214860)



technique




in scheme 2




+

ion



+ and






N

O O

O HF

NHN

[M+H]+ = 320

- CO2

N

O

F

NHN

mz = 276

mz = 278

N

O O

O HF

RI = 100 RI = 60

RI = 55

H

C2 H

4 N

N

H+ H+

H+

N

O O

F

NHN

H+

- H2 O

mz = 302RI = 8

rearrangment
























kJmol-1






species



method

431

Mass

spectr

a of

Peflox

acin

under

EI technique

PA (M) kJmol

-1

∆Hf(M+H)+

kJmol-1

Protonated Site

∆Hf(M) kcalmol

-1

Molecule

904

749

142

297

O12H

N1H

-116

Norfloxacin

916

753

151

314

O12H

N1H

-111

Pefloxacin

904

745

255

418

O12H

N1H

-88

Ciprofloxacin

908

715

2

192

O12H

N1H

-149

Levofloxacin












Table 8




15 eV

70 eV

mz

10

55

3

21

100

4

6

16

10

10

6

10

30

26

7

4

12

61

3

18

100

4

6

14

11

7

4

6

20

15

6

4

334

333 [M]+middot

291

290

289 [M-CO2]+

245

219

218 [M-CO2-C4H9N]+

203 [M-CO2-C4H9N-CH3]+

96

81

79

71 [C4H9N]+bull

70

57

56







800 eV (772 kJ mole-1





Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

-0307

0198

-0262

-0297

0178

-0206

0010

-0020

0056

C4

C4a

C5

C6

C7

C8

C8a

C21

C22

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

0337

-0119

-0016

0103

0081

-0050

0095

0162

-0002

04135

-0301

-0357

-0300

-0169

-0391

0128

0143

-0428

0144

0128

0193

0318

-0082

0000

0124

0218

-0171

0190

0151

-0003

0401

-0293

-0328

-0228

-0124

-0164

0114

0124

-0418

0126

0114

0183

-0019

0037

0016

0021

0137

-0121

0095

-0011

-0001

-0014

0008

0029

0072

0045

0227

-0014

-0019

0010

-0018

-0014

-0010







ion by the







ion at mz 218 with


CO2- C4H9N]+bull





[C4H9N]+bull



On the other



at mz=71 RI=20 in

compariso

n with

Norfloxaci

n the

absence of

ndashCH3

group lead

to produce

the

fragment

[M-

C2H4N]+

ion at mz

= 277

RI=59

Scheme 3 Main

fragmentat

ion

pathways

of

Pefloxacin

at 70 eV

N

O O

O HF

NN

M

=333

- CO2

N

O

F

NN

mz =289

C4 H

9 N

RI = 61 RI = 100

H

N

O

HF

NH2C

RI = 14

mz = 218

H3C

N

O

H

CH2

F

NH2C

mz =203RI = 11

+ +

+

+


mz

- CH

3

H2C

N

CH2

CH2H3C

N

H2CCH2

CH2

H2C

H

r ea r

ang

men

t

C4H9N +

N

O

F

NH2C

O

O H



The

appearance

energy (AE)

of the

fragment

[M-CO2]+bull

ion at

mz=289 is

calculated

(using the

heats of

formation of

∆Hf(M)

molecule

∆Hf (CO2)

and ∆Hf [M-

CO2]+bull

)and

is found to

be equal to

830 eV(801

kJmol-1

)

The

difference

between the

value for

AE [M-CO2]+bull












-1)

Neutral molecule


Molecular ion


∆ L

N1-C2 14016

C2-C3 13689

C3-C4 14885

C4-C4a 15009

C4a-C5 14182

C5-C6 14295

C6-C7 14435

C7-C8 14208

C8-C8a 14299

C8a-N1 14220

N1-C21 14819

C21-C22 15379

C3-C9 14953

C9-O10 13581

C9-O11 12293

C4-O12 12274

C6-F13 13223

C7-N14 14312

N14-C15 14704

C15-C16 15521

C16-N17 14676

N17-C19 14677

C19-C20 15526

C20-N14 14699

N17-C18 14640

N1-C2 14180

C2-C3 13665

C3-C4 14877

C4-C4a 15072

C4a-C5 14101

C5-C6 14324

C6-C7 14928

C7-C8 14547

C8-C8a 14088

C8a-N1 13994

N1-C21 14922

C21-C22 15372

C3-C9 15008

C9-O10 13534

C9-O11 12273

C4-O12 12226

C6-F13 13114

C7-N14 13624

N14-C15 15031

C15-C16 15508

C16-N17 14609

N17-C19 14600

C19-C20 15504

C20-N14 15020

N17-C18 14739

00164

-00024

-00008

00063

-00081

00029

00493

00339

-00211

-00226

00103

-00007

00055

-00047

-00020

-00048

-00109

-00688

00327

-00013

-00067

-00077

-00022

00321

00099


kJmol-1


to 68 kJmol-1







100)







+


+



molecule



[M+C2H5- CO2]+bull

ion

N

O O

O HF

NN

=334

- CO2

N

O

F

NN

mz =290

RI = 100 RI = 31

HH+

[M+H]+

N

O

CF

NN

H+

O

mz = 316

RI = 10

- H2 O

- C2 H

4 N

N

O O

O HF

H+

N

mz = 292

RI = 12

H+

H3C

mz















kJmol-1



-







It is









15 eV

70 eV

mz

11

62

11

67

18

100

11

68

5

7

9

4

4

5

6

6

8

19

14

74

13

71

19

100

11

69

5

8

9

4

5

5

5

6

9

20

332

331 [M]+

290

289 [M-C2H4N]+

288

287 [M-CO2]+

246

245 [M-CO2-C2H4N]+

231

230

229

218

215

204

202

201

57

56










eV(849 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

(e)

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C22

O10

C9

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0277 0206

-0266 0339

-0117 -0021 0133 0076

-0075 0100 0035

-0053 -0057 -0295 0418

-0370 -0295 -0159 -0387 0128 0098

-0312 0096 0127

-0125 0233

-0179 0206

-0085 -0029 0147 0157

-0059 0116

-0042 -0026 -0034 -0285 0380

-0297 0064

-0137 -0419 0133 0099

-0324 0100 0138

0152 0027 0087

-0133 0032

-0008 0014 0081 0016 0016

-0077 0027 0023 0010

-0038 0073 0359 0022

-0032 0005 0001

-0012 0004 0011
















at mz 287 with






ion indicates





















N

O O

O HF

NN

M

= 331

- CO2

N

O

F

NN

= 287

C2 H

4 N

N

O O

O HF

N

RI = 74

RI = 100

RI = 71

H

N

O

HF

RI = 69

C2 H

4 N

- CO2

+ +

H H

H rearengment

N

H rearengm

ent

mz 56RI = 20

mz

mz

mz = 245

mz = 289

H2C

NCH2

CH2




Neutral molecule


Molecular ion


∆ L




CO2)+bull








(050 eV)This














N1-C2 14017

C2-C3 1371

C3-C4 14908

C4-C4a 15019

C4a-C5 14169

C5-C6 1431

C6-C7 14441

C7-C8 14194

C8-C8a 14281

N1-C20 14534

C20-C21 15421

C21-C22 15186

C22-C20 15420

C3-C9 14939

C9-O10 13571

C9-O11 12308

C4-O12 12269

C6-F13 13203

C7-N14 14310

N14-C15 14700

C15-C16 15530

C16-N17 14670

N17-C18 14661

C18-C19 15528

C19-N14 14701

N1-C2 13703

C2-C3 14123

C3-C4 14229

C4-C4a 14585

C4a-C5 14303

C5-C6 14214

C6-C7 14567

C7-C8 14189

C8-C8a 14311

N1-C20 14762

C20-C21 15436

C21-C22 15157

C22-C20 15449

C3-C9 15069

C9-O10 13502

C9-O11 12250

C4-O12 13096

C6-F13 13167

C7-N14 14102

N14-C15 14754

C15-C16 15534

C16-N17 14645

N17-C18 14636

C18-C19 15533

C19-N14 14746

-00314

00413

-00679

-00434

00134

-00096

00126

-00005

00030

00228

00015

-00029

00029

00130

-00069

-00058

00827

-00036

-00208

00054

00004

-00025

-00025

00005

00045















+) cations transfer


+ molecules with



N

O O

O HF

NN

- CO2

N

O

F

NN

N

O O

O HF

N

H

C2 H

4 N

H H

H+

[M+H]+ = 332

RI = 100

H+

mz = 288RI = 52

H+

mz= 290RI = 17

- H2 O

N

O O

F

NN

H

H+

mz = 314RI = 6

445

The

proton


Ciprofloxacin










745kJmol-1

and 904 kJmol-1



kJmol-1


















15 e V

70 e V

mz

16

100

14

5

5

5

9

19

8

7

34

-

17

100

17

5

7

6

12

22

11

10

29

4

362

361[M]+bull

317[M-CO2]+bull

276

273

254

247


232

231

71(C4H9N)+bull

56










eV(801 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

O21

-0299

0201

-0261

0338

-0099

-0028

0112

0092

0079

0051

-0227

-0292

0181

-0209

0322

-0062

-0005

014

0081

0104

0057

-0252

0007

-002

0052

-0016

0037

0023

0028

-0011

0025

0006

-0025

C22

C24

C23

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

015

0091

0016

0416

-0295

-0366

-0297

-0167

-0395

0142

0144

-0429

0143

0142

0194

0155

0088

0011

0402

-0291

-0332

-0244

-0141

-0081

01

0133

-0434

0135

0108

0188

0005

-0003

-0005

-0014

0004

0034

0053

0026

0314

-0042

-0011

-0005

-0008

-0034

-0006




















) The difference



) gives the



(020

eV)

Scheme 7 Main



N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

M

= 361mz = 317

C4H9N

N

O

N

O

HF

CH3

mz = 246

RI= 100 RI= 17

RI = 20

++

H-Rearangment

+

mz = 71RI = 29

+

mz

CH2

N

H2C

CH2

CH3

NH2C

H2C

CH2

CH2

H




Neutral molecule


Molecular ion


∆ L

N1-C2 13975

C2-C3 13719

C3-C4 14898

C4-C4a 15017

C4a-C5 14187

C5-C6 14314

C6-C7 14450

C7-C8 14368

C8-C8a 14446

C8a-N1 14153

C8-O21 13588

O21-C22 14028

C22-C24 15634

C24-N1 14823

C24-C23 15475

C3-C9 14961

C9-O10 13569

C9-O11 12301

C4-O12 12276

C6-F13 13223

C7-N14 14236

N14-C15 14675

C15-C16 15526

C16-N17 14676

N17-C19 14678

C19-C20 15524

C19-N14 14680

N17-C18 14632

N1-C2 14088

C2-C3 13706

C3-C4 14890

C4-C4a 15094

C4a-C5 14207

C5-C6 14253

C6-C7 14713

C7-C8 14520

C8-C8a 14459

C8a-N1 14031

C8-O21 13472

O21-C22 14140

C22-C24 15611

C24-N1 14852

C24-C23 15482

C3-C9 15018

C9-O10 13532

C9-O11 12275

C4-O12 12239

C6-F13 13164

C7-N14 13877

N14-C15 14978

C15-C16 15561

C16-N17 14620

N17-C19 14630

C19-C20 15521

C19-N14 14955

N17-C18 14730

00113

-00013

-00008

00077

00020

-00061

00263

00152

00013

-00122

-00116

00112

-00023

00029

00007

00057

-00037

-00026

-00037

-00059

-00359

00303

00035

-00056

-00048

-00003

00275

00098















and 19 respectively







N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

mz = 318

RI= 14

H+

[M+H]+

mz = 362

RI = 100

N

O

N

NH3C

O

O

OH

F

CH3

H+

- H2 O

mz = 344RI = 5

- C2 H

4 N

N

O

O

O

OH

F

CH3

H+

N

CH3

mz= 320RI = 31

H+








atoms of the ring



908 kJmol-1



kJmol-1



CHAPTER (5)

CONCLUSIONS


[M]+bull



for Levofloxacin







spectra indicated













REFERNCES














New York NY (1969)



















pp142(1998)







Soc3(2006)


















Chemistry (2004)















24714(2003)













(1999)


867105(2008)






241359(2005)






153 37(1996)





1216 794(2009)



250 370(2006)





Chem46 363( 2005)


B 530186(1990)


759(2005)





(1993)




هقدهت هي



للحصىل على


2213





زشق السبع









جبهعخ ثب

كليخ العلم










[M-C2H4N]+ and [M-

CO2-C2H4N]+









[MH-CO2]+bull


+
















هي قجر













CONTENTS

Page

ABSTRACT і


11 Introduction 1




Ionization 6









Ionization 13





31 Apparatus 16

32 Materials 16



41 Results 18



42 Discussion 20




























REFRENCES 88

ARABIC SUMMARY


figure

Name

Page

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Figure 11

Figure 12

Figure 13

Figure 14

Figure 15




bull Path (a)





and Levofloxacin


used in this study













7

20

22

23

24

26

27

38

46

47

57

60

61

72

75

Figure 16

Figure 17

Scheme 1

Scheme 2

Scheme 3

Scheme 4

Scheme 5

Scheme 6

Scheme 7

Scheme 8



Schemes



technique



technique



technique



76

85

33

42

52

56

67

71

81

84

List of Tables

Table

Name

Page

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

Table 10

Table 11






























20

28

30

34

35

39

44

48

50

53

62

Table 12

Table 13

Table 14

Table 15

Table 16














64

68

77

79

82

CHAPTER (1)


11 Introduction











technique(1)







structure(2)












The


















The


are widely











phase(18)



compounds show that




























and HYin(24)










12 Aim of the Work






15 as well as 70 eV


technique






techniques






(ΔHf (M)+bull

)




investigation

CHAPTER (2)



Ionization






is formed


e-

[M] [M] +bull

+ 2 e-



can dissociate to




ion [F] +

[M]+bull

[F]+ + [N]


Also [M]+bull


and neutral


[M]+bull

[F]+bull





may


Io

ni

za

ti

on

E

ne

rg

y

(27)

Th

e

ion

izat

ion

ene

rgy

(IE

)

so

met

ime

s

call

ed

(les

s

cor

rect

ly)

the

ion

izat















principle(28-29)








showed


law of the form

σ (E) = C (E-Eo)n-1

(4)









which is formed

by the reaction

M+e- M

+bull + 2e

- (5)


IE[M]+bull

= ∆Hf[M]+bull

- ∆Hf[M] (6)

Where ∆Hf[M]+bull





[M]+bull

[F]+

+ [N]bull (7)



AE[F]+ = IE [F] +D[F-N] + Eexc (8)





(∆Eth) = ∆Hf[F]+ + ∆Hf[N] - ∆Hf[M] (9)





∆Hf[F]+ = IE[F] +∆Hf[F] (11)


Stevenson(32)



work of Audier(33)






molecular ion


spectra










is defined by



[A ndash B] +bull

A+ + B

bull (12)

odd even odd

[A ndash B] +bull

Abull + B

+ (13)

odd odd even

The fragment ion A+

or B+









Ionization






















CH4+ e- CH4

+bull CH3

+CH2

+ CH

++ 2e (14)

CH4+bull

+ CH4 CH5+ + CH3

bull (15)

CH3+ + CH4 C2H5

+ + H2 (16)


+




210 Proton Affinity





[BH]+ + M B+[M+H]

+ (17)




M + CH5+

[M+H]+ + CH4 (18)

M + H+ MH

+ (19)


+] = - PA

PA = - ∆Hordm































segments













CHAPTER (3)







software

31 Apparatus




positive ion mode










32 Materials






reagent gas




eV











CHAPTER (4)


41 Results











techniques














in


















literature

42 Discussion













Molecule

R1

R2

Norfloxacin

Pefloxacin

Ciprofloxacin

Levofloxacin

ethyl

ethyl

cyclopropyl


piperazinyl

4-methyl-piprazinyl

piperazinyl

4-methyl-piprazinyl









compounds




NN

N

F

CH3

O O

OH

PEFLOXACIN

H3C

NN

HN

F

O O

OH

CIPROFLOXACIN

NN

N

F

O O

OH

LEVOFLOXACIN

O

CH3H3C





compounds











chapter 2)







mz 320









15 e V

70 e V

mz

11

60

7

52

14

100

5

9

68

2

4

7

8

7

2

2

2

2

-

-

-

-

-

-

-

-

-

8

12

70

9

59

16

100

9

13

88

5

9

4

11

13

6

6

6

6

7

6

6

7

6

6

8

7

14

15

320

319 [M]+middot

278

277 [M-C2H4N]+

276

275 [M-CO2]+

245

234

233[M-CO2-C2H4N]+

219

218

217

204

203

190

189

176

175

161

95

85

83

81

73

71

69

57

56







The

removal

of an

electron

from an

organic

molecule

often

leads to

change in

its

relative










) (using




423

Fragm

entatio

n of

Norflo

xacin

using

EI

techniq

ue

Most

previous


(214850-51) where


However the present









respectively


[M-CO2]+bull



Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C9

O10

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0309

0199

-0264

0338

-0119

-0015

0102

0082

-0050

0096

0160

13002

0417

-0295

-0367

-0298

-0169

-0395

0127

0095

-0320

0095

0127

-0287

0175

-0202

0314

-0078

0000

0137

0173

-0145

0190

0149

-0004

0399

-0291

-0324

-0230

-0128

-0168

0082

0103

-0339

0105

0078

0022

-0024

0062

-0024

0041

0015

0035

0091

-0095

0094

-0011

-0006

-0018

0004

0043

0068

0041

0227

-0045

0008

-0019

0010

-0049







fragment (odd-




CO2]+bull



bull radical








+ ion through


(Scheme 1)




C3H7N (Scheme 1)


for



and ∆Hf(M)


) (Table





and



N

O O

O HF

NN

M

= 319

- CO2

N

O

F

NN

= 275

C2 H

4 N

= 277

N

O O

O HF

RI = 70 RI = 100

RI = 59

H

N

O

HF

RI = 88

C2H

4N

- CO2

= 233

NN

+ +

- C3 H

7 N

N

O

HF

N

mz mz

mz

mz = 218

RI = 9

mz

HH rearrangement

rearrangement

+

si m

pl e

cl e

av

ag

e



Table

5

Calcul

ated

∆Hf(M

)∆Hf(

M)+bull

an

d IE

values

for the

four

6-

fluoro

quinol

one

molec

ules

using

MND

O method

Neutral molecule




∆ L

N1-C2 14007

C2-C3 13700

C3-C4 14881

C4-C4a 15012

C4a-C5 14185

C5-C6 14294

C6-C7 14433

C7-C8 14203

C8-C8a 14304

C8a-N1 14204

N1-C20 14830

C20-C21 15379

C3-C9 14950

C9-O10 13571

C9-O11 12304

C4-O12 12275

C6-F13 13223

C7-N14 14306

N14-C15 14706

C15-C16 15517

C16-N17 14676

N17-C18 14677

C18-C19 15514 C19-N14 14706

N1-C2 14167

C2-C3 13650

C3-C4 14863

C4-C4a 15080

C4a-C5 14118

C5-C6 14299

C6-C7 14807

C7-C8 14391

C8-C8a 14142

C8a-N1 13980

N1-C20 14934

C20-C21 15374

C3-C9 15028

C9-O10 13527

C9-O11 12268

C4-O12 12237

C6-F13 13126

C7-N14 13740

N14-C15 14962

C15-C16 15615

C16-N17 14567

N17-C18 14571

C18-C19 15558 C19-N14 14935

00160

-00050

-00018

00068

-00067

00005

00374

00188

-00162

-00224

00104

-00005

00078

-00044

-00036

-00038

-00097

-00566

00256

00098

-00109

-00106

00044

00229

IE

eV k J mol-1

∆Hf(M)+bull

k J mol-1

∆Hf(M)

k J mol-1

Molecule




) and



CO2]+bull









81 782 305 -485

Norfloxacin

8 772 314 -464

Pefloxacin

88 849 485 -368

Ciprofloxacin

83 801 142 -631

Levofloxacin




-1) The


-1)


kJmol-1


ion

by 106 kJmol-1























mz RI[] mz RI[]

mz RI[] mz RI[]

97 17 163 8 218 15 236 32 237 6 250 6 252 5 258 7 264 9 270 8 272 5 274 6 275 9 276 60 277 23 278 55 279 13 290 10 292 9 302 8 304 20 306 12 316 5 318 10 320[M+H]

+ 100 321 18 334[M+CH3]

+ 14 348[M+C2H5]

+ 20

289 6 290 31 291 9 292 12 316 10 317 5 318 27 319 6 332 6 333 6 334[M+H]

+ 100 335 19 346 6 348[M+CH3]

+ 5 362[M+C2H5]

+ 21

276 10 287 8 288 52 289 14 290 17 302 5 304 5 314 6 316 18 317 9 318 38 319 9 320 14 330 5 332[M+H]

+ 100 333 18 334 6 346[M+CH3]

+ 17 360[M+C2H5]

+ 23 361 6

130 7 318 14 319 9 320 31 321 7 344 5 346 6 348 7 360 9 361 9 362[M+H]

+ 100 363 20 376[M+CH3]

+ 5 390[M+C2H5]

+ 19















(59)





authors( 214860)



technique




in scheme 2




+

ion



+ and






N

O O

O HF

NHN

[M+H]+ = 320

- CO2

N

O

F

NHN

mz = 276

mz = 278

N

O O

O HF

RI = 100 RI = 60

RI = 55

H

C2 H

4 N

N

H+ H+

H+

N

O O

F

NHN

H+

- H2 O

mz = 302RI = 8

rearrangment
























kJmol-1






species



method

431

Mass

spectr

a of

Peflox

acin

under

EI technique

PA (M) kJmol

-1

∆Hf(M+H)+

kJmol-1

Protonated Site

∆Hf(M) kcalmol

-1

Molecule

904

749

142

297

O12H

N1H

-116

Norfloxacin

916

753

151

314

O12H

N1H

-111

Pefloxacin

904

745

255

418

O12H

N1H

-88

Ciprofloxacin

908

715

2

192

O12H

N1H

-149

Levofloxacin












Table 8




15 eV

70 eV

mz

10

55

3

21

100

4

6

16

10

10

6

10

30

26

7

4

12

61

3

18

100

4

6

14

11

7

4

6

20

15

6

4

334

333 [M]+middot

291

290

289 [M-CO2]+

245

219

218 [M-CO2-C4H9N]+

203 [M-CO2-C4H9N-CH3]+

96

81

79

71 [C4H9N]+bull

70

57

56







800 eV (772 kJ mole-1





Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

-0307

0198

-0262

-0297

0178

-0206

0010

-0020

0056

C4

C4a

C5

C6

C7

C8

C8a

C21

C22

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

0337

-0119

-0016

0103

0081

-0050

0095

0162

-0002

04135

-0301

-0357

-0300

-0169

-0391

0128

0143

-0428

0144

0128

0193

0318

-0082

0000

0124

0218

-0171

0190

0151

-0003

0401

-0293

-0328

-0228

-0124

-0164

0114

0124

-0418

0126

0114

0183

-0019

0037

0016

0021

0137

-0121

0095

-0011

-0001

-0014

0008

0029

0072

0045

0227

-0014

-0019

0010

-0018

-0014

-0010







ion by the







ion at mz 218 with


CO2- C4H9N]+bull





[C4H9N]+bull



On the other



at mz=71 RI=20 in

compariso

n with

Norfloxaci

n the

absence of

ndashCH3

group lead

to produce

the

fragment

[M-

C2H4N]+

ion at mz

= 277

RI=59

Scheme 3 Main

fragmentat

ion

pathways

of

Pefloxacin

at 70 eV

N

O O

O HF

NN

M

=333

- CO2

N

O

F

NN

mz =289

C4 H

9 N

RI = 61 RI = 100

H

N

O

HF

NH2C

RI = 14

mz = 218

H3C

N

O

H

CH2

F

NH2C

mz =203RI = 11

+ +

+

+


mz

- CH

3

H2C

N

CH2

CH2H3C

N

H2CCH2

CH2

H2C

H

r ea r

ang

men

t

C4H9N +

N

O

F

NH2C

O

O H



The

appearance

energy (AE)

of the

fragment

[M-CO2]+bull

ion at

mz=289 is

calculated

(using the

heats of

formation of

∆Hf(M)

molecule

∆Hf (CO2)

and ∆Hf [M-

CO2]+bull

)and

is found to

be equal to

830 eV(801

kJmol-1

)

The

difference

between the

value for

AE [M-CO2]+bull












-1)

Neutral molecule


Molecular ion


∆ L

N1-C2 14016

C2-C3 13689

C3-C4 14885

C4-C4a 15009

C4a-C5 14182

C5-C6 14295

C6-C7 14435

C7-C8 14208

C8-C8a 14299

C8a-N1 14220

N1-C21 14819

C21-C22 15379

C3-C9 14953

C9-O10 13581

C9-O11 12293

C4-O12 12274

C6-F13 13223

C7-N14 14312

N14-C15 14704

C15-C16 15521

C16-N17 14676

N17-C19 14677

C19-C20 15526

C20-N14 14699

N17-C18 14640

N1-C2 14180

C2-C3 13665

C3-C4 14877

C4-C4a 15072

C4a-C5 14101

C5-C6 14324

C6-C7 14928

C7-C8 14547

C8-C8a 14088

C8a-N1 13994

N1-C21 14922

C21-C22 15372

C3-C9 15008

C9-O10 13534

C9-O11 12273

C4-O12 12226

C6-F13 13114

C7-N14 13624

N14-C15 15031

C15-C16 15508

C16-N17 14609

N17-C19 14600

C19-C20 15504

C20-N14 15020

N17-C18 14739

00164

-00024

-00008

00063

-00081

00029

00493

00339

-00211

-00226

00103

-00007

00055

-00047

-00020

-00048

-00109

-00688

00327

-00013

-00067

-00077

-00022

00321

00099


kJmol-1


to 68 kJmol-1







100)







+


+



molecule



[M+C2H5- CO2]+bull

ion

N

O O

O HF

NN

=334

- CO2

N

O

F

NN

mz =290

RI = 100 RI = 31

HH+

[M+H]+

N

O

CF

NN

H+

O

mz = 316

RI = 10

- H2 O

- C2 H

4 N

N

O O

O HF

H+

N

mz = 292

RI = 12

H+

H3C

mz















kJmol-1



-







It is









15 eV

70 eV

mz

11

62

11

67

18

100

11

68

5

7

9

4

4

5

6

6

8

19

14

74

13

71

19

100

11

69

5

8

9

4

5

5

5

6

9

20

332

331 [M]+

290

289 [M-C2H4N]+

288

287 [M-CO2]+

246

245 [M-CO2-C2H4N]+

231

230

229

218

215

204

202

201

57

56










eV(849 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

(e)

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C22

O10

C9

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0277 0206

-0266 0339

-0117 -0021 0133 0076

-0075 0100 0035

-0053 -0057 -0295 0418

-0370 -0295 -0159 -0387 0128 0098

-0312 0096 0127

-0125 0233

-0179 0206

-0085 -0029 0147 0157

-0059 0116

-0042 -0026 -0034 -0285 0380

-0297 0064

-0137 -0419 0133 0099

-0324 0100 0138

0152 0027 0087

-0133 0032

-0008 0014 0081 0016 0016

-0077 0027 0023 0010

-0038 0073 0359 0022

-0032 0005 0001

-0012 0004 0011
















at mz 287 with






ion indicates





















N

O O

O HF

NN

M

= 331

- CO2

N

O

F

NN

= 287

C2 H

4 N

N

O O

O HF

N

RI = 74

RI = 100

RI = 71

H

N

O

HF

RI = 69

C2 H

4 N

- CO2

+ +

H H

H rearengment

N

H rearengm

ent

mz 56RI = 20

mz

mz

mz = 245

mz = 289

H2C

NCH2

CH2




Neutral molecule


Molecular ion


∆ L




CO2)+bull








(050 eV)This














N1-C2 14017

C2-C3 1371

C3-C4 14908

C4-C4a 15019

C4a-C5 14169

C5-C6 1431

C6-C7 14441

C7-C8 14194

C8-C8a 14281

N1-C20 14534

C20-C21 15421

C21-C22 15186

C22-C20 15420

C3-C9 14939

C9-O10 13571

C9-O11 12308

C4-O12 12269

C6-F13 13203

C7-N14 14310

N14-C15 14700

C15-C16 15530

C16-N17 14670

N17-C18 14661

C18-C19 15528

C19-N14 14701

N1-C2 13703

C2-C3 14123

C3-C4 14229

C4-C4a 14585

C4a-C5 14303

C5-C6 14214

C6-C7 14567

C7-C8 14189

C8-C8a 14311

N1-C20 14762

C20-C21 15436

C21-C22 15157

C22-C20 15449

C3-C9 15069

C9-O10 13502

C9-O11 12250

C4-O12 13096

C6-F13 13167

C7-N14 14102

N14-C15 14754

C15-C16 15534

C16-N17 14645

N17-C18 14636

C18-C19 15533

C19-N14 14746

-00314

00413

-00679

-00434

00134

-00096

00126

-00005

00030

00228

00015

-00029

00029

00130

-00069

-00058

00827

-00036

-00208

00054

00004

-00025

-00025

00005

00045















+) cations transfer


+ molecules with



N

O O

O HF

NN

- CO2

N

O

F

NN

N

O O

O HF

N

H

C2 H

4 N

H H

H+

[M+H]+ = 332

RI = 100

H+

mz = 288RI = 52

H+

mz= 290RI = 17

- H2 O

N

O O

F

NN

H

H+

mz = 314RI = 6

445

The

proton


Ciprofloxacin










745kJmol-1

and 904 kJmol-1



kJmol-1


















15 e V

70 e V

mz

16

100

14

5

5

5

9

19

8

7

34

-

17

100

17

5

7

6

12

22

11

10

29

4

362

361[M]+bull

317[M-CO2]+bull

276

273

254

247


232

231

71(C4H9N)+bull

56










eV(801 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

O21

-0299

0201

-0261

0338

-0099

-0028

0112

0092

0079

0051

-0227

-0292

0181

-0209

0322

-0062

-0005

014

0081

0104

0057

-0252

0007

-002

0052

-0016

0037

0023

0028

-0011

0025

0006

-0025

C22

C24

C23

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

015

0091

0016

0416

-0295

-0366

-0297

-0167

-0395

0142

0144

-0429

0143

0142

0194

0155

0088

0011

0402

-0291

-0332

-0244

-0141

-0081

01

0133

-0434

0135

0108

0188

0005

-0003

-0005

-0014

0004

0034

0053

0026

0314

-0042

-0011

-0005

-0008

-0034

-0006




















) The difference



) gives the



(020

eV)

Scheme 7 Main



N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

M

= 361mz = 317

C4H9N

N

O

N

O

HF

CH3

mz = 246

RI= 100 RI= 17

RI = 20

++

H-Rearangment

+

mz = 71RI = 29

+

mz

CH2

N

H2C

CH2

CH3

NH2C

H2C

CH2

CH2

H




Neutral molecule


Molecular ion


∆ L

N1-C2 13975

C2-C3 13719

C3-C4 14898

C4-C4a 15017

C4a-C5 14187

C5-C6 14314

C6-C7 14450

C7-C8 14368

C8-C8a 14446

C8a-N1 14153

C8-O21 13588

O21-C22 14028

C22-C24 15634

C24-N1 14823

C24-C23 15475

C3-C9 14961

C9-O10 13569

C9-O11 12301

C4-O12 12276

C6-F13 13223

C7-N14 14236

N14-C15 14675

C15-C16 15526

C16-N17 14676

N17-C19 14678

C19-C20 15524

C19-N14 14680

N17-C18 14632

N1-C2 14088

C2-C3 13706

C3-C4 14890

C4-C4a 15094

C4a-C5 14207

C5-C6 14253

C6-C7 14713

C7-C8 14520

C8-C8a 14459

C8a-N1 14031

C8-O21 13472

O21-C22 14140

C22-C24 15611

C24-N1 14852

C24-C23 15482

C3-C9 15018

C9-O10 13532

C9-O11 12275

C4-O12 12239

C6-F13 13164

C7-N14 13877

N14-C15 14978

C15-C16 15561

C16-N17 14620

N17-C19 14630

C19-C20 15521

C19-N14 14955

N17-C18 14730

00113

-00013

-00008

00077

00020

-00061

00263

00152

00013

-00122

-00116

00112

-00023

00029

00007

00057

-00037

-00026

-00037

-00059

-00359

00303

00035

-00056

-00048

-00003

00275

00098















and 19 respectively







N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

mz = 318

RI= 14

H+

[M+H]+

mz = 362

RI = 100

N

O

N

NH3C

O

O

OH

F

CH3

H+

- H2 O

mz = 344RI = 5

- C2 H

4 N

N

O

O

O

OH

F

CH3

H+

N

CH3

mz= 320RI = 31

H+








atoms of the ring



908 kJmol-1



kJmol-1



CHAPTER (5)

CONCLUSIONS


[M]+bull



for Levofloxacin







spectra indicated













REFERNCES














New York NY (1969)



















pp142(1998)







Soc3(2006)


















Chemistry (2004)















24714(2003)













(1999)


867105(2008)






241359(2005)






153 37(1996)





1216 794(2009)



250 370(2006)





Chem46 363( 2005)


B 530186(1990)


759(2005)





(1993)




هقدهت هي



للحصىل على


2213





زشق السبع









جبهعخ ثب

كليخ العلم










[M-C2H4N]+ and [M-

CO2-C2H4N]+









[MH-CO2]+bull


+
















هي قجر















42 Discussion 20




























REFRENCES 88

ARABIC SUMMARY


figure

Name

Page

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Figure 11

Figure 12

Figure 13

Figure 14

Figure 15




bull Path (a)





and Levofloxacin


used in this study













7

20

22

23

24

26

27

38

46

47

57

60

61

72

75

Figure 16

Figure 17

Scheme 1

Scheme 2

Scheme 3

Scheme 4

Scheme 5

Scheme 6

Scheme 7

Scheme 8



Schemes



technique



technique



technique



76

85

33

42

52

56

67

71

81

84

List of Tables

Table

Name

Page

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

Table 10

Table 11






























20

28

30

34

35

39

44

48

50

53

62

Table 12

Table 13

Table 14

Table 15

Table 16














64

68

77

79

82

CHAPTER (1)


11 Introduction











technique(1)







structure(2)












The


















The


are widely











phase(18)



compounds show that




























and HYin(24)










12 Aim of the Work






15 as well as 70 eV


technique






techniques






(ΔHf (M)+bull

)




investigation

CHAPTER (2)



Ionization






is formed


e-

[M] [M] +bull

+ 2 e-



can dissociate to




ion [F] +

[M]+bull

[F]+ + [N]


Also [M]+bull


and neutral


[M]+bull

[F]+bull





may


Io

ni

za

ti

on

E

ne

rg

y

(27)

Th

e

ion

izat

ion

ene

rgy

(IE

)

so

met

ime

s

call

ed

(les

s

cor

rect

ly)

the

ion

izat















principle(28-29)








showed


law of the form

σ (E) = C (E-Eo)n-1

(4)









which is formed

by the reaction

M+e- M

+bull + 2e

- (5)


IE[M]+bull

= ∆Hf[M]+bull

- ∆Hf[M] (6)

Where ∆Hf[M]+bull





[M]+bull

[F]+

+ [N]bull (7)



AE[F]+ = IE [F] +D[F-N] + Eexc (8)





(∆Eth) = ∆Hf[F]+ + ∆Hf[N] - ∆Hf[M] (9)





∆Hf[F]+ = IE[F] +∆Hf[F] (11)


Stevenson(32)



work of Audier(33)






molecular ion


spectra










is defined by



[A ndash B] +bull

A+ + B

bull (12)

odd even odd

[A ndash B] +bull

Abull + B

+ (13)

odd odd even

The fragment ion A+

or B+









Ionization






















CH4+ e- CH4

+bull CH3

+CH2

+ CH

++ 2e (14)

CH4+bull

+ CH4 CH5+ + CH3

bull (15)

CH3+ + CH4 C2H5

+ + H2 (16)


+




210 Proton Affinity





[BH]+ + M B+[M+H]

+ (17)




M + CH5+

[M+H]+ + CH4 (18)

M + H+ MH

+ (19)


+] = - PA

PA = - ∆Hordm































segments













CHAPTER (3)







software

31 Apparatus




positive ion mode










32 Materials






reagent gas




eV











CHAPTER (4)


41 Results











techniques














in


















literature

42 Discussion













Molecule

R1

R2

Norfloxacin

Pefloxacin

Ciprofloxacin

Levofloxacin

ethyl

ethyl

cyclopropyl


piperazinyl

4-methyl-piprazinyl

piperazinyl

4-methyl-piprazinyl









compounds




NN

N

F

CH3

O O

OH

PEFLOXACIN

H3C

NN

HN

F

O O

OH

CIPROFLOXACIN

NN

N

F

O O

OH

LEVOFLOXACIN

O

CH3H3C





compounds











chapter 2)







mz 320









15 e V

70 e V

mz

11

60

7

52

14

100

5

9

68

2

4

7

8

7

2

2

2

2

-

-

-

-

-

-

-

-

-

8

12

70

9

59

16

100

9

13

88

5

9

4

11

13

6

6

6

6

7

6

6

7

6

6

8

7

14

15

320

319 [M]+middot

278

277 [M-C2H4N]+

276

275 [M-CO2]+

245

234

233[M-CO2-C2H4N]+

219

218

217

204

203

190

189

176

175

161

95

85

83

81

73

71

69

57

56







The

removal

of an

electron

from an

organic

molecule

often

leads to

change in

its

relative










) (using




423

Fragm

entatio

n of

Norflo

xacin

using

EI

techniq

ue

Most

previous


(214850-51) where


However the present









respectively


[M-CO2]+bull



Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C9

O10

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0309

0199

-0264

0338

-0119

-0015

0102

0082

-0050

0096

0160

13002

0417

-0295

-0367

-0298

-0169

-0395

0127

0095

-0320

0095

0127

-0287

0175

-0202

0314

-0078

0000

0137

0173

-0145

0190

0149

-0004

0399

-0291

-0324

-0230

-0128

-0168

0082

0103

-0339

0105

0078

0022

-0024

0062

-0024

0041

0015

0035

0091

-0095

0094

-0011

-0006

-0018

0004

0043

0068

0041

0227

-0045

0008

-0019

0010

-0049







fragment (odd-




CO2]+bull



bull radical








+ ion through


(Scheme 1)




C3H7N (Scheme 1)


for



and ∆Hf(M)


) (Table





and



N

O O

O HF

NN

M

= 319

- CO2

N

O

F

NN

= 275

C2 H

4 N

= 277

N

O O

O HF

RI = 70 RI = 100

RI = 59

H

N

O

HF

RI = 88

C2H

4N

- CO2

= 233

NN

+ +

- C3 H

7 N

N

O

HF

N

mz mz

mz

mz = 218

RI = 9

mz

HH rearrangement

rearrangement

+

si m

pl e

cl e

av

ag

e



Table

5

Calcul

ated

∆Hf(M

)∆Hf(

M)+bull

an

d IE

values

for the

four

6-

fluoro

quinol

one

molec

ules

using

MND

O method

Neutral molecule




∆ L

N1-C2 14007

C2-C3 13700

C3-C4 14881

C4-C4a 15012

C4a-C5 14185

C5-C6 14294

C6-C7 14433

C7-C8 14203

C8-C8a 14304

C8a-N1 14204

N1-C20 14830

C20-C21 15379

C3-C9 14950

C9-O10 13571

C9-O11 12304

C4-O12 12275

C6-F13 13223

C7-N14 14306

N14-C15 14706

C15-C16 15517

C16-N17 14676

N17-C18 14677

C18-C19 15514 C19-N14 14706

N1-C2 14167

C2-C3 13650

C3-C4 14863

C4-C4a 15080

C4a-C5 14118

C5-C6 14299

C6-C7 14807

C7-C8 14391

C8-C8a 14142

C8a-N1 13980

N1-C20 14934

C20-C21 15374

C3-C9 15028

C9-O10 13527

C9-O11 12268

C4-O12 12237

C6-F13 13126

C7-N14 13740

N14-C15 14962

C15-C16 15615

C16-N17 14567

N17-C18 14571

C18-C19 15558 C19-N14 14935

00160

-00050

-00018

00068

-00067

00005

00374

00188

-00162

-00224

00104

-00005

00078

-00044

-00036

-00038

-00097

-00566

00256

00098

-00109

-00106

00044

00229

IE

eV k J mol-1

∆Hf(M)+bull

k J mol-1

∆Hf(M)

k J mol-1

Molecule




) and



CO2]+bull









81 782 305 -485

Norfloxacin

8 772 314 -464

Pefloxacin

88 849 485 -368

Ciprofloxacin

83 801 142 -631

Levofloxacin




-1) The


-1)


kJmol-1


ion

by 106 kJmol-1























mz RI[] mz RI[]

mz RI[] mz RI[]

97 17 163 8 218 15 236 32 237 6 250 6 252 5 258 7 264 9 270 8 272 5 274 6 275 9 276 60 277 23 278 55 279 13 290 10 292 9 302 8 304 20 306 12 316 5 318 10 320[M+H]

+ 100 321 18 334[M+CH3]

+ 14 348[M+C2H5]

+ 20

289 6 290 31 291 9 292 12 316 10 317 5 318 27 319 6 332 6 333 6 334[M+H]

+ 100 335 19 346 6 348[M+CH3]

+ 5 362[M+C2H5]

+ 21

276 10 287 8 288 52 289 14 290 17 302 5 304 5 314 6 316 18 317 9 318 38 319 9 320 14 330 5 332[M+H]

+ 100 333 18 334 6 346[M+CH3]

+ 17 360[M+C2H5]

+ 23 361 6

130 7 318 14 319 9 320 31 321 7 344 5 346 6 348 7 360 9 361 9 362[M+H]

+ 100 363 20 376[M+CH3]

+ 5 390[M+C2H5]

+ 19















(59)





authors( 214860)



technique




in scheme 2




+

ion



+ and






N

O O

O HF

NHN

[M+H]+ = 320

- CO2

N

O

F

NHN

mz = 276

mz = 278

N

O O

O HF

RI = 100 RI = 60

RI = 55

H

C2 H

4 N

N

H+ H+

H+

N

O O

F

NHN

H+

- H2 O

mz = 302RI = 8

rearrangment
























kJmol-1






species



method

431

Mass

spectr

a of

Peflox

acin

under

EI technique

PA (M) kJmol

-1

∆Hf(M+H)+

kJmol-1

Protonated Site

∆Hf(M) kcalmol

-1

Molecule

904

749

142

297

O12H

N1H

-116

Norfloxacin

916

753

151

314

O12H

N1H

-111

Pefloxacin

904

745

255

418

O12H

N1H

-88

Ciprofloxacin

908

715

2

192

O12H

N1H

-149

Levofloxacin












Table 8




15 eV

70 eV

mz

10

55

3

21

100

4

6

16

10

10

6

10

30

26

7

4

12

61

3

18

100

4

6

14

11

7

4

6

20

15

6

4

334

333 [M]+middot

291

290

289 [M-CO2]+

245

219

218 [M-CO2-C4H9N]+

203 [M-CO2-C4H9N-CH3]+

96

81

79

71 [C4H9N]+bull

70

57

56







800 eV (772 kJ mole-1





Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

-0307

0198

-0262

-0297

0178

-0206

0010

-0020

0056

C4

C4a

C5

C6

C7

C8

C8a

C21

C22

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

0337

-0119

-0016

0103

0081

-0050

0095

0162

-0002

04135

-0301

-0357

-0300

-0169

-0391

0128

0143

-0428

0144

0128

0193

0318

-0082

0000

0124

0218

-0171

0190

0151

-0003

0401

-0293

-0328

-0228

-0124

-0164

0114

0124

-0418

0126

0114

0183

-0019

0037

0016

0021

0137

-0121

0095

-0011

-0001

-0014

0008

0029

0072

0045

0227

-0014

-0019

0010

-0018

-0014

-0010







ion by the







ion at mz 218 with


CO2- C4H9N]+bull





[C4H9N]+bull



On the other



at mz=71 RI=20 in

compariso

n with

Norfloxaci

n the

absence of

ndashCH3

group lead

to produce

the

fragment

[M-

C2H4N]+

ion at mz

= 277

RI=59

Scheme 3 Main

fragmentat

ion

pathways

of

Pefloxacin

at 70 eV

N

O O

O HF

NN

M

=333

- CO2

N

O

F

NN

mz =289

C4 H

9 N

RI = 61 RI = 100

H

N

O

HF

NH2C

RI = 14

mz = 218

H3C

N

O

H

CH2

F

NH2C

mz =203RI = 11

+ +

+

+


mz

- CH

3

H2C

N

CH2

CH2H3C

N

H2CCH2

CH2

H2C

H

r ea r

ang

men

t

C4H9N +

N

O

F

NH2C

O

O H



The

appearance

energy (AE)

of the

fragment

[M-CO2]+bull

ion at

mz=289 is

calculated

(using the

heats of

formation of

∆Hf(M)

molecule

∆Hf (CO2)

and ∆Hf [M-

CO2]+bull

)and

is found to

be equal to

830 eV(801

kJmol-1

)

The

difference

between the

value for

AE [M-CO2]+bull












-1)

Neutral molecule


Molecular ion


∆ L

N1-C2 14016

C2-C3 13689

C3-C4 14885

C4-C4a 15009

C4a-C5 14182

C5-C6 14295

C6-C7 14435

C7-C8 14208

C8-C8a 14299

C8a-N1 14220

N1-C21 14819

C21-C22 15379

C3-C9 14953

C9-O10 13581

C9-O11 12293

C4-O12 12274

C6-F13 13223

C7-N14 14312

N14-C15 14704

C15-C16 15521

C16-N17 14676

N17-C19 14677

C19-C20 15526

C20-N14 14699

N17-C18 14640

N1-C2 14180

C2-C3 13665

C3-C4 14877

C4-C4a 15072

C4a-C5 14101

C5-C6 14324

C6-C7 14928

C7-C8 14547

C8-C8a 14088

C8a-N1 13994

N1-C21 14922

C21-C22 15372

C3-C9 15008

C9-O10 13534

C9-O11 12273

C4-O12 12226

C6-F13 13114

C7-N14 13624

N14-C15 15031

C15-C16 15508

C16-N17 14609

N17-C19 14600

C19-C20 15504

C20-N14 15020

N17-C18 14739

00164

-00024

-00008

00063

-00081

00029

00493

00339

-00211

-00226

00103

-00007

00055

-00047

-00020

-00048

-00109

-00688

00327

-00013

-00067

-00077

-00022

00321

00099


kJmol-1


to 68 kJmol-1







100)







+


+



molecule



[M+C2H5- CO2]+bull

ion

N

O O

O HF

NN

=334

- CO2

N

O

F

NN

mz =290

RI = 100 RI = 31

HH+

[M+H]+

N

O

CF

NN

H+

O

mz = 316

RI = 10

- H2 O

- C2 H

4 N

N

O O

O HF

H+

N

mz = 292

RI = 12

H+

H3C

mz















kJmol-1



-







It is









15 eV

70 eV

mz

11

62

11

67

18

100

11

68

5

7

9

4

4

5

6

6

8

19

14

74

13

71

19

100

11

69

5

8

9

4

5

5

5

6

9

20

332

331 [M]+

290

289 [M-C2H4N]+

288

287 [M-CO2]+

246

245 [M-CO2-C2H4N]+

231

230

229

218

215

204

202

201

57

56










eV(849 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

(e)

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C22

O10

C9

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0277 0206

-0266 0339

-0117 -0021 0133 0076

-0075 0100 0035

-0053 -0057 -0295 0418

-0370 -0295 -0159 -0387 0128 0098

-0312 0096 0127

-0125 0233

-0179 0206

-0085 -0029 0147 0157

-0059 0116

-0042 -0026 -0034 -0285 0380

-0297 0064

-0137 -0419 0133 0099

-0324 0100 0138

0152 0027 0087

-0133 0032

-0008 0014 0081 0016 0016

-0077 0027 0023 0010

-0038 0073 0359 0022

-0032 0005 0001

-0012 0004 0011
















at mz 287 with






ion indicates





















N

O O

O HF

NN

M

= 331

- CO2

N

O

F

NN

= 287

C2 H

4 N

N

O O

O HF

N

RI = 74

RI = 100

RI = 71

H

N

O

HF

RI = 69

C2 H

4 N

- CO2

+ +

H H

H rearengment

N

H rearengm

ent

mz 56RI = 20

mz

mz

mz = 245

mz = 289

H2C

NCH2

CH2




Neutral molecule


Molecular ion


∆ L




CO2)+bull








(050 eV)This














N1-C2 14017

C2-C3 1371

C3-C4 14908

C4-C4a 15019

C4a-C5 14169

C5-C6 1431

C6-C7 14441

C7-C8 14194

C8-C8a 14281

N1-C20 14534

C20-C21 15421

C21-C22 15186

C22-C20 15420

C3-C9 14939

C9-O10 13571

C9-O11 12308

C4-O12 12269

C6-F13 13203

C7-N14 14310

N14-C15 14700

C15-C16 15530

C16-N17 14670

N17-C18 14661

C18-C19 15528

C19-N14 14701

N1-C2 13703

C2-C3 14123

C3-C4 14229

C4-C4a 14585

C4a-C5 14303

C5-C6 14214

C6-C7 14567

C7-C8 14189

C8-C8a 14311

N1-C20 14762

C20-C21 15436

C21-C22 15157

C22-C20 15449

C3-C9 15069

C9-O10 13502

C9-O11 12250

C4-O12 13096

C6-F13 13167

C7-N14 14102

N14-C15 14754

C15-C16 15534

C16-N17 14645

N17-C18 14636

C18-C19 15533

C19-N14 14746

-00314

00413

-00679

-00434

00134

-00096

00126

-00005

00030

00228

00015

-00029

00029

00130

-00069

-00058

00827

-00036

-00208

00054

00004

-00025

-00025

00005

00045















+) cations transfer


+ molecules with



N

O O

O HF

NN

- CO2

N

O

F

NN

N

O O

O HF

N

H

C2 H

4 N

H H

H+

[M+H]+ = 332

RI = 100

H+

mz = 288RI = 52

H+

mz= 290RI = 17

- H2 O

N

O O

F

NN

H

H+

mz = 314RI = 6

445

The

proton


Ciprofloxacin










745kJmol-1

and 904 kJmol-1



kJmol-1


















15 e V

70 e V

mz

16

100

14

5

5

5

9

19

8

7

34

-

17

100

17

5

7

6

12

22

11

10

29

4

362

361[M]+bull

317[M-CO2]+bull

276

273

254

247


232

231

71(C4H9N)+bull

56










eV(801 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

O21

-0299

0201

-0261

0338

-0099

-0028

0112

0092

0079

0051

-0227

-0292

0181

-0209

0322

-0062

-0005

014

0081

0104

0057

-0252

0007

-002

0052

-0016

0037

0023

0028

-0011

0025

0006

-0025

C22

C24

C23

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

015

0091

0016

0416

-0295

-0366

-0297

-0167

-0395

0142

0144

-0429

0143

0142

0194

0155

0088

0011

0402

-0291

-0332

-0244

-0141

-0081

01

0133

-0434

0135

0108

0188

0005

-0003

-0005

-0014

0004

0034

0053

0026

0314

-0042

-0011

-0005

-0008

-0034

-0006




















) The difference



) gives the



(020

eV)

Scheme 7 Main



N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

M

= 361mz = 317

C4H9N

N

O

N

O

HF

CH3

mz = 246

RI= 100 RI= 17

RI = 20

++

H-Rearangment

+

mz = 71RI = 29

+

mz

CH2

N

H2C

CH2

CH3

NH2C

H2C

CH2

CH2

H




Neutral molecule


Molecular ion


∆ L

N1-C2 13975

C2-C3 13719

C3-C4 14898

C4-C4a 15017

C4a-C5 14187

C5-C6 14314

C6-C7 14450

C7-C8 14368

C8-C8a 14446

C8a-N1 14153

C8-O21 13588

O21-C22 14028

C22-C24 15634

C24-N1 14823

C24-C23 15475

C3-C9 14961

C9-O10 13569

C9-O11 12301

C4-O12 12276

C6-F13 13223

C7-N14 14236

N14-C15 14675

C15-C16 15526

C16-N17 14676

N17-C19 14678

C19-C20 15524

C19-N14 14680

N17-C18 14632

N1-C2 14088

C2-C3 13706

C3-C4 14890

C4-C4a 15094

C4a-C5 14207

C5-C6 14253

C6-C7 14713

C7-C8 14520

C8-C8a 14459

C8a-N1 14031

C8-O21 13472

O21-C22 14140

C22-C24 15611

C24-N1 14852

C24-C23 15482

C3-C9 15018

C9-O10 13532

C9-O11 12275

C4-O12 12239

C6-F13 13164

C7-N14 13877

N14-C15 14978

C15-C16 15561

C16-N17 14620

N17-C19 14630

C19-C20 15521

C19-N14 14955

N17-C18 14730

00113

-00013

-00008

00077

00020

-00061

00263

00152

00013

-00122

-00116

00112

-00023

00029

00007

00057

-00037

-00026

-00037

-00059

-00359

00303

00035

-00056

-00048

-00003

00275

00098















and 19 respectively







N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

mz = 318

RI= 14

H+

[M+H]+

mz = 362

RI = 100

N

O

N

NH3C

O

O

OH

F

CH3

H+

- H2 O

mz = 344RI = 5

- C2 H

4 N

N

O

O

O

OH

F

CH3

H+

N

CH3

mz= 320RI = 31

H+








atoms of the ring



908 kJmol-1



kJmol-1



CHAPTER (5)

CONCLUSIONS


[M]+bull



for Levofloxacin







spectra indicated













REFERNCES














New York NY (1969)



















pp142(1998)







Soc3(2006)


















Chemistry (2004)















24714(2003)













(1999)


867105(2008)






241359(2005)






153 37(1996)





1216 794(2009)



250 370(2006)





Chem46 363( 2005)


B 530186(1990)


759(2005)





(1993)




هقدهت هي



للحصىل على


2213





زشق السبع









جبهعخ ثب

كليخ العلم










[M-C2H4N]+ and [M-

CO2-C2H4N]+









[MH-CO2]+bull


+
















هي قجر














figure

Name

Page

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Figure 11

Figure 12

Figure 13

Figure 14

Figure 15




bull Path (a)





and Levofloxacin


used in this study













7

20

22

23

24

26

27

38

46

47

57

60

61

72

75

Figure 16

Figure 17

Scheme 1

Scheme 2

Scheme 3

Scheme 4

Scheme 5

Scheme 6

Scheme 7

Scheme 8



Schemes



technique



technique



technique



76

85

33

42

52

56

67

71

81

84

List of Tables

Table

Name

Page

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

Table 10

Table 11






























20

28

30

34

35

39

44

48

50

53

62

Table 12

Table 13

Table 14

Table 15

Table 16














64

68

77

79

82

CHAPTER (1)


11 Introduction











technique(1)







structure(2)












The


















The


are widely











phase(18)



compounds show that




























and HYin(24)










12 Aim of the Work






15 as well as 70 eV


technique






techniques






(ΔHf (M)+bull

)




investigation

CHAPTER (2)



Ionization






is formed


e-

[M] [M] +bull

+ 2 e-



can dissociate to




ion [F] +

[M]+bull

[F]+ + [N]


Also [M]+bull


and neutral


[M]+bull

[F]+bull





may


Io

ni

za

ti

on

E

ne

rg

y

(27)

Th

e

ion

izat

ion

ene

rgy

(IE

)

so

met

ime

s

call

ed

(les

s

cor

rect

ly)

the

ion

izat















principle(28-29)








showed


law of the form

σ (E) = C (E-Eo)n-1

(4)









which is formed

by the reaction

M+e- M

+bull + 2e

- (5)


IE[M]+bull

= ∆Hf[M]+bull

- ∆Hf[M] (6)

Where ∆Hf[M]+bull





[M]+bull

[F]+

+ [N]bull (7)



AE[F]+ = IE [F] +D[F-N] + Eexc (8)





(∆Eth) = ∆Hf[F]+ + ∆Hf[N] - ∆Hf[M] (9)





∆Hf[F]+ = IE[F] +∆Hf[F] (11)


Stevenson(32)



work of Audier(33)






molecular ion


spectra










is defined by



[A ndash B] +bull

A+ + B

bull (12)

odd even odd

[A ndash B] +bull

Abull + B

+ (13)

odd odd even

The fragment ion A+

or B+









Ionization






















CH4+ e- CH4

+bull CH3

+CH2

+ CH

++ 2e (14)

CH4+bull

+ CH4 CH5+ + CH3

bull (15)

CH3+ + CH4 C2H5

+ + H2 (16)


+




210 Proton Affinity





[BH]+ + M B+[M+H]

+ (17)




M + CH5+

[M+H]+ + CH4 (18)

M + H+ MH

+ (19)


+] = - PA

PA = - ∆Hordm































segments













CHAPTER (3)







software

31 Apparatus




positive ion mode










32 Materials






reagent gas




eV











CHAPTER (4)


41 Results











techniques














in


















literature

42 Discussion













Molecule

R1

R2

Norfloxacin

Pefloxacin

Ciprofloxacin

Levofloxacin

ethyl

ethyl

cyclopropyl


piperazinyl

4-methyl-piprazinyl

piperazinyl

4-methyl-piprazinyl









compounds




NN

N

F

CH3

O O

OH

PEFLOXACIN

H3C

NN

HN

F

O O

OH

CIPROFLOXACIN

NN

N

F

O O

OH

LEVOFLOXACIN

O

CH3H3C





compounds











chapter 2)







mz 320









15 e V

70 e V

mz

11

60

7

52

14

100

5

9

68

2

4

7

8

7

2

2

2

2

-

-

-

-

-

-

-

-

-

8

12

70

9

59

16

100

9

13

88

5

9

4

11

13

6

6

6

6

7

6

6

7

6

6

8

7

14

15

320

319 [M]+middot

278

277 [M-C2H4N]+

276

275 [M-CO2]+

245

234

233[M-CO2-C2H4N]+

219

218

217

204

203

190

189

176

175

161

95

85

83

81

73

71

69

57

56







The

removal

of an

electron

from an

organic

molecule

often

leads to

change in

its

relative










) (using




423

Fragm

entatio

n of

Norflo

xacin

using

EI

techniq

ue

Most

previous


(214850-51) where


However the present









respectively


[M-CO2]+bull



Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C9

O10

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0309

0199

-0264

0338

-0119

-0015

0102

0082

-0050

0096

0160

13002

0417

-0295

-0367

-0298

-0169

-0395

0127

0095

-0320

0095

0127

-0287

0175

-0202

0314

-0078

0000

0137

0173

-0145

0190

0149

-0004

0399

-0291

-0324

-0230

-0128

-0168

0082

0103

-0339

0105

0078

0022

-0024

0062

-0024

0041

0015

0035

0091

-0095

0094

-0011

-0006

-0018

0004

0043

0068

0041

0227

-0045

0008

-0019

0010

-0049







fragment (odd-




CO2]+bull



bull radical








+ ion through


(Scheme 1)




C3H7N (Scheme 1)


for



and ∆Hf(M)


) (Table





and



N

O O

O HF

NN

M

= 319

- CO2

N

O

F

NN

= 275

C2 H

4 N

= 277

N

O O

O HF

RI = 70 RI = 100

RI = 59

H

N

O

HF

RI = 88

C2H

4N

- CO2

= 233

NN

+ +

- C3 H

7 N

N

O

HF

N

mz mz

mz

mz = 218

RI = 9

mz

HH rearrangement

rearrangement

+

si m

pl e

cl e

av

ag

e



Table

5

Calcul

ated

∆Hf(M

)∆Hf(

M)+bull

an

d IE

values

for the

four

6-

fluoro

quinol

one

molec

ules

using

MND

O method

Neutral molecule




∆ L

N1-C2 14007

C2-C3 13700

C3-C4 14881

C4-C4a 15012

C4a-C5 14185

C5-C6 14294

C6-C7 14433

C7-C8 14203

C8-C8a 14304

C8a-N1 14204

N1-C20 14830

C20-C21 15379

C3-C9 14950

C9-O10 13571

C9-O11 12304

C4-O12 12275

C6-F13 13223

C7-N14 14306

N14-C15 14706

C15-C16 15517

C16-N17 14676

N17-C18 14677

C18-C19 15514 C19-N14 14706

N1-C2 14167

C2-C3 13650

C3-C4 14863

C4-C4a 15080

C4a-C5 14118

C5-C6 14299

C6-C7 14807

C7-C8 14391

C8-C8a 14142

C8a-N1 13980

N1-C20 14934

C20-C21 15374

C3-C9 15028

C9-O10 13527

C9-O11 12268

C4-O12 12237

C6-F13 13126

C7-N14 13740

N14-C15 14962

C15-C16 15615

C16-N17 14567

N17-C18 14571

C18-C19 15558 C19-N14 14935

00160

-00050

-00018

00068

-00067

00005

00374

00188

-00162

-00224

00104

-00005

00078

-00044

-00036

-00038

-00097

-00566

00256

00098

-00109

-00106

00044

00229

IE

eV k J mol-1

∆Hf(M)+bull

k J mol-1

∆Hf(M)

k J mol-1

Molecule




) and



CO2]+bull









81 782 305 -485

Norfloxacin

8 772 314 -464

Pefloxacin

88 849 485 -368

Ciprofloxacin

83 801 142 -631

Levofloxacin




-1) The


-1)


kJmol-1


ion

by 106 kJmol-1























mz RI[] mz RI[]

mz RI[] mz RI[]

97 17 163 8 218 15 236 32 237 6 250 6 252 5 258 7 264 9 270 8 272 5 274 6 275 9 276 60 277 23 278 55 279 13 290 10 292 9 302 8 304 20 306 12 316 5 318 10 320[M+H]

+ 100 321 18 334[M+CH3]

+ 14 348[M+C2H5]

+ 20

289 6 290 31 291 9 292 12 316 10 317 5 318 27 319 6 332 6 333 6 334[M+H]

+ 100 335 19 346 6 348[M+CH3]

+ 5 362[M+C2H5]

+ 21

276 10 287 8 288 52 289 14 290 17 302 5 304 5 314 6 316 18 317 9 318 38 319 9 320 14 330 5 332[M+H]

+ 100 333 18 334 6 346[M+CH3]

+ 17 360[M+C2H5]

+ 23 361 6

130 7 318 14 319 9 320 31 321 7 344 5 346 6 348 7 360 9 361 9 362[M+H]

+ 100 363 20 376[M+CH3]

+ 5 390[M+C2H5]

+ 19















(59)





authors( 214860)



technique




in scheme 2




+

ion



+ and






N

O O

O HF

NHN

[M+H]+ = 320

- CO2

N

O

F

NHN

mz = 276

mz = 278

N

O O

O HF

RI = 100 RI = 60

RI = 55

H

C2 H

4 N

N

H+ H+

H+

N

O O

F

NHN

H+

- H2 O

mz = 302RI = 8

rearrangment
























kJmol-1






species



method

431

Mass

spectr

a of

Peflox

acin

under

EI technique

PA (M) kJmol

-1

∆Hf(M+H)+

kJmol-1

Protonated Site

∆Hf(M) kcalmol

-1

Molecule

904

749

142

297

O12H

N1H

-116

Norfloxacin

916

753

151

314

O12H

N1H

-111

Pefloxacin

904

745

255

418

O12H

N1H

-88

Ciprofloxacin

908

715

2

192

O12H

N1H

-149

Levofloxacin












Table 8




15 eV

70 eV

mz

10

55

3

21

100

4

6

16

10

10

6

10

30

26

7

4

12

61

3

18

100

4

6

14

11

7

4

6

20

15

6

4

334

333 [M]+middot

291

290

289 [M-CO2]+

245

219

218 [M-CO2-C4H9N]+

203 [M-CO2-C4H9N-CH3]+

96

81

79

71 [C4H9N]+bull

70

57

56







800 eV (772 kJ mole-1





Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

-0307

0198

-0262

-0297

0178

-0206

0010

-0020

0056

C4

C4a

C5

C6

C7

C8

C8a

C21

C22

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

0337

-0119

-0016

0103

0081

-0050

0095

0162

-0002

04135

-0301

-0357

-0300

-0169

-0391

0128

0143

-0428

0144

0128

0193

0318

-0082

0000

0124

0218

-0171

0190

0151

-0003

0401

-0293

-0328

-0228

-0124

-0164

0114

0124

-0418

0126

0114

0183

-0019

0037

0016

0021

0137

-0121

0095

-0011

-0001

-0014

0008

0029

0072

0045

0227

-0014

-0019

0010

-0018

-0014

-0010







ion by the







ion at mz 218 with


CO2- C4H9N]+bull





[C4H9N]+bull



On the other



at mz=71 RI=20 in

compariso

n with

Norfloxaci

n the

absence of

ndashCH3

group lead

to produce

the

fragment

[M-

C2H4N]+

ion at mz

= 277

RI=59

Scheme 3 Main

fragmentat

ion

pathways

of

Pefloxacin

at 70 eV

N

O O

O HF

NN

M

=333

- CO2

N

O

F

NN

mz =289

C4 H

9 N

RI = 61 RI = 100

H

N

O

HF

NH2C

RI = 14

mz = 218

H3C

N

O

H

CH2

F

NH2C

mz =203RI = 11

+ +

+

+


mz

- CH

3

H2C

N

CH2

CH2H3C

N

H2CCH2

CH2

H2C

H

r ea r

ang

men

t

C4H9N +

N

O

F

NH2C

O

O H



The

appearance

energy (AE)

of the

fragment

[M-CO2]+bull

ion at

mz=289 is

calculated

(using the

heats of

formation of

∆Hf(M)

molecule

∆Hf (CO2)

and ∆Hf [M-

CO2]+bull

)and

is found to

be equal to

830 eV(801

kJmol-1

)

The

difference

between the

value for

AE [M-CO2]+bull












-1)

Neutral molecule


Molecular ion


∆ L

N1-C2 14016

C2-C3 13689

C3-C4 14885

C4-C4a 15009

C4a-C5 14182

C5-C6 14295

C6-C7 14435

C7-C8 14208

C8-C8a 14299

C8a-N1 14220

N1-C21 14819

C21-C22 15379

C3-C9 14953

C9-O10 13581

C9-O11 12293

C4-O12 12274

C6-F13 13223

C7-N14 14312

N14-C15 14704

C15-C16 15521

C16-N17 14676

N17-C19 14677

C19-C20 15526

C20-N14 14699

N17-C18 14640

N1-C2 14180

C2-C3 13665

C3-C4 14877

C4-C4a 15072

C4a-C5 14101

C5-C6 14324

C6-C7 14928

C7-C8 14547

C8-C8a 14088

C8a-N1 13994

N1-C21 14922

C21-C22 15372

C3-C9 15008

C9-O10 13534

C9-O11 12273

C4-O12 12226

C6-F13 13114

C7-N14 13624

N14-C15 15031

C15-C16 15508

C16-N17 14609

N17-C19 14600

C19-C20 15504

C20-N14 15020

N17-C18 14739

00164

-00024

-00008

00063

-00081

00029

00493

00339

-00211

-00226

00103

-00007

00055

-00047

-00020

-00048

-00109

-00688

00327

-00013

-00067

-00077

-00022

00321

00099


kJmol-1


to 68 kJmol-1







100)







+


+



molecule



[M+C2H5- CO2]+bull

ion

N

O O

O HF

NN

=334

- CO2

N

O

F

NN

mz =290

RI = 100 RI = 31

HH+

[M+H]+

N

O

CF

NN

H+

O

mz = 316

RI = 10

- H2 O

- C2 H

4 N

N

O O

O HF

H+

N

mz = 292

RI = 12

H+

H3C

mz















kJmol-1



-







It is









15 eV

70 eV

mz

11

62

11

67

18

100

11

68

5

7

9

4

4

5

6

6

8

19

14

74

13

71

19

100

11

69

5

8

9

4

5

5

5

6

9

20

332

331 [M]+

290

289 [M-C2H4N]+

288

287 [M-CO2]+

246

245 [M-CO2-C2H4N]+

231

230

229

218

215

204

202

201

57

56










eV(849 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

(e)

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C22

O10

C9

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0277 0206

-0266 0339

-0117 -0021 0133 0076

-0075 0100 0035

-0053 -0057 -0295 0418

-0370 -0295 -0159 -0387 0128 0098

-0312 0096 0127

-0125 0233

-0179 0206

-0085 -0029 0147 0157

-0059 0116

-0042 -0026 -0034 -0285 0380

-0297 0064

-0137 -0419 0133 0099

-0324 0100 0138

0152 0027 0087

-0133 0032

-0008 0014 0081 0016 0016

-0077 0027 0023 0010

-0038 0073 0359 0022

-0032 0005 0001

-0012 0004 0011
















at mz 287 with






ion indicates





















N

O O

O HF

NN

M

= 331

- CO2

N

O

F

NN

= 287

C2 H

4 N

N

O O

O HF

N

RI = 74

RI = 100

RI = 71

H

N

O

HF

RI = 69

C2 H

4 N

- CO2

+ +

H H

H rearengment

N

H rearengm

ent

mz 56RI = 20

mz

mz

mz = 245

mz = 289

H2C

NCH2

CH2




Neutral molecule


Molecular ion


∆ L




CO2)+bull








(050 eV)This














N1-C2 14017

C2-C3 1371

C3-C4 14908

C4-C4a 15019

C4a-C5 14169

C5-C6 1431

C6-C7 14441

C7-C8 14194

C8-C8a 14281

N1-C20 14534

C20-C21 15421

C21-C22 15186

C22-C20 15420

C3-C9 14939

C9-O10 13571

C9-O11 12308

C4-O12 12269

C6-F13 13203

C7-N14 14310

N14-C15 14700

C15-C16 15530

C16-N17 14670

N17-C18 14661

C18-C19 15528

C19-N14 14701

N1-C2 13703

C2-C3 14123

C3-C4 14229

C4-C4a 14585

C4a-C5 14303

C5-C6 14214

C6-C7 14567

C7-C8 14189

C8-C8a 14311

N1-C20 14762

C20-C21 15436

C21-C22 15157

C22-C20 15449

C3-C9 15069

C9-O10 13502

C9-O11 12250

C4-O12 13096

C6-F13 13167

C7-N14 14102

N14-C15 14754

C15-C16 15534

C16-N17 14645

N17-C18 14636

C18-C19 15533

C19-N14 14746

-00314

00413

-00679

-00434

00134

-00096

00126

-00005

00030

00228

00015

-00029

00029

00130

-00069

-00058

00827

-00036

-00208

00054

00004

-00025

-00025

00005

00045















+) cations transfer


+ molecules with



N

O O

O HF

NN

- CO2

N

O

F

NN

N

O O

O HF

N

H

C2 H

4 N

H H

H+

[M+H]+ = 332

RI = 100

H+

mz = 288RI = 52

H+

mz= 290RI = 17

- H2 O

N

O O

F

NN

H

H+

mz = 314RI = 6

445

The

proton


Ciprofloxacin










745kJmol-1

and 904 kJmol-1



kJmol-1


















15 e V

70 e V

mz

16

100

14

5

5

5

9

19

8

7

34

-

17

100

17

5

7

6

12

22

11

10

29

4

362

361[M]+bull

317[M-CO2]+bull

276

273

254

247


232

231

71(C4H9N)+bull

56










eV(801 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

O21

-0299

0201

-0261

0338

-0099

-0028

0112

0092

0079

0051

-0227

-0292

0181

-0209

0322

-0062

-0005

014

0081

0104

0057

-0252

0007

-002

0052

-0016

0037

0023

0028

-0011

0025

0006

-0025

C22

C24

C23

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

015

0091

0016

0416

-0295

-0366

-0297

-0167

-0395

0142

0144

-0429

0143

0142

0194

0155

0088

0011

0402

-0291

-0332

-0244

-0141

-0081

01

0133

-0434

0135

0108

0188

0005

-0003

-0005

-0014

0004

0034

0053

0026

0314

-0042

-0011

-0005

-0008

-0034

-0006




















) The difference



) gives the



(020

eV)

Scheme 7 Main



N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

M

= 361mz = 317

C4H9N

N

O

N

O

HF

CH3

mz = 246

RI= 100 RI= 17

RI = 20

++

H-Rearangment

+

mz = 71RI = 29

+

mz

CH2

N

H2C

CH2

CH3

NH2C

H2C

CH2

CH2

H




Neutral molecule


Molecular ion


∆ L

N1-C2 13975

C2-C3 13719

C3-C4 14898

C4-C4a 15017

C4a-C5 14187

C5-C6 14314

C6-C7 14450

C7-C8 14368

C8-C8a 14446

C8a-N1 14153

C8-O21 13588

O21-C22 14028

C22-C24 15634

C24-N1 14823

C24-C23 15475

C3-C9 14961

C9-O10 13569

C9-O11 12301

C4-O12 12276

C6-F13 13223

C7-N14 14236

N14-C15 14675

C15-C16 15526

C16-N17 14676

N17-C19 14678

C19-C20 15524

C19-N14 14680

N17-C18 14632

N1-C2 14088

C2-C3 13706

C3-C4 14890

C4-C4a 15094

C4a-C5 14207

C5-C6 14253

C6-C7 14713

C7-C8 14520

C8-C8a 14459

C8a-N1 14031

C8-O21 13472

O21-C22 14140

C22-C24 15611

C24-N1 14852

C24-C23 15482

C3-C9 15018

C9-O10 13532

C9-O11 12275

C4-O12 12239

C6-F13 13164

C7-N14 13877

N14-C15 14978

C15-C16 15561

C16-N17 14620

N17-C19 14630

C19-C20 15521

C19-N14 14955

N17-C18 14730

00113

-00013

-00008

00077

00020

-00061

00263

00152

00013

-00122

-00116

00112

-00023

00029

00007

00057

-00037

-00026

-00037

-00059

-00359

00303

00035

-00056

-00048

-00003

00275

00098















and 19 respectively







N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

mz = 318

RI= 14

H+

[M+H]+

mz = 362

RI = 100

N

O

N

NH3C

O

O

OH

F

CH3

H+

- H2 O

mz = 344RI = 5

- C2 H

4 N

N

O

O

O

OH

F

CH3

H+

N

CH3

mz= 320RI = 31

H+








atoms of the ring



908 kJmol-1



kJmol-1



CHAPTER (5)

CONCLUSIONS


[M]+bull



for Levofloxacin







spectra indicated













REFERNCES














New York NY (1969)



















pp142(1998)







Soc3(2006)


















Chemistry (2004)















24714(2003)













(1999)


867105(2008)






241359(2005)






153 37(1996)





1216 794(2009)



250 370(2006)





Chem46 363( 2005)


B 530186(1990)


759(2005)





(1993)




هقدهت هي



للحصىل على


2213





زشق السبع









جبهعخ ثب

كليخ العلم










[M-C2H4N]+ and [M-

CO2-C2H4N]+









[MH-CO2]+bull


+
















هي قجر













Figure 16

Figure 17

Scheme 1

Scheme 2

Scheme 3

Scheme 4

Scheme 5

Scheme 6

Scheme 7

Scheme 8



Schemes



technique



technique



technique



76

85

33

42

52

56

67

71

81

84

List of Tables

Table

Name

Page

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

Table 10

Table 11






























20

28

30

34

35

39

44

48

50

53

62

Table 12

Table 13

Table 14

Table 15

Table 16














64

68

77

79

82

CHAPTER (1)


11 Introduction











technique(1)







structure(2)












The


















The


are widely











phase(18)



compounds show that




























and HYin(24)










12 Aim of the Work






15 as well as 70 eV


technique






techniques






(ΔHf (M)+bull

)




investigation

CHAPTER (2)



Ionization






is formed


e-

[M] [M] +bull

+ 2 e-



can dissociate to




ion [F] +

[M]+bull

[F]+ + [N]


Also [M]+bull


and neutral


[M]+bull

[F]+bull





may


Io

ni

za

ti

on

E

ne

rg

y

(27)

Th

e

ion

izat

ion

ene

rgy

(IE

)

so

met

ime

s

call

ed

(les

s

cor

rect

ly)

the

ion

izat















principle(28-29)








showed


law of the form

σ (E) = C (E-Eo)n-1

(4)









which is formed

by the reaction

M+e- M

+bull + 2e

- (5)


IE[M]+bull

= ∆Hf[M]+bull

- ∆Hf[M] (6)

Where ∆Hf[M]+bull





[M]+bull

[F]+

+ [N]bull (7)



AE[F]+ = IE [F] +D[F-N] + Eexc (8)





(∆Eth) = ∆Hf[F]+ + ∆Hf[N] - ∆Hf[M] (9)





∆Hf[F]+ = IE[F] +∆Hf[F] (11)


Stevenson(32)



work of Audier(33)






molecular ion


spectra










is defined by



[A ndash B] +bull

A+ + B

bull (12)

odd even odd

[A ndash B] +bull

Abull + B

+ (13)

odd odd even

The fragment ion A+

or B+









Ionization






















CH4+ e- CH4

+bull CH3

+CH2

+ CH

++ 2e (14)

CH4+bull

+ CH4 CH5+ + CH3

bull (15)

CH3+ + CH4 C2H5

+ + H2 (16)


+




210 Proton Affinity





[BH]+ + M B+[M+H]

+ (17)




M + CH5+

[M+H]+ + CH4 (18)

M + H+ MH

+ (19)


+] = - PA

PA = - ∆Hordm































segments













CHAPTER (3)







software

31 Apparatus




positive ion mode










32 Materials






reagent gas




eV











CHAPTER (4)


41 Results











techniques














in


















literature

42 Discussion













Molecule

R1

R2

Norfloxacin

Pefloxacin

Ciprofloxacin

Levofloxacin

ethyl

ethyl

cyclopropyl


piperazinyl

4-methyl-piprazinyl

piperazinyl

4-methyl-piprazinyl









compounds




NN

N

F

CH3

O O

OH

PEFLOXACIN

H3C

NN

HN

F

O O

OH

CIPROFLOXACIN

NN

N

F

O O

OH

LEVOFLOXACIN

O

CH3H3C





compounds











chapter 2)







mz 320









15 e V

70 e V

mz

11

60

7

52

14

100

5

9

68

2

4

7

8

7

2

2

2

2

-

-

-

-

-

-

-

-

-

8

12

70

9

59

16

100

9

13

88

5

9

4

11

13

6

6

6

6

7

6

6

7

6

6

8

7

14

15

320

319 [M]+middot

278

277 [M-C2H4N]+

276

275 [M-CO2]+

245

234

233[M-CO2-C2H4N]+

219

218

217

204

203

190

189

176

175

161

95

85

83

81

73

71

69

57

56







The

removal

of an

electron

from an

organic

molecule

often

leads to

change in

its

relative










) (using




423

Fragm

entatio

n of

Norflo

xacin

using

EI

techniq

ue

Most

previous


(214850-51) where


However the present









respectively


[M-CO2]+bull



Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C9

O10

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0309

0199

-0264

0338

-0119

-0015

0102

0082

-0050

0096

0160

13002

0417

-0295

-0367

-0298

-0169

-0395

0127

0095

-0320

0095

0127

-0287

0175

-0202

0314

-0078

0000

0137

0173

-0145

0190

0149

-0004

0399

-0291

-0324

-0230

-0128

-0168

0082

0103

-0339

0105

0078

0022

-0024

0062

-0024

0041

0015

0035

0091

-0095

0094

-0011

-0006

-0018

0004

0043

0068

0041

0227

-0045

0008

-0019

0010

-0049







fragment (odd-




CO2]+bull



bull radical








+ ion through


(Scheme 1)




C3H7N (Scheme 1)


for



and ∆Hf(M)


) (Table





and



N

O O

O HF

NN

M

= 319

- CO2

N

O

F

NN

= 275

C2 H

4 N

= 277

N

O O

O HF

RI = 70 RI = 100

RI = 59

H

N

O

HF

RI = 88

C2H

4N

- CO2

= 233

NN

+ +

- C3 H

7 N

N

O

HF

N

mz mz

mz

mz = 218

RI = 9

mz

HH rearrangement

rearrangement

+

si m

pl e

cl e

av

ag

e



Table

5

Calcul

ated

∆Hf(M

)∆Hf(

M)+bull

an

d IE

values

for the

four

6-

fluoro

quinol

one

molec

ules

using

MND

O method

Neutral molecule




∆ L

N1-C2 14007

C2-C3 13700

C3-C4 14881

C4-C4a 15012

C4a-C5 14185

C5-C6 14294

C6-C7 14433

C7-C8 14203

C8-C8a 14304

C8a-N1 14204

N1-C20 14830

C20-C21 15379

C3-C9 14950

C9-O10 13571

C9-O11 12304

C4-O12 12275

C6-F13 13223

C7-N14 14306

N14-C15 14706

C15-C16 15517

C16-N17 14676

N17-C18 14677

C18-C19 15514 C19-N14 14706

N1-C2 14167

C2-C3 13650

C3-C4 14863

C4-C4a 15080

C4a-C5 14118

C5-C6 14299

C6-C7 14807

C7-C8 14391

C8-C8a 14142

C8a-N1 13980

N1-C20 14934

C20-C21 15374

C3-C9 15028

C9-O10 13527

C9-O11 12268

C4-O12 12237

C6-F13 13126

C7-N14 13740

N14-C15 14962

C15-C16 15615

C16-N17 14567

N17-C18 14571

C18-C19 15558 C19-N14 14935

00160

-00050

-00018

00068

-00067

00005

00374

00188

-00162

-00224

00104

-00005

00078

-00044

-00036

-00038

-00097

-00566

00256

00098

-00109

-00106

00044

00229

IE

eV k J mol-1

∆Hf(M)+bull

k J mol-1

∆Hf(M)

k J mol-1

Molecule




) and



CO2]+bull









81 782 305 -485

Norfloxacin

8 772 314 -464

Pefloxacin

88 849 485 -368

Ciprofloxacin

83 801 142 -631

Levofloxacin




-1) The


-1)


kJmol-1


ion

by 106 kJmol-1























mz RI[] mz RI[]

mz RI[] mz RI[]

97 17 163 8 218 15 236 32 237 6 250 6 252 5 258 7 264 9 270 8 272 5 274 6 275 9 276 60 277 23 278 55 279 13 290 10 292 9 302 8 304 20 306 12 316 5 318 10 320[M+H]

+ 100 321 18 334[M+CH3]

+ 14 348[M+C2H5]

+ 20

289 6 290 31 291 9 292 12 316 10 317 5 318 27 319 6 332 6 333 6 334[M+H]

+ 100 335 19 346 6 348[M+CH3]

+ 5 362[M+C2H5]

+ 21

276 10 287 8 288 52 289 14 290 17 302 5 304 5 314 6 316 18 317 9 318 38 319 9 320 14 330 5 332[M+H]

+ 100 333 18 334 6 346[M+CH3]

+ 17 360[M+C2H5]

+ 23 361 6

130 7 318 14 319 9 320 31 321 7 344 5 346 6 348 7 360 9 361 9 362[M+H]

+ 100 363 20 376[M+CH3]

+ 5 390[M+C2H5]

+ 19















(59)





authors( 214860)



technique




in scheme 2




+

ion



+ and






N

O O

O HF

NHN

[M+H]+ = 320

- CO2

N

O

F

NHN

mz = 276

mz = 278

N

O O

O HF

RI = 100 RI = 60

RI = 55

H

C2 H

4 N

N

H+ H+

H+

N

O O

F

NHN

H+

- H2 O

mz = 302RI = 8

rearrangment
























kJmol-1






species



method

431

Mass

spectr

a of

Peflox

acin

under

EI technique

PA (M) kJmol

-1

∆Hf(M+H)+

kJmol-1

Protonated Site

∆Hf(M) kcalmol

-1

Molecule

904

749

142

297

O12H

N1H

-116

Norfloxacin

916

753

151

314

O12H

N1H

-111

Pefloxacin

904

745

255

418

O12H

N1H

-88

Ciprofloxacin

908

715

2

192

O12H

N1H

-149

Levofloxacin












Table 8




15 eV

70 eV

mz

10

55

3

21

100

4

6

16

10

10

6

10

30

26

7

4

12

61

3

18

100

4

6

14

11

7

4

6

20

15

6

4

334

333 [M]+middot

291

290

289 [M-CO2]+

245

219

218 [M-CO2-C4H9N]+

203 [M-CO2-C4H9N-CH3]+

96

81

79

71 [C4H9N]+bull

70

57

56







800 eV (772 kJ mole-1





Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

-0307

0198

-0262

-0297

0178

-0206

0010

-0020

0056

C4

C4a

C5

C6

C7

C8

C8a

C21

C22

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

0337

-0119

-0016

0103

0081

-0050

0095

0162

-0002

04135

-0301

-0357

-0300

-0169

-0391

0128

0143

-0428

0144

0128

0193

0318

-0082

0000

0124

0218

-0171

0190

0151

-0003

0401

-0293

-0328

-0228

-0124

-0164

0114

0124

-0418

0126

0114

0183

-0019

0037

0016

0021

0137

-0121

0095

-0011

-0001

-0014

0008

0029

0072

0045

0227

-0014

-0019

0010

-0018

-0014

-0010







ion by the







ion at mz 218 with


CO2- C4H9N]+bull





[C4H9N]+bull



On the other



at mz=71 RI=20 in

compariso

n with

Norfloxaci

n the

absence of

ndashCH3

group lead

to produce

the

fragment

[M-

C2H4N]+

ion at mz

= 277

RI=59

Scheme 3 Main

fragmentat

ion

pathways

of

Pefloxacin

at 70 eV

N

O O

O HF

NN

M

=333

- CO2

N

O

F

NN

mz =289

C4 H

9 N

RI = 61 RI = 100

H

N

O

HF

NH2C

RI = 14

mz = 218

H3C

N

O

H

CH2

F

NH2C

mz =203RI = 11

+ +

+

+


mz

- CH

3

H2C

N

CH2

CH2H3C

N

H2CCH2

CH2

H2C

H

r ea r

ang

men

t

C4H9N +

N

O

F

NH2C

O

O H



The

appearance

energy (AE)

of the

fragment

[M-CO2]+bull

ion at

mz=289 is

calculated

(using the

heats of

formation of

∆Hf(M)

molecule

∆Hf (CO2)

and ∆Hf [M-

CO2]+bull

)and

is found to

be equal to

830 eV(801

kJmol-1

)

The

difference

between the

value for

AE [M-CO2]+bull












-1)

Neutral molecule


Molecular ion


∆ L

N1-C2 14016

C2-C3 13689

C3-C4 14885

C4-C4a 15009

C4a-C5 14182

C5-C6 14295

C6-C7 14435

C7-C8 14208

C8-C8a 14299

C8a-N1 14220

N1-C21 14819

C21-C22 15379

C3-C9 14953

C9-O10 13581

C9-O11 12293

C4-O12 12274

C6-F13 13223

C7-N14 14312

N14-C15 14704

C15-C16 15521

C16-N17 14676

N17-C19 14677

C19-C20 15526

C20-N14 14699

N17-C18 14640

N1-C2 14180

C2-C3 13665

C3-C4 14877

C4-C4a 15072

C4a-C5 14101

C5-C6 14324

C6-C7 14928

C7-C8 14547

C8-C8a 14088

C8a-N1 13994

N1-C21 14922

C21-C22 15372

C3-C9 15008

C9-O10 13534

C9-O11 12273

C4-O12 12226

C6-F13 13114

C7-N14 13624

N14-C15 15031

C15-C16 15508

C16-N17 14609

N17-C19 14600

C19-C20 15504

C20-N14 15020

N17-C18 14739

00164

-00024

-00008

00063

-00081

00029

00493

00339

-00211

-00226

00103

-00007

00055

-00047

-00020

-00048

-00109

-00688

00327

-00013

-00067

-00077

-00022

00321

00099


kJmol-1


to 68 kJmol-1







100)







+


+



molecule



[M+C2H5- CO2]+bull

ion

N

O O

O HF

NN

=334

- CO2

N

O

F

NN

mz =290

RI = 100 RI = 31

HH+

[M+H]+

N

O

CF

NN

H+

O

mz = 316

RI = 10

- H2 O

- C2 H

4 N

N

O O

O HF

H+

N

mz = 292

RI = 12

H+

H3C

mz















kJmol-1



-







It is









15 eV

70 eV

mz

11

62

11

67

18

100

11

68

5

7

9

4

4

5

6

6

8

19

14

74

13

71

19

100

11

69

5

8

9

4

5

5

5

6

9

20

332

331 [M]+

290

289 [M-C2H4N]+

288

287 [M-CO2]+

246

245 [M-CO2-C2H4N]+

231

230

229

218

215

204

202

201

57

56










eV(849 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

(e)

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C22

O10

C9

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0277 0206

-0266 0339

-0117 -0021 0133 0076

-0075 0100 0035

-0053 -0057 -0295 0418

-0370 -0295 -0159 -0387 0128 0098

-0312 0096 0127

-0125 0233

-0179 0206

-0085 -0029 0147 0157

-0059 0116

-0042 -0026 -0034 -0285 0380

-0297 0064

-0137 -0419 0133 0099

-0324 0100 0138

0152 0027 0087

-0133 0032

-0008 0014 0081 0016 0016

-0077 0027 0023 0010

-0038 0073 0359 0022

-0032 0005 0001

-0012 0004 0011
















at mz 287 with






ion indicates





















N

O O

O HF

NN

M

= 331

- CO2

N

O

F

NN

= 287

C2 H

4 N

N

O O

O HF

N

RI = 74

RI = 100

RI = 71

H

N

O

HF

RI = 69

C2 H

4 N

- CO2

+ +

H H

H rearengment

N

H rearengm

ent

mz 56RI = 20

mz

mz

mz = 245

mz = 289

H2C

NCH2

CH2




Neutral molecule


Molecular ion


∆ L




CO2)+bull








(050 eV)This














N1-C2 14017

C2-C3 1371

C3-C4 14908

C4-C4a 15019

C4a-C5 14169

C5-C6 1431

C6-C7 14441

C7-C8 14194

C8-C8a 14281

N1-C20 14534

C20-C21 15421

C21-C22 15186

C22-C20 15420

C3-C9 14939

C9-O10 13571

C9-O11 12308

C4-O12 12269

C6-F13 13203

C7-N14 14310

N14-C15 14700

C15-C16 15530

C16-N17 14670

N17-C18 14661

C18-C19 15528

C19-N14 14701

N1-C2 13703

C2-C3 14123

C3-C4 14229

C4-C4a 14585

C4a-C5 14303

C5-C6 14214

C6-C7 14567

C7-C8 14189

C8-C8a 14311

N1-C20 14762

C20-C21 15436

C21-C22 15157

C22-C20 15449

C3-C9 15069

C9-O10 13502

C9-O11 12250

C4-O12 13096

C6-F13 13167

C7-N14 14102

N14-C15 14754

C15-C16 15534

C16-N17 14645

N17-C18 14636

C18-C19 15533

C19-N14 14746

-00314

00413

-00679

-00434

00134

-00096

00126

-00005

00030

00228

00015

-00029

00029

00130

-00069

-00058

00827

-00036

-00208

00054

00004

-00025

-00025

00005

00045















+) cations transfer


+ molecules with



N

O O

O HF

NN

- CO2

N

O

F

NN

N

O O

O HF

N

H

C2 H

4 N

H H

H+

[M+H]+ = 332

RI = 100

H+

mz = 288RI = 52

H+

mz= 290RI = 17

- H2 O

N

O O

F

NN

H

H+

mz = 314RI = 6

445

The

proton


Ciprofloxacin










745kJmol-1

and 904 kJmol-1



kJmol-1


















15 e V

70 e V

mz

16

100

14

5

5

5

9

19

8

7

34

-

17

100

17

5

7

6

12

22

11

10

29

4

362

361[M]+bull

317[M-CO2]+bull

276

273

254

247


232

231

71(C4H9N)+bull

56










eV(801 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

O21

-0299

0201

-0261

0338

-0099

-0028

0112

0092

0079

0051

-0227

-0292

0181

-0209

0322

-0062

-0005

014

0081

0104

0057

-0252

0007

-002

0052

-0016

0037

0023

0028

-0011

0025

0006

-0025

C22

C24

C23

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

015

0091

0016

0416

-0295

-0366

-0297

-0167

-0395

0142

0144

-0429

0143

0142

0194

0155

0088

0011

0402

-0291

-0332

-0244

-0141

-0081

01

0133

-0434

0135

0108

0188

0005

-0003

-0005

-0014

0004

0034

0053

0026

0314

-0042

-0011

-0005

-0008

-0034

-0006




















) The difference



) gives the



(020

eV)

Scheme 7 Main



N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

M

= 361mz = 317

C4H9N

N

O

N

O

HF

CH3

mz = 246

RI= 100 RI= 17

RI = 20

++

H-Rearangment

+

mz = 71RI = 29

+

mz

CH2

N

H2C

CH2

CH3

NH2C

H2C

CH2

CH2

H




Neutral molecule


Molecular ion


∆ L

N1-C2 13975

C2-C3 13719

C3-C4 14898

C4-C4a 15017

C4a-C5 14187

C5-C6 14314

C6-C7 14450

C7-C8 14368

C8-C8a 14446

C8a-N1 14153

C8-O21 13588

O21-C22 14028

C22-C24 15634

C24-N1 14823

C24-C23 15475

C3-C9 14961

C9-O10 13569

C9-O11 12301

C4-O12 12276

C6-F13 13223

C7-N14 14236

N14-C15 14675

C15-C16 15526

C16-N17 14676

N17-C19 14678

C19-C20 15524

C19-N14 14680

N17-C18 14632

N1-C2 14088

C2-C3 13706

C3-C4 14890

C4-C4a 15094

C4a-C5 14207

C5-C6 14253

C6-C7 14713

C7-C8 14520

C8-C8a 14459

C8a-N1 14031

C8-O21 13472

O21-C22 14140

C22-C24 15611

C24-N1 14852

C24-C23 15482

C3-C9 15018

C9-O10 13532

C9-O11 12275

C4-O12 12239

C6-F13 13164

C7-N14 13877

N14-C15 14978

C15-C16 15561

C16-N17 14620

N17-C19 14630

C19-C20 15521

C19-N14 14955

N17-C18 14730

00113

-00013

-00008

00077

00020

-00061

00263

00152

00013

-00122

-00116

00112

-00023

00029

00007

00057

-00037

-00026

-00037

-00059

-00359

00303

00035

-00056

-00048

-00003

00275

00098















and 19 respectively







N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

mz = 318

RI= 14

H+

[M+H]+

mz = 362

RI = 100

N

O

N

NH3C

O

O

OH

F

CH3

H+

- H2 O

mz = 344RI = 5

- C2 H

4 N

N

O

O

O

OH

F

CH3

H+

N

CH3

mz= 320RI = 31

H+








atoms of the ring



908 kJmol-1



kJmol-1



CHAPTER (5)

CONCLUSIONS


[M]+bull



for Levofloxacin







spectra indicated













REFERNCES














New York NY (1969)



















pp142(1998)







Soc3(2006)


















Chemistry (2004)















24714(2003)













(1999)


867105(2008)






241359(2005)






153 37(1996)





1216 794(2009)



250 370(2006)





Chem46 363( 2005)


B 530186(1990)


759(2005)





(1993)




هقدهت هي



للحصىل على


2213





زشق السبع









جبهعخ ثب

كليخ العلم










[M-C2H4N]+ and [M-

CO2-C2H4N]+









[MH-CO2]+bull


+
















هي قجر













List of Tables

Table

Name

Page

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

Table 10

Table 11






























20

28

30

34

35

39

44

48

50

53

62

Table 12

Table 13

Table 14

Table 15

Table 16














64

68

77

79

82

CHAPTER (1)


11 Introduction











technique(1)







structure(2)












The


















The


are widely











phase(18)



compounds show that




























and HYin(24)










12 Aim of the Work






15 as well as 70 eV


technique






techniques






(ΔHf (M)+bull

)




investigation

CHAPTER (2)



Ionization






is formed


e-

[M] [M] +bull

+ 2 e-



can dissociate to




ion [F] +

[M]+bull

[F]+ + [N]


Also [M]+bull


and neutral


[M]+bull

[F]+bull





may


Io

ni

za

ti

on

E

ne

rg

y

(27)

Th

e

ion

izat

ion

ene

rgy

(IE

)

so

met

ime

s

call

ed

(les

s

cor

rect

ly)

the

ion

izat















principle(28-29)








showed


law of the form

σ (E) = C (E-Eo)n-1

(4)









which is formed

by the reaction

M+e- M

+bull + 2e

- (5)


IE[M]+bull

= ∆Hf[M]+bull

- ∆Hf[M] (6)

Where ∆Hf[M]+bull





[M]+bull

[F]+

+ [N]bull (7)



AE[F]+ = IE [F] +D[F-N] + Eexc (8)





(∆Eth) = ∆Hf[F]+ + ∆Hf[N] - ∆Hf[M] (9)





∆Hf[F]+ = IE[F] +∆Hf[F] (11)


Stevenson(32)



work of Audier(33)






molecular ion


spectra










is defined by



[A ndash B] +bull

A+ + B

bull (12)

odd even odd

[A ndash B] +bull

Abull + B

+ (13)

odd odd even

The fragment ion A+

or B+









Ionization






















CH4+ e- CH4

+bull CH3

+CH2

+ CH

++ 2e (14)

CH4+bull

+ CH4 CH5+ + CH3

bull (15)

CH3+ + CH4 C2H5

+ + H2 (16)


+




210 Proton Affinity





[BH]+ + M B+[M+H]

+ (17)




M + CH5+

[M+H]+ + CH4 (18)

M + H+ MH

+ (19)


+] = - PA

PA = - ∆Hordm































segments













CHAPTER (3)







software

31 Apparatus




positive ion mode










32 Materials






reagent gas




eV











CHAPTER (4)


41 Results











techniques














in


















literature

42 Discussion













Molecule

R1

R2

Norfloxacin

Pefloxacin

Ciprofloxacin

Levofloxacin

ethyl

ethyl

cyclopropyl


piperazinyl

4-methyl-piprazinyl

piperazinyl

4-methyl-piprazinyl









compounds




NN

N

F

CH3

O O

OH

PEFLOXACIN

H3C

NN

HN

F

O O

OH

CIPROFLOXACIN

NN

N

F

O O

OH

LEVOFLOXACIN

O

CH3H3C





compounds











chapter 2)







mz 320









15 e V

70 e V

mz

11

60

7

52

14

100

5

9

68

2

4

7

8

7

2

2

2

2

-

-

-

-

-

-

-

-

-

8

12

70

9

59

16

100

9

13

88

5

9

4

11

13

6

6

6

6

7

6

6

7

6

6

8

7

14

15

320

319 [M]+middot

278

277 [M-C2H4N]+

276

275 [M-CO2]+

245

234

233[M-CO2-C2H4N]+

219

218

217

204

203

190

189

176

175

161

95

85

83

81

73

71

69

57

56







The

removal

of an

electron

from an

organic

molecule

often

leads to

change in

its

relative










) (using




423

Fragm

entatio

n of

Norflo

xacin

using

EI

techniq

ue

Most

previous


(214850-51) where


However the present









respectively


[M-CO2]+bull



Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C9

O10

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0309

0199

-0264

0338

-0119

-0015

0102

0082

-0050

0096

0160

13002

0417

-0295

-0367

-0298

-0169

-0395

0127

0095

-0320

0095

0127

-0287

0175

-0202

0314

-0078

0000

0137

0173

-0145

0190

0149

-0004

0399

-0291

-0324

-0230

-0128

-0168

0082

0103

-0339

0105

0078

0022

-0024

0062

-0024

0041

0015

0035

0091

-0095

0094

-0011

-0006

-0018

0004

0043

0068

0041

0227

-0045

0008

-0019

0010

-0049







fragment (odd-




CO2]+bull



bull radical








+ ion through


(Scheme 1)




C3H7N (Scheme 1)


for



and ∆Hf(M)


) (Table





and



N

O O

O HF

NN

M

= 319

- CO2

N

O

F

NN

= 275

C2 H

4 N

= 277

N

O O

O HF

RI = 70 RI = 100

RI = 59

H

N

O

HF

RI = 88

C2H

4N

- CO2

= 233

NN

+ +

- C3 H

7 N

N

O

HF

N

mz mz

mz

mz = 218

RI = 9

mz

HH rearrangement

rearrangement

+

si m

pl e

cl e

av

ag

e



Table

5

Calcul

ated

∆Hf(M

)∆Hf(

M)+bull

an

d IE

values

for the

four

6-

fluoro

quinol

one

molec

ules

using

MND

O method

Neutral molecule




∆ L

N1-C2 14007

C2-C3 13700

C3-C4 14881

C4-C4a 15012

C4a-C5 14185

C5-C6 14294

C6-C7 14433

C7-C8 14203

C8-C8a 14304

C8a-N1 14204

N1-C20 14830

C20-C21 15379

C3-C9 14950

C9-O10 13571

C9-O11 12304

C4-O12 12275

C6-F13 13223

C7-N14 14306

N14-C15 14706

C15-C16 15517

C16-N17 14676

N17-C18 14677

C18-C19 15514 C19-N14 14706

N1-C2 14167

C2-C3 13650

C3-C4 14863

C4-C4a 15080

C4a-C5 14118

C5-C6 14299

C6-C7 14807

C7-C8 14391

C8-C8a 14142

C8a-N1 13980

N1-C20 14934

C20-C21 15374

C3-C9 15028

C9-O10 13527

C9-O11 12268

C4-O12 12237

C6-F13 13126

C7-N14 13740

N14-C15 14962

C15-C16 15615

C16-N17 14567

N17-C18 14571

C18-C19 15558 C19-N14 14935

00160

-00050

-00018

00068

-00067

00005

00374

00188

-00162

-00224

00104

-00005

00078

-00044

-00036

-00038

-00097

-00566

00256

00098

-00109

-00106

00044

00229

IE

eV k J mol-1

∆Hf(M)+bull

k J mol-1

∆Hf(M)

k J mol-1

Molecule




) and



CO2]+bull









81 782 305 -485

Norfloxacin

8 772 314 -464

Pefloxacin

88 849 485 -368

Ciprofloxacin

83 801 142 -631

Levofloxacin




-1) The


-1)


kJmol-1


ion

by 106 kJmol-1























mz RI[] mz RI[]

mz RI[] mz RI[]

97 17 163 8 218 15 236 32 237 6 250 6 252 5 258 7 264 9 270 8 272 5 274 6 275 9 276 60 277 23 278 55 279 13 290 10 292 9 302 8 304 20 306 12 316 5 318 10 320[M+H]

+ 100 321 18 334[M+CH3]

+ 14 348[M+C2H5]

+ 20

289 6 290 31 291 9 292 12 316 10 317 5 318 27 319 6 332 6 333 6 334[M+H]

+ 100 335 19 346 6 348[M+CH3]

+ 5 362[M+C2H5]

+ 21

276 10 287 8 288 52 289 14 290 17 302 5 304 5 314 6 316 18 317 9 318 38 319 9 320 14 330 5 332[M+H]

+ 100 333 18 334 6 346[M+CH3]

+ 17 360[M+C2H5]

+ 23 361 6

130 7 318 14 319 9 320 31 321 7 344 5 346 6 348 7 360 9 361 9 362[M+H]

+ 100 363 20 376[M+CH3]

+ 5 390[M+C2H5]

+ 19















(59)





authors( 214860)



technique




in scheme 2




+

ion



+ and






N

O O

O HF

NHN

[M+H]+ = 320

- CO2

N

O

F

NHN

mz = 276

mz = 278

N

O O

O HF

RI = 100 RI = 60

RI = 55

H

C2 H

4 N

N

H+ H+

H+

N

O O

F

NHN

H+

- H2 O

mz = 302RI = 8

rearrangment
























kJmol-1






species



method

431

Mass

spectr

a of

Peflox

acin

under

EI technique

PA (M) kJmol

-1

∆Hf(M+H)+

kJmol-1

Protonated Site

∆Hf(M) kcalmol

-1

Molecule

904

749

142

297

O12H

N1H

-116

Norfloxacin

916

753

151

314

O12H

N1H

-111

Pefloxacin

904

745

255

418

O12H

N1H

-88

Ciprofloxacin

908

715

2

192

O12H

N1H

-149

Levofloxacin












Table 8




15 eV

70 eV

mz

10

55

3

21

100

4

6

16

10

10

6

10

30

26

7

4

12

61

3

18

100

4

6

14

11

7

4

6

20

15

6

4

334

333 [M]+middot

291

290

289 [M-CO2]+

245

219

218 [M-CO2-C4H9N]+

203 [M-CO2-C4H9N-CH3]+

96

81

79

71 [C4H9N]+bull

70

57

56







800 eV (772 kJ mole-1





Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

-0307

0198

-0262

-0297

0178

-0206

0010

-0020

0056

C4

C4a

C5

C6

C7

C8

C8a

C21

C22

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

0337

-0119

-0016

0103

0081

-0050

0095

0162

-0002

04135

-0301

-0357

-0300

-0169

-0391

0128

0143

-0428

0144

0128

0193

0318

-0082

0000

0124

0218

-0171

0190

0151

-0003

0401

-0293

-0328

-0228

-0124

-0164

0114

0124

-0418

0126

0114

0183

-0019

0037

0016

0021

0137

-0121

0095

-0011

-0001

-0014

0008

0029

0072

0045

0227

-0014

-0019

0010

-0018

-0014

-0010







ion by the







ion at mz 218 with


CO2- C4H9N]+bull





[C4H9N]+bull



On the other



at mz=71 RI=20 in

compariso

n with

Norfloxaci

n the

absence of

ndashCH3

group lead

to produce

the

fragment

[M-

C2H4N]+

ion at mz

= 277

RI=59

Scheme 3 Main

fragmentat

ion

pathways

of

Pefloxacin

at 70 eV

N

O O

O HF

NN

M

=333

- CO2

N

O

F

NN

mz =289

C4 H

9 N

RI = 61 RI = 100

H

N

O

HF

NH2C

RI = 14

mz = 218

H3C

N

O

H

CH2

F

NH2C

mz =203RI = 11

+ +

+

+


mz

- CH

3

H2C

N

CH2

CH2H3C

N

H2CCH2

CH2

H2C

H

r ea r

ang

men

t

C4H9N +

N

O

F

NH2C

O

O H



The

appearance

energy (AE)

of the

fragment

[M-CO2]+bull

ion at

mz=289 is

calculated

(using the

heats of

formation of

∆Hf(M)

molecule

∆Hf (CO2)

and ∆Hf [M-

CO2]+bull

)and

is found to

be equal to

830 eV(801

kJmol-1

)

The

difference

between the

value for

AE [M-CO2]+bull












-1)

Neutral molecule


Molecular ion


∆ L

N1-C2 14016

C2-C3 13689

C3-C4 14885

C4-C4a 15009

C4a-C5 14182

C5-C6 14295

C6-C7 14435

C7-C8 14208

C8-C8a 14299

C8a-N1 14220

N1-C21 14819

C21-C22 15379

C3-C9 14953

C9-O10 13581

C9-O11 12293

C4-O12 12274

C6-F13 13223

C7-N14 14312

N14-C15 14704

C15-C16 15521

C16-N17 14676

N17-C19 14677

C19-C20 15526

C20-N14 14699

N17-C18 14640

N1-C2 14180

C2-C3 13665

C3-C4 14877

C4-C4a 15072

C4a-C5 14101

C5-C6 14324

C6-C7 14928

C7-C8 14547

C8-C8a 14088

C8a-N1 13994

N1-C21 14922

C21-C22 15372

C3-C9 15008

C9-O10 13534

C9-O11 12273

C4-O12 12226

C6-F13 13114

C7-N14 13624

N14-C15 15031

C15-C16 15508

C16-N17 14609

N17-C19 14600

C19-C20 15504

C20-N14 15020

N17-C18 14739

00164

-00024

-00008

00063

-00081

00029

00493

00339

-00211

-00226

00103

-00007

00055

-00047

-00020

-00048

-00109

-00688

00327

-00013

-00067

-00077

-00022

00321

00099


kJmol-1


to 68 kJmol-1







100)







+


+



molecule



[M+C2H5- CO2]+bull

ion

N

O O

O HF

NN

=334

- CO2

N

O

F

NN

mz =290

RI = 100 RI = 31

HH+

[M+H]+

N

O

CF

NN

H+

O

mz = 316

RI = 10

- H2 O

- C2 H

4 N

N

O O

O HF

H+

N

mz = 292

RI = 12

H+

H3C

mz















kJmol-1



-







It is









15 eV

70 eV

mz

11

62

11

67

18

100

11

68

5

7

9

4

4

5

6

6

8

19

14

74

13

71

19

100

11

69

5

8

9

4

5

5

5

6

9

20

332

331 [M]+

290

289 [M-C2H4N]+

288

287 [M-CO2]+

246

245 [M-CO2-C2H4N]+

231

230

229

218

215

204

202

201

57

56










eV(849 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

(e)

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C22

O10

C9

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0277 0206

-0266 0339

-0117 -0021 0133 0076

-0075 0100 0035

-0053 -0057 -0295 0418

-0370 -0295 -0159 -0387 0128 0098

-0312 0096 0127

-0125 0233

-0179 0206

-0085 -0029 0147 0157

-0059 0116

-0042 -0026 -0034 -0285 0380

-0297 0064

-0137 -0419 0133 0099

-0324 0100 0138

0152 0027 0087

-0133 0032

-0008 0014 0081 0016 0016

-0077 0027 0023 0010

-0038 0073 0359 0022

-0032 0005 0001

-0012 0004 0011
















at mz 287 with






ion indicates





















N

O O

O HF

NN

M

= 331

- CO2

N

O

F

NN

= 287

C2 H

4 N

N

O O

O HF

N

RI = 74

RI = 100

RI = 71

H

N

O

HF

RI = 69

C2 H

4 N

- CO2

+ +

H H

H rearengment

N

H rearengm

ent

mz 56RI = 20

mz

mz

mz = 245

mz = 289

H2C

NCH2

CH2




Neutral molecule


Molecular ion


∆ L




CO2)+bull








(050 eV)This














N1-C2 14017

C2-C3 1371

C3-C4 14908

C4-C4a 15019

C4a-C5 14169

C5-C6 1431

C6-C7 14441

C7-C8 14194

C8-C8a 14281

N1-C20 14534

C20-C21 15421

C21-C22 15186

C22-C20 15420

C3-C9 14939

C9-O10 13571

C9-O11 12308

C4-O12 12269

C6-F13 13203

C7-N14 14310

N14-C15 14700

C15-C16 15530

C16-N17 14670

N17-C18 14661

C18-C19 15528

C19-N14 14701

N1-C2 13703

C2-C3 14123

C3-C4 14229

C4-C4a 14585

C4a-C5 14303

C5-C6 14214

C6-C7 14567

C7-C8 14189

C8-C8a 14311

N1-C20 14762

C20-C21 15436

C21-C22 15157

C22-C20 15449

C3-C9 15069

C9-O10 13502

C9-O11 12250

C4-O12 13096

C6-F13 13167

C7-N14 14102

N14-C15 14754

C15-C16 15534

C16-N17 14645

N17-C18 14636

C18-C19 15533

C19-N14 14746

-00314

00413

-00679

-00434

00134

-00096

00126

-00005

00030

00228

00015

-00029

00029

00130

-00069

-00058

00827

-00036

-00208

00054

00004

-00025

-00025

00005

00045















+) cations transfer


+ molecules with



N

O O

O HF

NN

- CO2

N

O

F

NN

N

O O

O HF

N

H

C2 H

4 N

H H

H+

[M+H]+ = 332

RI = 100

H+

mz = 288RI = 52

H+

mz= 290RI = 17

- H2 O

N

O O

F

NN

H

H+

mz = 314RI = 6

445

The

proton


Ciprofloxacin










745kJmol-1

and 904 kJmol-1



kJmol-1


















15 e V

70 e V

mz

16

100

14

5

5

5

9

19

8

7

34

-

17

100

17

5

7

6

12

22

11

10

29

4

362

361[M]+bull

317[M-CO2]+bull

276

273

254

247


232

231

71(C4H9N)+bull

56










eV(801 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

O21

-0299

0201

-0261

0338

-0099

-0028

0112

0092

0079

0051

-0227

-0292

0181

-0209

0322

-0062

-0005

014

0081

0104

0057

-0252

0007

-002

0052

-0016

0037

0023

0028

-0011

0025

0006

-0025

C22

C24

C23

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

015

0091

0016

0416

-0295

-0366

-0297

-0167

-0395

0142

0144

-0429

0143

0142

0194

0155

0088

0011

0402

-0291

-0332

-0244

-0141

-0081

01

0133

-0434

0135

0108

0188

0005

-0003

-0005

-0014

0004

0034

0053

0026

0314

-0042

-0011

-0005

-0008

-0034

-0006




















) The difference



) gives the



(020

eV)

Scheme 7 Main



N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

M

= 361mz = 317

C4H9N

N

O

N

O

HF

CH3

mz = 246

RI= 100 RI= 17

RI = 20

++

H-Rearangment

+

mz = 71RI = 29

+

mz

CH2

N

H2C

CH2

CH3

NH2C

H2C

CH2

CH2

H




Neutral molecule


Molecular ion


∆ L

N1-C2 13975

C2-C3 13719

C3-C4 14898

C4-C4a 15017

C4a-C5 14187

C5-C6 14314

C6-C7 14450

C7-C8 14368

C8-C8a 14446

C8a-N1 14153

C8-O21 13588

O21-C22 14028

C22-C24 15634

C24-N1 14823

C24-C23 15475

C3-C9 14961

C9-O10 13569

C9-O11 12301

C4-O12 12276

C6-F13 13223

C7-N14 14236

N14-C15 14675

C15-C16 15526

C16-N17 14676

N17-C19 14678

C19-C20 15524

C19-N14 14680

N17-C18 14632

N1-C2 14088

C2-C3 13706

C3-C4 14890

C4-C4a 15094

C4a-C5 14207

C5-C6 14253

C6-C7 14713

C7-C8 14520

C8-C8a 14459

C8a-N1 14031

C8-O21 13472

O21-C22 14140

C22-C24 15611

C24-N1 14852

C24-C23 15482

C3-C9 15018

C9-O10 13532

C9-O11 12275

C4-O12 12239

C6-F13 13164

C7-N14 13877

N14-C15 14978

C15-C16 15561

C16-N17 14620

N17-C19 14630

C19-C20 15521

C19-N14 14955

N17-C18 14730

00113

-00013

-00008

00077

00020

-00061

00263

00152

00013

-00122

-00116

00112

-00023

00029

00007

00057

-00037

-00026

-00037

-00059

-00359

00303

00035

-00056

-00048

-00003

00275

00098















and 19 respectively







N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

mz = 318

RI= 14

H+

[M+H]+

mz = 362

RI = 100

N

O

N

NH3C

O

O

OH

F

CH3

H+

- H2 O

mz = 344RI = 5

- C2 H

4 N

N

O

O

O

OH

F

CH3

H+

N

CH3

mz= 320RI = 31

H+








atoms of the ring



908 kJmol-1



kJmol-1



CHAPTER (5)

CONCLUSIONS


[M]+bull



for Levofloxacin







spectra indicated













REFERNCES














New York NY (1969)



















pp142(1998)







Soc3(2006)


















Chemistry (2004)















24714(2003)













(1999)


867105(2008)






241359(2005)






153 37(1996)





1216 794(2009)



250 370(2006)





Chem46 363( 2005)


B 530186(1990)


759(2005)





(1993)




هقدهت هي



للحصىل على


2213





زشق السبع









جبهعخ ثب

كليخ العلم










[M-C2H4N]+ and [M-

CO2-C2H4N]+









[MH-CO2]+bull


+
















هي قجر













Table 12

Table 13

Table 14

Table 15

Table 16














64

68

77

79

82

CHAPTER (1)


11 Introduction











technique(1)







structure(2)












The


















The


are widely











phase(18)



compounds show that




























and HYin(24)










12 Aim of the Work






15 as well as 70 eV


technique






techniques






(ΔHf (M)+bull

)




investigation

CHAPTER (2)



Ionization






is formed


e-

[M] [M] +bull

+ 2 e-



can dissociate to




ion [F] +

[M]+bull

[F]+ + [N]


Also [M]+bull


and neutral


[M]+bull

[F]+bull





may


Io

ni

za

ti

on

E

ne

rg

y

(27)

Th

e

ion

izat

ion

ene

rgy

(IE

)

so

met

ime

s

call

ed

(les

s

cor

rect

ly)

the

ion

izat















principle(28-29)








showed


law of the form

σ (E) = C (E-Eo)n-1

(4)









which is formed

by the reaction

M+e- M

+bull + 2e

- (5)


IE[M]+bull

= ∆Hf[M]+bull

- ∆Hf[M] (6)

Where ∆Hf[M]+bull





[M]+bull

[F]+

+ [N]bull (7)



AE[F]+ = IE [F] +D[F-N] + Eexc (8)





(∆Eth) = ∆Hf[F]+ + ∆Hf[N] - ∆Hf[M] (9)





∆Hf[F]+ = IE[F] +∆Hf[F] (11)


Stevenson(32)



work of Audier(33)






molecular ion


spectra










is defined by



[A ndash B] +bull

A+ + B

bull (12)

odd even odd

[A ndash B] +bull

Abull + B

+ (13)

odd odd even

The fragment ion A+

or B+









Ionization






















CH4+ e- CH4

+bull CH3

+CH2

+ CH

++ 2e (14)

CH4+bull

+ CH4 CH5+ + CH3

bull (15)

CH3+ + CH4 C2H5

+ + H2 (16)


+




210 Proton Affinity





[BH]+ + M B+[M+H]

+ (17)




M + CH5+

[M+H]+ + CH4 (18)

M + H+ MH

+ (19)


+] = - PA

PA = - ∆Hordm































segments













CHAPTER (3)







software

31 Apparatus




positive ion mode










32 Materials






reagent gas




eV











CHAPTER (4)


41 Results











techniques














in


















literature

42 Discussion













Molecule

R1

R2

Norfloxacin

Pefloxacin

Ciprofloxacin

Levofloxacin

ethyl

ethyl

cyclopropyl


piperazinyl

4-methyl-piprazinyl

piperazinyl

4-methyl-piprazinyl









compounds




NN

N

F

CH3

O O

OH

PEFLOXACIN

H3C

NN

HN

F

O O

OH

CIPROFLOXACIN

NN

N

F

O O

OH

LEVOFLOXACIN

O

CH3H3C





compounds











chapter 2)







mz 320









15 e V

70 e V

mz

11

60

7

52

14

100

5

9

68

2

4

7

8

7

2

2

2

2

-

-

-

-

-

-

-

-

-

8

12

70

9

59

16

100

9

13

88

5

9

4

11

13

6

6

6

6

7

6

6

7

6

6

8

7

14

15

320

319 [M]+middot

278

277 [M-C2H4N]+

276

275 [M-CO2]+

245

234

233[M-CO2-C2H4N]+

219

218

217

204

203

190

189

176

175

161

95

85

83

81

73

71

69

57

56







The

removal

of an

electron

from an

organic

molecule

often

leads to

change in

its

relative










) (using




423

Fragm

entatio

n of

Norflo

xacin

using

EI

techniq

ue

Most

previous


(214850-51) where


However the present









respectively


[M-CO2]+bull



Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C9

O10

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0309

0199

-0264

0338

-0119

-0015

0102

0082

-0050

0096

0160

13002

0417

-0295

-0367

-0298

-0169

-0395

0127

0095

-0320

0095

0127

-0287

0175

-0202

0314

-0078

0000

0137

0173

-0145

0190

0149

-0004

0399

-0291

-0324

-0230

-0128

-0168

0082

0103

-0339

0105

0078

0022

-0024

0062

-0024

0041

0015

0035

0091

-0095

0094

-0011

-0006

-0018

0004

0043

0068

0041

0227

-0045

0008

-0019

0010

-0049







fragment (odd-




CO2]+bull



bull radical








+ ion through


(Scheme 1)




C3H7N (Scheme 1)


for



and ∆Hf(M)


) (Table





and



N

O O

O HF

NN

M

= 319

- CO2

N

O

F

NN

= 275

C2 H

4 N

= 277

N

O O

O HF

RI = 70 RI = 100

RI = 59

H

N

O

HF

RI = 88

C2H

4N

- CO2

= 233

NN

+ +

- C3 H

7 N

N

O

HF

N

mz mz

mz

mz = 218

RI = 9

mz

HH rearrangement

rearrangement

+

si m

pl e

cl e

av

ag

e



Table

5

Calcul

ated

∆Hf(M

)∆Hf(

M)+bull

an

d IE

values

for the

four

6-

fluoro

quinol

one

molec

ules

using

MND

O method

Neutral molecule




∆ L

N1-C2 14007

C2-C3 13700

C3-C4 14881

C4-C4a 15012

C4a-C5 14185

C5-C6 14294

C6-C7 14433

C7-C8 14203

C8-C8a 14304

C8a-N1 14204

N1-C20 14830

C20-C21 15379

C3-C9 14950

C9-O10 13571

C9-O11 12304

C4-O12 12275

C6-F13 13223

C7-N14 14306

N14-C15 14706

C15-C16 15517

C16-N17 14676

N17-C18 14677

C18-C19 15514 C19-N14 14706

N1-C2 14167

C2-C3 13650

C3-C4 14863

C4-C4a 15080

C4a-C5 14118

C5-C6 14299

C6-C7 14807

C7-C8 14391

C8-C8a 14142

C8a-N1 13980

N1-C20 14934

C20-C21 15374

C3-C9 15028

C9-O10 13527

C9-O11 12268

C4-O12 12237

C6-F13 13126

C7-N14 13740

N14-C15 14962

C15-C16 15615

C16-N17 14567

N17-C18 14571

C18-C19 15558 C19-N14 14935

00160

-00050

-00018

00068

-00067

00005

00374

00188

-00162

-00224

00104

-00005

00078

-00044

-00036

-00038

-00097

-00566

00256

00098

-00109

-00106

00044

00229

IE

eV k J mol-1

∆Hf(M)+bull

k J mol-1

∆Hf(M)

k J mol-1

Molecule




) and



CO2]+bull









81 782 305 -485

Norfloxacin

8 772 314 -464

Pefloxacin

88 849 485 -368

Ciprofloxacin

83 801 142 -631

Levofloxacin




-1) The


-1)


kJmol-1


ion

by 106 kJmol-1























mz RI[] mz RI[]

mz RI[] mz RI[]

97 17 163 8 218 15 236 32 237 6 250 6 252 5 258 7 264 9 270 8 272 5 274 6 275 9 276 60 277 23 278 55 279 13 290 10 292 9 302 8 304 20 306 12 316 5 318 10 320[M+H]

+ 100 321 18 334[M+CH3]

+ 14 348[M+C2H5]

+ 20

289 6 290 31 291 9 292 12 316 10 317 5 318 27 319 6 332 6 333 6 334[M+H]

+ 100 335 19 346 6 348[M+CH3]

+ 5 362[M+C2H5]

+ 21

276 10 287 8 288 52 289 14 290 17 302 5 304 5 314 6 316 18 317 9 318 38 319 9 320 14 330 5 332[M+H]

+ 100 333 18 334 6 346[M+CH3]

+ 17 360[M+C2H5]

+ 23 361 6

130 7 318 14 319 9 320 31 321 7 344 5 346 6 348 7 360 9 361 9 362[M+H]

+ 100 363 20 376[M+CH3]

+ 5 390[M+C2H5]

+ 19















(59)





authors( 214860)



technique




in scheme 2




+

ion



+ and






N

O O

O HF

NHN

[M+H]+ = 320

- CO2

N

O

F

NHN

mz = 276

mz = 278

N

O O

O HF

RI = 100 RI = 60

RI = 55

H

C2 H

4 N

N

H+ H+

H+

N

O O

F

NHN

H+

- H2 O

mz = 302RI = 8

rearrangment
























kJmol-1






species



method

431

Mass

spectr

a of

Peflox

acin

under

EI technique

PA (M) kJmol

-1

∆Hf(M+H)+

kJmol-1

Protonated Site

∆Hf(M) kcalmol

-1

Molecule

904

749

142

297

O12H

N1H

-116

Norfloxacin

916

753

151

314

O12H

N1H

-111

Pefloxacin

904

745

255

418

O12H

N1H

-88

Ciprofloxacin

908

715

2

192

O12H

N1H

-149

Levofloxacin












Table 8




15 eV

70 eV

mz

10

55

3

21

100

4

6

16

10

10

6

10

30

26

7

4

12

61

3

18

100

4

6

14

11

7

4

6

20

15

6

4

334

333 [M]+middot

291

290

289 [M-CO2]+

245

219

218 [M-CO2-C4H9N]+

203 [M-CO2-C4H9N-CH3]+

96

81

79

71 [C4H9N]+bull

70

57

56







800 eV (772 kJ mole-1





Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

-0307

0198

-0262

-0297

0178

-0206

0010

-0020

0056

C4

C4a

C5

C6

C7

C8

C8a

C21

C22

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

0337

-0119

-0016

0103

0081

-0050

0095

0162

-0002

04135

-0301

-0357

-0300

-0169

-0391

0128

0143

-0428

0144

0128

0193

0318

-0082

0000

0124

0218

-0171

0190

0151

-0003

0401

-0293

-0328

-0228

-0124

-0164

0114

0124

-0418

0126

0114

0183

-0019

0037

0016

0021

0137

-0121

0095

-0011

-0001

-0014

0008

0029

0072

0045

0227

-0014

-0019

0010

-0018

-0014

-0010







ion by the







ion at mz 218 with


CO2- C4H9N]+bull





[C4H9N]+bull



On the other



at mz=71 RI=20 in

compariso

n with

Norfloxaci

n the

absence of

ndashCH3

group lead

to produce

the

fragment

[M-

C2H4N]+

ion at mz

= 277

RI=59

Scheme 3 Main

fragmentat

ion

pathways

of

Pefloxacin

at 70 eV

N

O O

O HF

NN

M

=333

- CO2

N

O

F

NN

mz =289

C4 H

9 N

RI = 61 RI = 100

H

N

O

HF

NH2C

RI = 14

mz = 218

H3C

N

O

H

CH2

F

NH2C

mz =203RI = 11

+ +

+

+


mz

- CH

3

H2C

N

CH2

CH2H3C

N

H2CCH2

CH2

H2C

H

r ea r

ang

men

t

C4H9N +

N

O

F

NH2C

O

O H



The

appearance

energy (AE)

of the

fragment

[M-CO2]+bull

ion at

mz=289 is

calculated

(using the

heats of

formation of

∆Hf(M)

molecule

∆Hf (CO2)

and ∆Hf [M-

CO2]+bull

)and

is found to

be equal to

830 eV(801

kJmol-1

)

The

difference

between the

value for

AE [M-CO2]+bull












-1)

Neutral molecule


Molecular ion


∆ L

N1-C2 14016

C2-C3 13689

C3-C4 14885

C4-C4a 15009

C4a-C5 14182

C5-C6 14295

C6-C7 14435

C7-C8 14208

C8-C8a 14299

C8a-N1 14220

N1-C21 14819

C21-C22 15379

C3-C9 14953

C9-O10 13581

C9-O11 12293

C4-O12 12274

C6-F13 13223

C7-N14 14312

N14-C15 14704

C15-C16 15521

C16-N17 14676

N17-C19 14677

C19-C20 15526

C20-N14 14699

N17-C18 14640

N1-C2 14180

C2-C3 13665

C3-C4 14877

C4-C4a 15072

C4a-C5 14101

C5-C6 14324

C6-C7 14928

C7-C8 14547

C8-C8a 14088

C8a-N1 13994

N1-C21 14922

C21-C22 15372

C3-C9 15008

C9-O10 13534

C9-O11 12273

C4-O12 12226

C6-F13 13114

C7-N14 13624

N14-C15 15031

C15-C16 15508

C16-N17 14609

N17-C19 14600

C19-C20 15504

C20-N14 15020

N17-C18 14739

00164

-00024

-00008

00063

-00081

00029

00493

00339

-00211

-00226

00103

-00007

00055

-00047

-00020

-00048

-00109

-00688

00327

-00013

-00067

-00077

-00022

00321

00099


kJmol-1


to 68 kJmol-1







100)







+


+



molecule



[M+C2H5- CO2]+bull

ion

N

O O

O HF

NN

=334

- CO2

N

O

F

NN

mz =290

RI = 100 RI = 31

HH+

[M+H]+

N

O

CF

NN

H+

O

mz = 316

RI = 10

- H2 O

- C2 H

4 N

N

O O

O HF

H+

N

mz = 292

RI = 12

H+

H3C

mz















kJmol-1



-







It is









15 eV

70 eV

mz

11

62

11

67

18

100

11

68

5

7

9

4

4

5

6

6

8

19

14

74

13

71

19

100

11

69

5

8

9

4

5

5

5

6

9

20

332

331 [M]+

290

289 [M-C2H4N]+

288

287 [M-CO2]+

246

245 [M-CO2-C2H4N]+

231

230

229

218

215

204

202

201

57

56










eV(849 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

(e)

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C22

O10

C9

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0277 0206

-0266 0339

-0117 -0021 0133 0076

-0075 0100 0035

-0053 -0057 -0295 0418

-0370 -0295 -0159 -0387 0128 0098

-0312 0096 0127

-0125 0233

-0179 0206

-0085 -0029 0147 0157

-0059 0116

-0042 -0026 -0034 -0285 0380

-0297 0064

-0137 -0419 0133 0099

-0324 0100 0138

0152 0027 0087

-0133 0032

-0008 0014 0081 0016 0016

-0077 0027 0023 0010

-0038 0073 0359 0022

-0032 0005 0001

-0012 0004 0011
















at mz 287 with






ion indicates





















N

O O

O HF

NN

M

= 331

- CO2

N

O

F

NN

= 287

C2 H

4 N

N

O O

O HF

N

RI = 74

RI = 100

RI = 71

H

N

O

HF

RI = 69

C2 H

4 N

- CO2

+ +

H H

H rearengment

N

H rearengm

ent

mz 56RI = 20

mz

mz

mz = 245

mz = 289

H2C

NCH2

CH2




Neutral molecule


Molecular ion


∆ L




CO2)+bull








(050 eV)This














N1-C2 14017

C2-C3 1371

C3-C4 14908

C4-C4a 15019

C4a-C5 14169

C5-C6 1431

C6-C7 14441

C7-C8 14194

C8-C8a 14281

N1-C20 14534

C20-C21 15421

C21-C22 15186

C22-C20 15420

C3-C9 14939

C9-O10 13571

C9-O11 12308

C4-O12 12269

C6-F13 13203

C7-N14 14310

N14-C15 14700

C15-C16 15530

C16-N17 14670

N17-C18 14661

C18-C19 15528

C19-N14 14701

N1-C2 13703

C2-C3 14123

C3-C4 14229

C4-C4a 14585

C4a-C5 14303

C5-C6 14214

C6-C7 14567

C7-C8 14189

C8-C8a 14311

N1-C20 14762

C20-C21 15436

C21-C22 15157

C22-C20 15449

C3-C9 15069

C9-O10 13502

C9-O11 12250

C4-O12 13096

C6-F13 13167

C7-N14 14102

N14-C15 14754

C15-C16 15534

C16-N17 14645

N17-C18 14636

C18-C19 15533

C19-N14 14746

-00314

00413

-00679

-00434

00134

-00096

00126

-00005

00030

00228

00015

-00029

00029

00130

-00069

-00058

00827

-00036

-00208

00054

00004

-00025

-00025

00005

00045















+) cations transfer


+ molecules with



N

O O

O HF

NN

- CO2

N

O

F

NN

N

O O

O HF

N

H

C2 H

4 N

H H

H+

[M+H]+ = 332

RI = 100

H+

mz = 288RI = 52

H+

mz= 290RI = 17

- H2 O

N

O O

F

NN

H

H+

mz = 314RI = 6

445

The

proton


Ciprofloxacin










745kJmol-1

and 904 kJmol-1



kJmol-1


















15 e V

70 e V

mz

16

100

14

5

5

5

9

19

8

7

34

-

17

100

17

5

7

6

12

22

11

10

29

4

362

361[M]+bull

317[M-CO2]+bull

276

273

254

247


232

231

71(C4H9N)+bull

56










eV(801 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

O21

-0299

0201

-0261

0338

-0099

-0028

0112

0092

0079

0051

-0227

-0292

0181

-0209

0322

-0062

-0005

014

0081

0104

0057

-0252

0007

-002

0052

-0016

0037

0023

0028

-0011

0025

0006

-0025

C22

C24

C23

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

015

0091

0016

0416

-0295

-0366

-0297

-0167

-0395

0142

0144

-0429

0143

0142

0194

0155

0088

0011

0402

-0291

-0332

-0244

-0141

-0081

01

0133

-0434

0135

0108

0188

0005

-0003

-0005

-0014

0004

0034

0053

0026

0314

-0042

-0011

-0005

-0008

-0034

-0006




















) The difference



) gives the



(020

eV)

Scheme 7 Main



N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

M

= 361mz = 317

C4H9N

N

O

N

O

HF

CH3

mz = 246

RI= 100 RI= 17

RI = 20

++

H-Rearangment

+

mz = 71RI = 29

+

mz

CH2

N

H2C

CH2

CH3

NH2C

H2C

CH2

CH2

H




Neutral molecule


Molecular ion


∆ L

N1-C2 13975

C2-C3 13719

C3-C4 14898

C4-C4a 15017

C4a-C5 14187

C5-C6 14314

C6-C7 14450

C7-C8 14368

C8-C8a 14446

C8a-N1 14153

C8-O21 13588

O21-C22 14028

C22-C24 15634

C24-N1 14823

C24-C23 15475

C3-C9 14961

C9-O10 13569

C9-O11 12301

C4-O12 12276

C6-F13 13223

C7-N14 14236

N14-C15 14675

C15-C16 15526

C16-N17 14676

N17-C19 14678

C19-C20 15524

C19-N14 14680

N17-C18 14632

N1-C2 14088

C2-C3 13706

C3-C4 14890

C4-C4a 15094

C4a-C5 14207

C5-C6 14253

C6-C7 14713

C7-C8 14520

C8-C8a 14459

C8a-N1 14031

C8-O21 13472

O21-C22 14140

C22-C24 15611

C24-N1 14852

C24-C23 15482

C3-C9 15018

C9-O10 13532

C9-O11 12275

C4-O12 12239

C6-F13 13164

C7-N14 13877

N14-C15 14978

C15-C16 15561

C16-N17 14620

N17-C19 14630

C19-C20 15521

C19-N14 14955

N17-C18 14730

00113

-00013

-00008

00077

00020

-00061

00263

00152

00013

-00122

-00116

00112

-00023

00029

00007

00057

-00037

-00026

-00037

-00059

-00359

00303

00035

-00056

-00048

-00003

00275

00098















and 19 respectively







N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

mz = 318

RI= 14

H+

[M+H]+

mz = 362

RI = 100

N

O

N

NH3C

O

O

OH

F

CH3

H+

- H2 O

mz = 344RI = 5

- C2 H

4 N

N

O

O

O

OH

F

CH3

H+

N

CH3

mz= 320RI = 31

H+








atoms of the ring



908 kJmol-1



kJmol-1



CHAPTER (5)

CONCLUSIONS


[M]+bull



for Levofloxacin







spectra indicated













REFERNCES














New York NY (1969)



















pp142(1998)







Soc3(2006)


















Chemistry (2004)















24714(2003)













(1999)


867105(2008)






241359(2005)






153 37(1996)





1216 794(2009)



250 370(2006)





Chem46 363( 2005)


B 530186(1990)


759(2005)





(1993)




هقدهت هي



للحصىل على


2213





زشق السبع









جبهعخ ثب

كليخ العلم










[M-C2H4N]+ and [M-

CO2-C2H4N]+









[MH-CO2]+bull


+
















هي قجر













CHAPTER (1)


11 Introduction











technique(1)







structure(2)












The


















The


are widely











phase(18)



compounds show that




























and HYin(24)










12 Aim of the Work






15 as well as 70 eV


technique






techniques






(ΔHf (M)+bull

)




investigation

CHAPTER (2)



Ionization






is formed


e-

[M] [M] +bull

+ 2 e-



can dissociate to




ion [F] +

[M]+bull

[F]+ + [N]


Also [M]+bull


and neutral


[M]+bull

[F]+bull





may


Io

ni

za

ti

on

E

ne

rg

y

(27)

Th

e

ion

izat

ion

ene

rgy

(IE

)

so

met

ime

s

call

ed

(les

s

cor

rect

ly)

the

ion

izat















principle(28-29)








showed


law of the form

σ (E) = C (E-Eo)n-1

(4)









which is formed

by the reaction

M+e- M

+bull + 2e

- (5)


IE[M]+bull

= ∆Hf[M]+bull

- ∆Hf[M] (6)

Where ∆Hf[M]+bull





[M]+bull

[F]+

+ [N]bull (7)



AE[F]+ = IE [F] +D[F-N] + Eexc (8)





(∆Eth) = ∆Hf[F]+ + ∆Hf[N] - ∆Hf[M] (9)





∆Hf[F]+ = IE[F] +∆Hf[F] (11)


Stevenson(32)



work of Audier(33)






molecular ion


spectra










is defined by



[A ndash B] +bull

A+ + B

bull (12)

odd even odd

[A ndash B] +bull

Abull + B

+ (13)

odd odd even

The fragment ion A+

or B+









Ionization






















CH4+ e- CH4

+bull CH3

+CH2

+ CH

++ 2e (14)

CH4+bull

+ CH4 CH5+ + CH3

bull (15)

CH3+ + CH4 C2H5

+ + H2 (16)


+




210 Proton Affinity





[BH]+ + M B+[M+H]

+ (17)




M + CH5+

[M+H]+ + CH4 (18)

M + H+ MH

+ (19)


+] = - PA

PA = - ∆Hordm































segments













CHAPTER (3)







software

31 Apparatus




positive ion mode










32 Materials






reagent gas




eV











CHAPTER (4)


41 Results











techniques














in


















literature

42 Discussion













Molecule

R1

R2

Norfloxacin

Pefloxacin

Ciprofloxacin

Levofloxacin

ethyl

ethyl

cyclopropyl


piperazinyl

4-methyl-piprazinyl

piperazinyl

4-methyl-piprazinyl









compounds




NN

N

F

CH3

O O

OH

PEFLOXACIN

H3C

NN

HN

F

O O

OH

CIPROFLOXACIN

NN

N

F

O O

OH

LEVOFLOXACIN

O

CH3H3C





compounds











chapter 2)







mz 320









15 e V

70 e V

mz

11

60

7

52

14

100

5

9

68

2

4

7

8

7

2

2

2

2

-

-

-

-

-

-

-

-

-

8

12

70

9

59

16

100

9

13

88

5

9

4

11

13

6

6

6

6

7

6

6

7

6

6

8

7

14

15

320

319 [M]+middot

278

277 [M-C2H4N]+

276

275 [M-CO2]+

245

234

233[M-CO2-C2H4N]+

219

218

217

204

203

190

189

176

175

161

95

85

83

81

73

71

69

57

56







The

removal

of an

electron

from an

organic

molecule

often

leads to

change in

its

relative










) (using




423

Fragm

entatio

n of

Norflo

xacin

using

EI

techniq

ue

Most

previous


(214850-51) where


However the present









respectively


[M-CO2]+bull



Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C9

O10

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0309

0199

-0264

0338

-0119

-0015

0102

0082

-0050

0096

0160

13002

0417

-0295

-0367

-0298

-0169

-0395

0127

0095

-0320

0095

0127

-0287

0175

-0202

0314

-0078

0000

0137

0173

-0145

0190

0149

-0004

0399

-0291

-0324

-0230

-0128

-0168

0082

0103

-0339

0105

0078

0022

-0024

0062

-0024

0041

0015

0035

0091

-0095

0094

-0011

-0006

-0018

0004

0043

0068

0041

0227

-0045

0008

-0019

0010

-0049







fragment (odd-




CO2]+bull



bull radical








+ ion through


(Scheme 1)




C3H7N (Scheme 1)


for



and ∆Hf(M)


) (Table





and



N

O O

O HF

NN

M

= 319

- CO2

N

O

F

NN

= 275

C2 H

4 N

= 277

N

O O

O HF

RI = 70 RI = 100

RI = 59

H

N

O

HF

RI = 88

C2H

4N

- CO2

= 233

NN

+ +

- C3 H

7 N

N

O

HF

N

mz mz

mz

mz = 218

RI = 9

mz

HH rearrangement

rearrangement

+

si m

pl e

cl e

av

ag

e



Table

5

Calcul

ated

∆Hf(M

)∆Hf(

M)+bull

an

d IE

values

for the

four

6-

fluoro

quinol

one

molec

ules

using

MND

O method

Neutral molecule




∆ L

N1-C2 14007

C2-C3 13700

C3-C4 14881

C4-C4a 15012

C4a-C5 14185

C5-C6 14294

C6-C7 14433

C7-C8 14203

C8-C8a 14304

C8a-N1 14204

N1-C20 14830

C20-C21 15379

C3-C9 14950

C9-O10 13571

C9-O11 12304

C4-O12 12275

C6-F13 13223

C7-N14 14306

N14-C15 14706

C15-C16 15517

C16-N17 14676

N17-C18 14677

C18-C19 15514 C19-N14 14706

N1-C2 14167

C2-C3 13650

C3-C4 14863

C4-C4a 15080

C4a-C5 14118

C5-C6 14299

C6-C7 14807

C7-C8 14391

C8-C8a 14142

C8a-N1 13980

N1-C20 14934

C20-C21 15374

C3-C9 15028

C9-O10 13527

C9-O11 12268

C4-O12 12237

C6-F13 13126

C7-N14 13740

N14-C15 14962

C15-C16 15615

C16-N17 14567

N17-C18 14571

C18-C19 15558 C19-N14 14935

00160

-00050

-00018

00068

-00067

00005

00374

00188

-00162

-00224

00104

-00005

00078

-00044

-00036

-00038

-00097

-00566

00256

00098

-00109

-00106

00044

00229

IE

eV k J mol-1

∆Hf(M)+bull

k J mol-1

∆Hf(M)

k J mol-1

Molecule




) and



CO2]+bull









81 782 305 -485

Norfloxacin

8 772 314 -464

Pefloxacin

88 849 485 -368

Ciprofloxacin

83 801 142 -631

Levofloxacin




-1) The


-1)


kJmol-1


ion

by 106 kJmol-1























mz RI[] mz RI[]

mz RI[] mz RI[]

97 17 163 8 218 15 236 32 237 6 250 6 252 5 258 7 264 9 270 8 272 5 274 6 275 9 276 60 277 23 278 55 279 13 290 10 292 9 302 8 304 20 306 12 316 5 318 10 320[M+H]

+ 100 321 18 334[M+CH3]

+ 14 348[M+C2H5]

+ 20

289 6 290 31 291 9 292 12 316 10 317 5 318 27 319 6 332 6 333 6 334[M+H]

+ 100 335 19 346 6 348[M+CH3]

+ 5 362[M+C2H5]

+ 21

276 10 287 8 288 52 289 14 290 17 302 5 304 5 314 6 316 18 317 9 318 38 319 9 320 14 330 5 332[M+H]

+ 100 333 18 334 6 346[M+CH3]

+ 17 360[M+C2H5]

+ 23 361 6

130 7 318 14 319 9 320 31 321 7 344 5 346 6 348 7 360 9 361 9 362[M+H]

+ 100 363 20 376[M+CH3]

+ 5 390[M+C2H5]

+ 19















(59)





authors( 214860)



technique




in scheme 2




+

ion



+ and






N

O O

O HF

NHN

[M+H]+ = 320

- CO2

N

O

F

NHN

mz = 276

mz = 278

N

O O

O HF

RI = 100 RI = 60

RI = 55

H

C2 H

4 N

N

H+ H+

H+

N

O O

F

NHN

H+

- H2 O

mz = 302RI = 8

rearrangment
























kJmol-1






species



method

431

Mass

spectr

a of

Peflox

acin

under

EI technique

PA (M) kJmol

-1

∆Hf(M+H)+

kJmol-1

Protonated Site

∆Hf(M) kcalmol

-1

Molecule

904

749

142

297

O12H

N1H

-116

Norfloxacin

916

753

151

314

O12H

N1H

-111

Pefloxacin

904

745

255

418

O12H

N1H

-88

Ciprofloxacin

908

715

2

192

O12H

N1H

-149

Levofloxacin












Table 8




15 eV

70 eV

mz

10

55

3

21

100

4

6

16

10

10

6

10

30

26

7

4

12

61

3

18

100

4

6

14

11

7

4

6

20

15

6

4

334

333 [M]+middot

291

290

289 [M-CO2]+

245

219

218 [M-CO2-C4H9N]+

203 [M-CO2-C4H9N-CH3]+

96

81

79

71 [C4H9N]+bull

70

57

56







800 eV (772 kJ mole-1





Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

-0307

0198

-0262

-0297

0178

-0206

0010

-0020

0056

C4

C4a

C5

C6

C7

C8

C8a

C21

C22

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

0337

-0119

-0016

0103

0081

-0050

0095

0162

-0002

04135

-0301

-0357

-0300

-0169

-0391

0128

0143

-0428

0144

0128

0193

0318

-0082

0000

0124

0218

-0171

0190

0151

-0003

0401

-0293

-0328

-0228

-0124

-0164

0114

0124

-0418

0126

0114

0183

-0019

0037

0016

0021

0137

-0121

0095

-0011

-0001

-0014

0008

0029

0072

0045

0227

-0014

-0019

0010

-0018

-0014

-0010







ion by the







ion at mz 218 with


CO2- C4H9N]+bull





[C4H9N]+bull



On the other



at mz=71 RI=20 in

compariso

n with

Norfloxaci

n the

absence of

ndashCH3

group lead

to produce

the

fragment

[M-

C2H4N]+

ion at mz

= 277

RI=59

Scheme 3 Main

fragmentat

ion

pathways

of

Pefloxacin

at 70 eV

N

O O

O HF

NN

M

=333

- CO2

N

O

F

NN

mz =289

C4 H

9 N

RI = 61 RI = 100

H

N

O

HF

NH2C

RI = 14

mz = 218

H3C

N

O

H

CH2

F

NH2C

mz =203RI = 11

+ +

+

+


mz

- CH

3

H2C

N

CH2

CH2H3C

N

H2CCH2

CH2

H2C

H

r ea r

ang

men

t

C4H9N +

N

O

F

NH2C

O

O H



The

appearance

energy (AE)

of the

fragment

[M-CO2]+bull

ion at

mz=289 is

calculated

(using the

heats of

formation of

∆Hf(M)

molecule

∆Hf (CO2)

and ∆Hf [M-

CO2]+bull

)and

is found to

be equal to

830 eV(801

kJmol-1

)

The

difference

between the

value for

AE [M-CO2]+bull












-1)

Neutral molecule


Molecular ion


∆ L

N1-C2 14016

C2-C3 13689

C3-C4 14885

C4-C4a 15009

C4a-C5 14182

C5-C6 14295

C6-C7 14435

C7-C8 14208

C8-C8a 14299

C8a-N1 14220

N1-C21 14819

C21-C22 15379

C3-C9 14953

C9-O10 13581

C9-O11 12293

C4-O12 12274

C6-F13 13223

C7-N14 14312

N14-C15 14704

C15-C16 15521

C16-N17 14676

N17-C19 14677

C19-C20 15526

C20-N14 14699

N17-C18 14640

N1-C2 14180

C2-C3 13665

C3-C4 14877

C4-C4a 15072

C4a-C5 14101

C5-C6 14324

C6-C7 14928

C7-C8 14547

C8-C8a 14088

C8a-N1 13994

N1-C21 14922

C21-C22 15372

C3-C9 15008

C9-O10 13534

C9-O11 12273

C4-O12 12226

C6-F13 13114

C7-N14 13624

N14-C15 15031

C15-C16 15508

C16-N17 14609

N17-C19 14600

C19-C20 15504

C20-N14 15020

N17-C18 14739

00164

-00024

-00008

00063

-00081

00029

00493

00339

-00211

-00226

00103

-00007

00055

-00047

-00020

-00048

-00109

-00688

00327

-00013

-00067

-00077

-00022

00321

00099


kJmol-1


to 68 kJmol-1







100)







+


+



molecule



[M+C2H5- CO2]+bull

ion

N

O O

O HF

NN

=334

- CO2

N

O

F

NN

mz =290

RI = 100 RI = 31

HH+

[M+H]+

N

O

CF

NN

H+

O

mz = 316

RI = 10

- H2 O

- C2 H

4 N

N

O O

O HF

H+

N

mz = 292

RI = 12

H+

H3C

mz















kJmol-1



-







It is









15 eV

70 eV

mz

11

62

11

67

18

100

11

68

5

7

9

4

4

5

6

6

8

19

14

74

13

71

19

100

11

69

5

8

9

4

5

5

5

6

9

20

332

331 [M]+

290

289 [M-C2H4N]+

288

287 [M-CO2]+

246

245 [M-CO2-C2H4N]+

231

230

229

218

215

204

202

201

57

56










eV(849 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

(e)

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C22

O10

C9

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0277 0206

-0266 0339

-0117 -0021 0133 0076

-0075 0100 0035

-0053 -0057 -0295 0418

-0370 -0295 -0159 -0387 0128 0098

-0312 0096 0127

-0125 0233

-0179 0206

-0085 -0029 0147 0157

-0059 0116

-0042 -0026 -0034 -0285 0380

-0297 0064

-0137 -0419 0133 0099

-0324 0100 0138

0152 0027 0087

-0133 0032

-0008 0014 0081 0016 0016

-0077 0027 0023 0010

-0038 0073 0359 0022

-0032 0005 0001

-0012 0004 0011
















at mz 287 with






ion indicates





















N

O O

O HF

NN

M

= 331

- CO2

N

O

F

NN

= 287

C2 H

4 N

N

O O

O HF

N

RI = 74

RI = 100

RI = 71

H

N

O

HF

RI = 69

C2 H

4 N

- CO2

+ +

H H

H rearengment

N

H rearengm

ent

mz 56RI = 20

mz

mz

mz = 245

mz = 289

H2C

NCH2

CH2




Neutral molecule


Molecular ion


∆ L




CO2)+bull








(050 eV)This














N1-C2 14017

C2-C3 1371

C3-C4 14908

C4-C4a 15019

C4a-C5 14169

C5-C6 1431

C6-C7 14441

C7-C8 14194

C8-C8a 14281

N1-C20 14534

C20-C21 15421

C21-C22 15186

C22-C20 15420

C3-C9 14939

C9-O10 13571

C9-O11 12308

C4-O12 12269

C6-F13 13203

C7-N14 14310

N14-C15 14700

C15-C16 15530

C16-N17 14670

N17-C18 14661

C18-C19 15528

C19-N14 14701

N1-C2 13703

C2-C3 14123

C3-C4 14229

C4-C4a 14585

C4a-C5 14303

C5-C6 14214

C6-C7 14567

C7-C8 14189

C8-C8a 14311

N1-C20 14762

C20-C21 15436

C21-C22 15157

C22-C20 15449

C3-C9 15069

C9-O10 13502

C9-O11 12250

C4-O12 13096

C6-F13 13167

C7-N14 14102

N14-C15 14754

C15-C16 15534

C16-N17 14645

N17-C18 14636

C18-C19 15533

C19-N14 14746

-00314

00413

-00679

-00434

00134

-00096

00126

-00005

00030

00228

00015

-00029

00029

00130

-00069

-00058

00827

-00036

-00208

00054

00004

-00025

-00025

00005

00045















+) cations transfer


+ molecules with



N

O O

O HF

NN

- CO2

N

O

F

NN

N

O O

O HF

N

H

C2 H

4 N

H H

H+

[M+H]+ = 332

RI = 100

H+

mz = 288RI = 52

H+

mz= 290RI = 17

- H2 O

N

O O

F

NN

H

H+

mz = 314RI = 6

445

The

proton


Ciprofloxacin










745kJmol-1

and 904 kJmol-1



kJmol-1


















15 e V

70 e V

mz

16

100

14

5

5

5

9

19

8

7

34

-

17

100

17

5

7

6

12

22

11

10

29

4

362

361[M]+bull

317[M-CO2]+bull

276

273

254

247


232

231

71(C4H9N)+bull

56










eV(801 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

O21

-0299

0201

-0261

0338

-0099

-0028

0112

0092

0079

0051

-0227

-0292

0181

-0209

0322

-0062

-0005

014

0081

0104

0057

-0252

0007

-002

0052

-0016

0037

0023

0028

-0011

0025

0006

-0025

C22

C24

C23

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

015

0091

0016

0416

-0295

-0366

-0297

-0167

-0395

0142

0144

-0429

0143

0142

0194

0155

0088

0011

0402

-0291

-0332

-0244

-0141

-0081

01

0133

-0434

0135

0108

0188

0005

-0003

-0005

-0014

0004

0034

0053

0026

0314

-0042

-0011

-0005

-0008

-0034

-0006




















) The difference



) gives the



(020

eV)

Scheme 7 Main



N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

M

= 361mz = 317

C4H9N

N

O

N

O

HF

CH3

mz = 246

RI= 100 RI= 17

RI = 20

++

H-Rearangment

+

mz = 71RI = 29

+

mz

CH2

N

H2C

CH2

CH3

NH2C

H2C

CH2

CH2

H




Neutral molecule


Molecular ion


∆ L

N1-C2 13975

C2-C3 13719

C3-C4 14898

C4-C4a 15017

C4a-C5 14187

C5-C6 14314

C6-C7 14450

C7-C8 14368

C8-C8a 14446

C8a-N1 14153

C8-O21 13588

O21-C22 14028

C22-C24 15634

C24-N1 14823

C24-C23 15475

C3-C9 14961

C9-O10 13569

C9-O11 12301

C4-O12 12276

C6-F13 13223

C7-N14 14236

N14-C15 14675

C15-C16 15526

C16-N17 14676

N17-C19 14678

C19-C20 15524

C19-N14 14680

N17-C18 14632

N1-C2 14088

C2-C3 13706

C3-C4 14890

C4-C4a 15094

C4a-C5 14207

C5-C6 14253

C6-C7 14713

C7-C8 14520

C8-C8a 14459

C8a-N1 14031

C8-O21 13472

O21-C22 14140

C22-C24 15611

C24-N1 14852

C24-C23 15482

C3-C9 15018

C9-O10 13532

C9-O11 12275

C4-O12 12239

C6-F13 13164

C7-N14 13877

N14-C15 14978

C15-C16 15561

C16-N17 14620

N17-C19 14630

C19-C20 15521

C19-N14 14955

N17-C18 14730

00113

-00013

-00008

00077

00020

-00061

00263

00152

00013

-00122

-00116

00112

-00023

00029

00007

00057

-00037

-00026

-00037

-00059

-00359

00303

00035

-00056

-00048

-00003

00275

00098















and 19 respectively







N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

mz = 318

RI= 14

H+

[M+H]+

mz = 362

RI = 100

N

O

N

NH3C

O

O

OH

F

CH3

H+

- H2 O

mz = 344RI = 5

- C2 H

4 N

N

O

O

O

OH

F

CH3

H+

N

CH3

mz= 320RI = 31

H+








atoms of the ring



908 kJmol-1



kJmol-1



CHAPTER (5)

CONCLUSIONS


[M]+bull



for Levofloxacin







spectra indicated













REFERNCES














New York NY (1969)



















pp142(1998)







Soc3(2006)


















Chemistry (2004)















24714(2003)













(1999)


867105(2008)






241359(2005)






153 37(1996)





1216 794(2009)



250 370(2006)





Chem46 363( 2005)


B 530186(1990)


759(2005)





(1993)




هقدهت هي



للحصىل على


2213





زشق السبع









جبهعخ ثب

كليخ العلم










[M-C2H4N]+ and [M-

CO2-C2H4N]+









[MH-CO2]+bull


+
















هي قجر






























The


are widely











phase(18)



compounds show that




























and HYin(24)










12 Aim of the Work






15 as well as 70 eV


technique






techniques






(ΔHf (M)+bull

)




investigation

CHAPTER (2)



Ionization






is formed


e-

[M] [M] +bull

+ 2 e-



can dissociate to




ion [F] +

[M]+bull

[F]+ + [N]


Also [M]+bull


and neutral


[M]+bull

[F]+bull





may


Io

ni

za

ti

on

E

ne

rg

y

(27)

Th

e

ion

izat

ion

ene

rgy

(IE

)

so

met

ime

s

call

ed

(les

s

cor

rect

ly)

the

ion

izat















principle(28-29)








showed


law of the form

σ (E) = C (E-Eo)n-1

(4)









which is formed

by the reaction

M+e- M

+bull + 2e

- (5)


IE[M]+bull

= ∆Hf[M]+bull

- ∆Hf[M] (6)

Where ∆Hf[M]+bull





[M]+bull

[F]+

+ [N]bull (7)



AE[F]+ = IE [F] +D[F-N] + Eexc (8)





(∆Eth) = ∆Hf[F]+ + ∆Hf[N] - ∆Hf[M] (9)





∆Hf[F]+ = IE[F] +∆Hf[F] (11)


Stevenson(32)



work of Audier(33)






molecular ion


spectra










is defined by



[A ndash B] +bull

A+ + B

bull (12)

odd even odd

[A ndash B] +bull

Abull + B

+ (13)

odd odd even

The fragment ion A+

or B+









Ionization






















CH4+ e- CH4

+bull CH3

+CH2

+ CH

++ 2e (14)

CH4+bull

+ CH4 CH5+ + CH3

bull (15)

CH3+ + CH4 C2H5

+ + H2 (16)


+




210 Proton Affinity





[BH]+ + M B+[M+H]

+ (17)




M + CH5+

[M+H]+ + CH4 (18)

M + H+ MH

+ (19)


+] = - PA

PA = - ∆Hordm































segments













CHAPTER (3)







software

31 Apparatus




positive ion mode










32 Materials






reagent gas




eV











CHAPTER (4)


41 Results











techniques














in


















literature

42 Discussion













Molecule

R1

R2

Norfloxacin

Pefloxacin

Ciprofloxacin

Levofloxacin

ethyl

ethyl

cyclopropyl


piperazinyl

4-methyl-piprazinyl

piperazinyl

4-methyl-piprazinyl









compounds




NN

N

F

CH3

O O

OH

PEFLOXACIN

H3C

NN

HN

F

O O

OH

CIPROFLOXACIN

NN

N

F

O O

OH

LEVOFLOXACIN

O

CH3H3C





compounds











chapter 2)







mz 320









15 e V

70 e V

mz

11

60

7

52

14

100

5

9

68

2

4

7

8

7

2

2

2

2

-

-

-

-

-

-

-

-

-

8

12

70

9

59

16

100

9

13

88

5

9

4

11

13

6

6

6

6

7

6

6

7

6

6

8

7

14

15

320

319 [M]+middot

278

277 [M-C2H4N]+

276

275 [M-CO2]+

245

234

233[M-CO2-C2H4N]+

219

218

217

204

203

190

189

176

175

161

95

85

83

81

73

71

69

57

56







The

removal

of an

electron

from an

organic

molecule

often

leads to

change in

its

relative










) (using




423

Fragm

entatio

n of

Norflo

xacin

using

EI

techniq

ue

Most

previous


(214850-51) where


However the present









respectively


[M-CO2]+bull



Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C9

O10

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0309

0199

-0264

0338

-0119

-0015

0102

0082

-0050

0096

0160

13002

0417

-0295

-0367

-0298

-0169

-0395

0127

0095

-0320

0095

0127

-0287

0175

-0202

0314

-0078

0000

0137

0173

-0145

0190

0149

-0004

0399

-0291

-0324

-0230

-0128

-0168

0082

0103

-0339

0105

0078

0022

-0024

0062

-0024

0041

0015

0035

0091

-0095

0094

-0011

-0006

-0018

0004

0043

0068

0041

0227

-0045

0008

-0019

0010

-0049







fragment (odd-




CO2]+bull



bull radical








+ ion through


(Scheme 1)




C3H7N (Scheme 1)


for



and ∆Hf(M)


) (Table





and



N

O O

O HF

NN

M

= 319

- CO2

N

O

F

NN

= 275

C2 H

4 N

= 277

N

O O

O HF

RI = 70 RI = 100

RI = 59

H

N

O

HF

RI = 88

C2H

4N

- CO2

= 233

NN

+ +

- C3 H

7 N

N

O

HF

N

mz mz

mz

mz = 218

RI = 9

mz

HH rearrangement

rearrangement

+

si m

pl e

cl e

av

ag

e



Table

5

Calcul

ated

∆Hf(M

)∆Hf(

M)+bull

an

d IE

values

for the

four

6-

fluoro

quinol

one

molec

ules

using

MND

O method

Neutral molecule




∆ L

N1-C2 14007

C2-C3 13700

C3-C4 14881

C4-C4a 15012

C4a-C5 14185

C5-C6 14294

C6-C7 14433

C7-C8 14203

C8-C8a 14304

C8a-N1 14204

N1-C20 14830

C20-C21 15379

C3-C9 14950

C9-O10 13571

C9-O11 12304

C4-O12 12275

C6-F13 13223

C7-N14 14306

N14-C15 14706

C15-C16 15517

C16-N17 14676

N17-C18 14677

C18-C19 15514 C19-N14 14706

N1-C2 14167

C2-C3 13650

C3-C4 14863

C4-C4a 15080

C4a-C5 14118

C5-C6 14299

C6-C7 14807

C7-C8 14391

C8-C8a 14142

C8a-N1 13980

N1-C20 14934

C20-C21 15374

C3-C9 15028

C9-O10 13527

C9-O11 12268

C4-O12 12237

C6-F13 13126

C7-N14 13740

N14-C15 14962

C15-C16 15615

C16-N17 14567

N17-C18 14571

C18-C19 15558 C19-N14 14935

00160

-00050

-00018

00068

-00067

00005

00374

00188

-00162

-00224

00104

-00005

00078

-00044

-00036

-00038

-00097

-00566

00256

00098

-00109

-00106

00044

00229

IE

eV k J mol-1

∆Hf(M)+bull

k J mol-1

∆Hf(M)

k J mol-1

Molecule




) and



CO2]+bull









81 782 305 -485

Norfloxacin

8 772 314 -464

Pefloxacin

88 849 485 -368

Ciprofloxacin

83 801 142 -631

Levofloxacin




-1) The


-1)


kJmol-1


ion

by 106 kJmol-1























mz RI[] mz RI[]

mz RI[] mz RI[]

97 17 163 8 218 15 236 32 237 6 250 6 252 5 258 7 264 9 270 8 272 5 274 6 275 9 276 60 277 23 278 55 279 13 290 10 292 9 302 8 304 20 306 12 316 5 318 10 320[M+H]

+ 100 321 18 334[M+CH3]

+ 14 348[M+C2H5]

+ 20

289 6 290 31 291 9 292 12 316 10 317 5 318 27 319 6 332 6 333 6 334[M+H]

+ 100 335 19 346 6 348[M+CH3]

+ 5 362[M+C2H5]

+ 21

276 10 287 8 288 52 289 14 290 17 302 5 304 5 314 6 316 18 317 9 318 38 319 9 320 14 330 5 332[M+H]

+ 100 333 18 334 6 346[M+CH3]

+ 17 360[M+C2H5]

+ 23 361 6

130 7 318 14 319 9 320 31 321 7 344 5 346 6 348 7 360 9 361 9 362[M+H]

+ 100 363 20 376[M+CH3]

+ 5 390[M+C2H5]

+ 19















(59)





authors( 214860)



technique




in scheme 2




+

ion



+ and






N

O O

O HF

NHN

[M+H]+ = 320

- CO2

N

O

F

NHN

mz = 276

mz = 278

N

O O

O HF

RI = 100 RI = 60

RI = 55

H

C2 H

4 N

N

H+ H+

H+

N

O O

F

NHN

H+

- H2 O

mz = 302RI = 8

rearrangment
























kJmol-1






species



method

431

Mass

spectr

a of

Peflox

acin

under

EI technique

PA (M) kJmol

-1

∆Hf(M+H)+

kJmol-1

Protonated Site

∆Hf(M) kcalmol

-1

Molecule

904

749

142

297

O12H

N1H

-116

Norfloxacin

916

753

151

314

O12H

N1H

-111

Pefloxacin

904

745

255

418

O12H

N1H

-88

Ciprofloxacin

908

715

2

192

O12H

N1H

-149

Levofloxacin












Table 8




15 eV

70 eV

mz

10

55

3

21

100

4

6

16

10

10

6

10

30

26

7

4

12

61

3

18

100

4

6

14

11

7

4

6

20

15

6

4

334

333 [M]+middot

291

290

289 [M-CO2]+

245

219

218 [M-CO2-C4H9N]+

203 [M-CO2-C4H9N-CH3]+

96

81

79

71 [C4H9N]+bull

70

57

56







800 eV (772 kJ mole-1





Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

-0307

0198

-0262

-0297

0178

-0206

0010

-0020

0056

C4

C4a

C5

C6

C7

C8

C8a

C21

C22

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

0337

-0119

-0016

0103

0081

-0050

0095

0162

-0002

04135

-0301

-0357

-0300

-0169

-0391

0128

0143

-0428

0144

0128

0193

0318

-0082

0000

0124

0218

-0171

0190

0151

-0003

0401

-0293

-0328

-0228

-0124

-0164

0114

0124

-0418

0126

0114

0183

-0019

0037

0016

0021

0137

-0121

0095

-0011

-0001

-0014

0008

0029

0072

0045

0227

-0014

-0019

0010

-0018

-0014

-0010







ion by the







ion at mz 218 with


CO2- C4H9N]+bull





[C4H9N]+bull



On the other



at mz=71 RI=20 in

compariso

n with

Norfloxaci

n the

absence of

ndashCH3

group lead

to produce

the

fragment

[M-

C2H4N]+

ion at mz

= 277

RI=59

Scheme 3 Main

fragmentat

ion

pathways

of

Pefloxacin

at 70 eV

N

O O

O HF

NN

M

=333

- CO2

N

O

F

NN

mz =289

C4 H

9 N

RI = 61 RI = 100

H

N

O

HF

NH2C

RI = 14

mz = 218

H3C

N

O

H

CH2

F

NH2C

mz =203RI = 11

+ +

+

+


mz

- CH

3

H2C

N

CH2

CH2H3C

N

H2CCH2

CH2

H2C

H

r ea r

ang

men

t

C4H9N +

N

O

F

NH2C

O

O H



The

appearance

energy (AE)

of the

fragment

[M-CO2]+bull

ion at

mz=289 is

calculated

(using the

heats of

formation of

∆Hf(M)

molecule

∆Hf (CO2)

and ∆Hf [M-

CO2]+bull

)and

is found to

be equal to

830 eV(801

kJmol-1

)

The

difference

between the

value for

AE [M-CO2]+bull












-1)

Neutral molecule


Molecular ion


∆ L

N1-C2 14016

C2-C3 13689

C3-C4 14885

C4-C4a 15009

C4a-C5 14182

C5-C6 14295

C6-C7 14435

C7-C8 14208

C8-C8a 14299

C8a-N1 14220

N1-C21 14819

C21-C22 15379

C3-C9 14953

C9-O10 13581

C9-O11 12293

C4-O12 12274

C6-F13 13223

C7-N14 14312

N14-C15 14704

C15-C16 15521

C16-N17 14676

N17-C19 14677

C19-C20 15526

C20-N14 14699

N17-C18 14640

N1-C2 14180

C2-C3 13665

C3-C4 14877

C4-C4a 15072

C4a-C5 14101

C5-C6 14324

C6-C7 14928

C7-C8 14547

C8-C8a 14088

C8a-N1 13994

N1-C21 14922

C21-C22 15372

C3-C9 15008

C9-O10 13534

C9-O11 12273

C4-O12 12226

C6-F13 13114

C7-N14 13624

N14-C15 15031

C15-C16 15508

C16-N17 14609

N17-C19 14600

C19-C20 15504

C20-N14 15020

N17-C18 14739

00164

-00024

-00008

00063

-00081

00029

00493

00339

-00211

-00226

00103

-00007

00055

-00047

-00020

-00048

-00109

-00688

00327

-00013

-00067

-00077

-00022

00321

00099


kJmol-1


to 68 kJmol-1







100)







+


+



molecule



[M+C2H5- CO2]+bull

ion

N

O O

O HF

NN

=334

- CO2

N

O

F

NN

mz =290

RI = 100 RI = 31

HH+

[M+H]+

N

O

CF

NN

H+

O

mz = 316

RI = 10

- H2 O

- C2 H

4 N

N

O O

O HF

H+

N

mz = 292

RI = 12

H+

H3C

mz















kJmol-1



-







It is









15 eV

70 eV

mz

11

62

11

67

18

100

11

68

5

7

9

4

4

5

6

6

8

19

14

74

13

71

19

100

11

69

5

8

9

4

5

5

5

6

9

20

332

331 [M]+

290

289 [M-C2H4N]+

288

287 [M-CO2]+

246

245 [M-CO2-C2H4N]+

231

230

229

218

215

204

202

201

57

56










eV(849 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

(e)

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C22

O10

C9

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0277 0206

-0266 0339

-0117 -0021 0133 0076

-0075 0100 0035

-0053 -0057 -0295 0418

-0370 -0295 -0159 -0387 0128 0098

-0312 0096 0127

-0125 0233

-0179 0206

-0085 -0029 0147 0157

-0059 0116

-0042 -0026 -0034 -0285 0380

-0297 0064

-0137 -0419 0133 0099

-0324 0100 0138

0152 0027 0087

-0133 0032

-0008 0014 0081 0016 0016

-0077 0027 0023 0010

-0038 0073 0359 0022

-0032 0005 0001

-0012 0004 0011
















at mz 287 with






ion indicates





















N

O O

O HF

NN

M

= 331

- CO2

N

O

F

NN

= 287

C2 H

4 N

N

O O

O HF

N

RI = 74

RI = 100

RI = 71

H

N

O

HF

RI = 69

C2 H

4 N

- CO2

+ +

H H

H rearengment

N

H rearengm

ent

mz 56RI = 20

mz

mz

mz = 245

mz = 289

H2C

NCH2

CH2




Neutral molecule


Molecular ion


∆ L




CO2)+bull








(050 eV)This














N1-C2 14017

C2-C3 1371

C3-C4 14908

C4-C4a 15019

C4a-C5 14169

C5-C6 1431

C6-C7 14441

C7-C8 14194

C8-C8a 14281

N1-C20 14534

C20-C21 15421

C21-C22 15186

C22-C20 15420

C3-C9 14939

C9-O10 13571

C9-O11 12308

C4-O12 12269

C6-F13 13203

C7-N14 14310

N14-C15 14700

C15-C16 15530

C16-N17 14670

N17-C18 14661

C18-C19 15528

C19-N14 14701

N1-C2 13703

C2-C3 14123

C3-C4 14229

C4-C4a 14585

C4a-C5 14303

C5-C6 14214

C6-C7 14567

C7-C8 14189

C8-C8a 14311

N1-C20 14762

C20-C21 15436

C21-C22 15157

C22-C20 15449

C3-C9 15069

C9-O10 13502

C9-O11 12250

C4-O12 13096

C6-F13 13167

C7-N14 14102

N14-C15 14754

C15-C16 15534

C16-N17 14645

N17-C18 14636

C18-C19 15533

C19-N14 14746

-00314

00413

-00679

-00434

00134

-00096

00126

-00005

00030

00228

00015

-00029

00029

00130

-00069

-00058

00827

-00036

-00208

00054

00004

-00025

-00025

00005

00045















+) cations transfer


+ molecules with



N

O O

O HF

NN

- CO2

N

O

F

NN

N

O O

O HF

N

H

C2 H

4 N

H H

H+

[M+H]+ = 332

RI = 100

H+

mz = 288RI = 52

H+

mz= 290RI = 17

- H2 O

N

O O

F

NN

H

H+

mz = 314RI = 6

445

The

proton


Ciprofloxacin










745kJmol-1

and 904 kJmol-1



kJmol-1


















15 e V

70 e V

mz

16

100

14

5

5

5

9

19

8

7

34

-

17

100

17

5

7

6

12

22

11

10

29

4

362

361[M]+bull

317[M-CO2]+bull

276

273

254

247


232

231

71(C4H9N)+bull

56










eV(801 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

O21

-0299

0201

-0261

0338

-0099

-0028

0112

0092

0079

0051

-0227

-0292

0181

-0209

0322

-0062

-0005

014

0081

0104

0057

-0252

0007

-002

0052

-0016

0037

0023

0028

-0011

0025

0006

-0025

C22

C24

C23

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

015

0091

0016

0416

-0295

-0366

-0297

-0167

-0395

0142

0144

-0429

0143

0142

0194

0155

0088

0011

0402

-0291

-0332

-0244

-0141

-0081

01

0133

-0434

0135

0108

0188

0005

-0003

-0005

-0014

0004

0034

0053

0026

0314

-0042

-0011

-0005

-0008

-0034

-0006




















) The difference



) gives the



(020

eV)

Scheme 7 Main



N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

M

= 361mz = 317

C4H9N

N

O

N

O

HF

CH3

mz = 246

RI= 100 RI= 17

RI = 20

++

H-Rearangment

+

mz = 71RI = 29

+

mz

CH2

N

H2C

CH2

CH3

NH2C

H2C

CH2

CH2

H




Neutral molecule


Molecular ion


∆ L

N1-C2 13975

C2-C3 13719

C3-C4 14898

C4-C4a 15017

C4a-C5 14187

C5-C6 14314

C6-C7 14450

C7-C8 14368

C8-C8a 14446

C8a-N1 14153

C8-O21 13588

O21-C22 14028

C22-C24 15634

C24-N1 14823

C24-C23 15475

C3-C9 14961

C9-O10 13569

C9-O11 12301

C4-O12 12276

C6-F13 13223

C7-N14 14236

N14-C15 14675

C15-C16 15526

C16-N17 14676

N17-C19 14678

C19-C20 15524

C19-N14 14680

N17-C18 14632

N1-C2 14088

C2-C3 13706

C3-C4 14890

C4-C4a 15094

C4a-C5 14207

C5-C6 14253

C6-C7 14713

C7-C8 14520

C8-C8a 14459

C8a-N1 14031

C8-O21 13472

O21-C22 14140

C22-C24 15611

C24-N1 14852

C24-C23 15482

C3-C9 15018

C9-O10 13532

C9-O11 12275

C4-O12 12239

C6-F13 13164

C7-N14 13877

N14-C15 14978

C15-C16 15561

C16-N17 14620

N17-C19 14630

C19-C20 15521

C19-N14 14955

N17-C18 14730

00113

-00013

-00008

00077

00020

-00061

00263

00152

00013

-00122

-00116

00112

-00023

00029

00007

00057

-00037

-00026

-00037

-00059

-00359

00303

00035

-00056

-00048

-00003

00275

00098















and 19 respectively







N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

mz = 318

RI= 14

H+

[M+H]+

mz = 362

RI = 100

N

O

N

NH3C

O

O

OH

F

CH3

H+

- H2 O

mz = 344RI = 5

- C2 H

4 N

N

O

O

O

OH

F

CH3

H+

N

CH3

mz= 320RI = 31

H+








atoms of the ring



908 kJmol-1



kJmol-1



CHAPTER (5)

CONCLUSIONS


[M]+bull



for Levofloxacin







spectra indicated













REFERNCES














New York NY (1969)



















pp142(1998)







Soc3(2006)


















Chemistry (2004)















24714(2003)













(1999)


867105(2008)






241359(2005)






153 37(1996)





1216 794(2009)



250 370(2006)





Chem46 363( 2005)


B 530186(1990)


759(2005)





(1993)




هقدهت هي



للحصىل على


2213





زشق السبع









جبهعخ ثب

كليخ العلم










[M-C2H4N]+ and [M-

CO2-C2H4N]+









[MH-CO2]+bull


+
















هي قجر




































and HYin(24)










12 Aim of the Work






15 as well as 70 eV


technique






techniques






(ΔHf (M)+bull

)




investigation

CHAPTER (2)



Ionization






is formed


e-

[M] [M] +bull

+ 2 e-



can dissociate to




ion [F] +

[M]+bull

[F]+ + [N]


Also [M]+bull


and neutral


[M]+bull

[F]+bull





may


Io

ni

za

ti

on

E

ne

rg

y

(27)

Th

e

ion

izat

ion

ene

rgy

(IE

)

so

met

ime

s

call

ed

(les

s

cor

rect

ly)

the

ion

izat















principle(28-29)








showed


law of the form

σ (E) = C (E-Eo)n-1

(4)









which is formed

by the reaction

M+e- M

+bull + 2e

- (5)


IE[M]+bull

= ∆Hf[M]+bull

- ∆Hf[M] (6)

Where ∆Hf[M]+bull





[M]+bull

[F]+

+ [N]bull (7)



AE[F]+ = IE [F] +D[F-N] + Eexc (8)





(∆Eth) = ∆Hf[F]+ + ∆Hf[N] - ∆Hf[M] (9)





∆Hf[F]+ = IE[F] +∆Hf[F] (11)


Stevenson(32)



work of Audier(33)






molecular ion


spectra










is defined by



[A ndash B] +bull

A+ + B

bull (12)

odd even odd

[A ndash B] +bull

Abull + B

+ (13)

odd odd even

The fragment ion A+

or B+









Ionization






















CH4+ e- CH4

+bull CH3

+CH2

+ CH

++ 2e (14)

CH4+bull

+ CH4 CH5+ + CH3

bull (15)

CH3+ + CH4 C2H5

+ + H2 (16)


+




210 Proton Affinity





[BH]+ + M B+[M+H]

+ (17)




M + CH5+

[M+H]+ + CH4 (18)

M + H+ MH

+ (19)


+] = - PA

PA = - ∆Hordm































segments













CHAPTER (3)







software

31 Apparatus




positive ion mode










32 Materials






reagent gas




eV











CHAPTER (4)


41 Results











techniques














in


















literature

42 Discussion













Molecule

R1

R2

Norfloxacin

Pefloxacin

Ciprofloxacin

Levofloxacin

ethyl

ethyl

cyclopropyl


piperazinyl

4-methyl-piprazinyl

piperazinyl

4-methyl-piprazinyl









compounds




NN

N

F

CH3

O O

OH

PEFLOXACIN

H3C

NN

HN

F

O O

OH

CIPROFLOXACIN

NN

N

F

O O

OH

LEVOFLOXACIN

O

CH3H3C





compounds











chapter 2)







mz 320









15 e V

70 e V

mz

11

60

7

52

14

100

5

9

68

2

4

7

8

7

2

2

2

2

-

-

-

-

-

-

-

-

-

8

12

70

9

59

16

100

9

13

88

5

9

4

11

13

6

6

6

6

7

6

6

7

6

6

8

7

14

15

320

319 [M]+middot

278

277 [M-C2H4N]+

276

275 [M-CO2]+

245

234

233[M-CO2-C2H4N]+

219

218

217

204

203

190

189

176

175

161

95

85

83

81

73

71

69

57

56







The

removal

of an

electron

from an

organic

molecule

often

leads to

change in

its

relative










) (using




423

Fragm

entatio

n of

Norflo

xacin

using

EI

techniq

ue

Most

previous


(214850-51) where


However the present









respectively


[M-CO2]+bull



Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C9

O10

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0309

0199

-0264

0338

-0119

-0015

0102

0082

-0050

0096

0160

13002

0417

-0295

-0367

-0298

-0169

-0395

0127

0095

-0320

0095

0127

-0287

0175

-0202

0314

-0078

0000

0137

0173

-0145

0190

0149

-0004

0399

-0291

-0324

-0230

-0128

-0168

0082

0103

-0339

0105

0078

0022

-0024

0062

-0024

0041

0015

0035

0091

-0095

0094

-0011

-0006

-0018

0004

0043

0068

0041

0227

-0045

0008

-0019

0010

-0049







fragment (odd-




CO2]+bull



bull radical








+ ion through


(Scheme 1)




C3H7N (Scheme 1)


for



and ∆Hf(M)


) (Table





and



N

O O

O HF

NN

M

= 319

- CO2

N

O

F

NN

= 275

C2 H

4 N

= 277

N

O O

O HF

RI = 70 RI = 100

RI = 59

H

N

O

HF

RI = 88

C2H

4N

- CO2

= 233

NN

+ +

- C3 H

7 N

N

O

HF

N

mz mz

mz

mz = 218

RI = 9

mz

HH rearrangement

rearrangement

+

si m

pl e

cl e

av

ag

e



Table

5

Calcul

ated

∆Hf(M

)∆Hf(

M)+bull

an

d IE

values

for the

four

6-

fluoro

quinol

one

molec

ules

using

MND

O method

Neutral molecule




∆ L

N1-C2 14007

C2-C3 13700

C3-C4 14881

C4-C4a 15012

C4a-C5 14185

C5-C6 14294

C6-C7 14433

C7-C8 14203

C8-C8a 14304

C8a-N1 14204

N1-C20 14830

C20-C21 15379

C3-C9 14950

C9-O10 13571

C9-O11 12304

C4-O12 12275

C6-F13 13223

C7-N14 14306

N14-C15 14706

C15-C16 15517

C16-N17 14676

N17-C18 14677

C18-C19 15514 C19-N14 14706

N1-C2 14167

C2-C3 13650

C3-C4 14863

C4-C4a 15080

C4a-C5 14118

C5-C6 14299

C6-C7 14807

C7-C8 14391

C8-C8a 14142

C8a-N1 13980

N1-C20 14934

C20-C21 15374

C3-C9 15028

C9-O10 13527

C9-O11 12268

C4-O12 12237

C6-F13 13126

C7-N14 13740

N14-C15 14962

C15-C16 15615

C16-N17 14567

N17-C18 14571

C18-C19 15558 C19-N14 14935

00160

-00050

-00018

00068

-00067

00005

00374

00188

-00162

-00224

00104

-00005

00078

-00044

-00036

-00038

-00097

-00566

00256

00098

-00109

-00106

00044

00229

IE

eV k J mol-1

∆Hf(M)+bull

k J mol-1

∆Hf(M)

k J mol-1

Molecule




) and



CO2]+bull









81 782 305 -485

Norfloxacin

8 772 314 -464

Pefloxacin

88 849 485 -368

Ciprofloxacin

83 801 142 -631

Levofloxacin




-1) The


-1)


kJmol-1


ion

by 106 kJmol-1























mz RI[] mz RI[]

mz RI[] mz RI[]

97 17 163 8 218 15 236 32 237 6 250 6 252 5 258 7 264 9 270 8 272 5 274 6 275 9 276 60 277 23 278 55 279 13 290 10 292 9 302 8 304 20 306 12 316 5 318 10 320[M+H]

+ 100 321 18 334[M+CH3]

+ 14 348[M+C2H5]

+ 20

289 6 290 31 291 9 292 12 316 10 317 5 318 27 319 6 332 6 333 6 334[M+H]

+ 100 335 19 346 6 348[M+CH3]

+ 5 362[M+C2H5]

+ 21

276 10 287 8 288 52 289 14 290 17 302 5 304 5 314 6 316 18 317 9 318 38 319 9 320 14 330 5 332[M+H]

+ 100 333 18 334 6 346[M+CH3]

+ 17 360[M+C2H5]

+ 23 361 6

130 7 318 14 319 9 320 31 321 7 344 5 346 6 348 7 360 9 361 9 362[M+H]

+ 100 363 20 376[M+CH3]

+ 5 390[M+C2H5]

+ 19















(59)





authors( 214860)



technique




in scheme 2




+

ion



+ and






N

O O

O HF

NHN

[M+H]+ = 320

- CO2

N

O

F

NHN

mz = 276

mz = 278

N

O O

O HF

RI = 100 RI = 60

RI = 55

H

C2 H

4 N

N

H+ H+

H+

N

O O

F

NHN

H+

- H2 O

mz = 302RI = 8

rearrangment
























kJmol-1






species



method

431

Mass

spectr

a of

Peflox

acin

under

EI technique

PA (M) kJmol

-1

∆Hf(M+H)+

kJmol-1

Protonated Site

∆Hf(M) kcalmol

-1

Molecule

904

749

142

297

O12H

N1H

-116

Norfloxacin

916

753

151

314

O12H

N1H

-111

Pefloxacin

904

745

255

418

O12H

N1H

-88

Ciprofloxacin

908

715

2

192

O12H

N1H

-149

Levofloxacin












Table 8




15 eV

70 eV

mz

10

55

3

21

100

4

6

16

10

10

6

10

30

26

7

4

12

61

3

18

100

4

6

14

11

7

4

6

20

15

6

4

334

333 [M]+middot

291

290

289 [M-CO2]+

245

219

218 [M-CO2-C4H9N]+

203 [M-CO2-C4H9N-CH3]+

96

81

79

71 [C4H9N]+bull

70

57

56







800 eV (772 kJ mole-1





Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

-0307

0198

-0262

-0297

0178

-0206

0010

-0020

0056

C4

C4a

C5

C6

C7

C8

C8a

C21

C22

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

0337

-0119

-0016

0103

0081

-0050

0095

0162

-0002

04135

-0301

-0357

-0300

-0169

-0391

0128

0143

-0428

0144

0128

0193

0318

-0082

0000

0124

0218

-0171

0190

0151

-0003

0401

-0293

-0328

-0228

-0124

-0164

0114

0124

-0418

0126

0114

0183

-0019

0037

0016

0021

0137

-0121

0095

-0011

-0001

-0014

0008

0029

0072

0045

0227

-0014

-0019

0010

-0018

-0014

-0010







ion by the







ion at mz 218 with


CO2- C4H9N]+bull





[C4H9N]+bull



On the other



at mz=71 RI=20 in

compariso

n with

Norfloxaci

n the

absence of

ndashCH3

group lead

to produce

the

fragment

[M-

C2H4N]+

ion at mz

= 277

RI=59

Scheme 3 Main

fragmentat

ion

pathways

of

Pefloxacin

at 70 eV

N

O O

O HF

NN

M

=333

- CO2

N

O

F

NN

mz =289

C4 H

9 N

RI = 61 RI = 100

H

N

O

HF

NH2C

RI = 14

mz = 218

H3C

N

O

H

CH2

F

NH2C

mz =203RI = 11

+ +

+

+


mz

- CH

3

H2C

N

CH2

CH2H3C

N

H2CCH2

CH2

H2C

H

r ea r

ang

men

t

C4H9N +

N

O

F

NH2C

O

O H



The

appearance

energy (AE)

of the

fragment

[M-CO2]+bull

ion at

mz=289 is

calculated

(using the

heats of

formation of

∆Hf(M)

molecule

∆Hf (CO2)

and ∆Hf [M-

CO2]+bull

)and

is found to

be equal to

830 eV(801

kJmol-1

)

The

difference

between the

value for

AE [M-CO2]+bull












-1)

Neutral molecule


Molecular ion


∆ L

N1-C2 14016

C2-C3 13689

C3-C4 14885

C4-C4a 15009

C4a-C5 14182

C5-C6 14295

C6-C7 14435

C7-C8 14208

C8-C8a 14299

C8a-N1 14220

N1-C21 14819

C21-C22 15379

C3-C9 14953

C9-O10 13581

C9-O11 12293

C4-O12 12274

C6-F13 13223

C7-N14 14312

N14-C15 14704

C15-C16 15521

C16-N17 14676

N17-C19 14677

C19-C20 15526

C20-N14 14699

N17-C18 14640

N1-C2 14180

C2-C3 13665

C3-C4 14877

C4-C4a 15072

C4a-C5 14101

C5-C6 14324

C6-C7 14928

C7-C8 14547

C8-C8a 14088

C8a-N1 13994

N1-C21 14922

C21-C22 15372

C3-C9 15008

C9-O10 13534

C9-O11 12273

C4-O12 12226

C6-F13 13114

C7-N14 13624

N14-C15 15031

C15-C16 15508

C16-N17 14609

N17-C19 14600

C19-C20 15504

C20-N14 15020

N17-C18 14739

00164

-00024

-00008

00063

-00081

00029

00493

00339

-00211

-00226

00103

-00007

00055

-00047

-00020

-00048

-00109

-00688

00327

-00013

-00067

-00077

-00022

00321

00099


kJmol-1


to 68 kJmol-1







100)







+


+



molecule



[M+C2H5- CO2]+bull

ion

N

O O

O HF

NN

=334

- CO2

N

O

F

NN

mz =290

RI = 100 RI = 31

HH+

[M+H]+

N

O

CF

NN

H+

O

mz = 316

RI = 10

- H2 O

- C2 H

4 N

N

O O

O HF

H+

N

mz = 292

RI = 12

H+

H3C

mz















kJmol-1



-







It is









15 eV

70 eV

mz

11

62

11

67

18

100

11

68

5

7

9

4

4

5

6

6

8

19

14

74

13

71

19

100

11

69

5

8

9

4

5

5

5

6

9

20

332

331 [M]+

290

289 [M-C2H4N]+

288

287 [M-CO2]+

246

245 [M-CO2-C2H4N]+

231

230

229

218

215

204

202

201

57

56










eV(849 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

(e)

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C22

O10

C9

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0277 0206

-0266 0339

-0117 -0021 0133 0076

-0075 0100 0035

-0053 -0057 -0295 0418

-0370 -0295 -0159 -0387 0128 0098

-0312 0096 0127

-0125 0233

-0179 0206

-0085 -0029 0147 0157

-0059 0116

-0042 -0026 -0034 -0285 0380

-0297 0064

-0137 -0419 0133 0099

-0324 0100 0138

0152 0027 0087

-0133 0032

-0008 0014 0081 0016 0016

-0077 0027 0023 0010

-0038 0073 0359 0022

-0032 0005 0001

-0012 0004 0011
















at mz 287 with






ion indicates





















N

O O

O HF

NN

M

= 331

- CO2

N

O

F

NN

= 287

C2 H

4 N

N

O O

O HF

N

RI = 74

RI = 100

RI = 71

H

N

O

HF

RI = 69

C2 H

4 N

- CO2

+ +

H H

H rearengment

N

H rearengm

ent

mz 56RI = 20

mz

mz

mz = 245

mz = 289

H2C

NCH2

CH2




Neutral molecule


Molecular ion


∆ L




CO2)+bull








(050 eV)This














N1-C2 14017

C2-C3 1371

C3-C4 14908

C4-C4a 15019

C4a-C5 14169

C5-C6 1431

C6-C7 14441

C7-C8 14194

C8-C8a 14281

N1-C20 14534

C20-C21 15421

C21-C22 15186

C22-C20 15420

C3-C9 14939

C9-O10 13571

C9-O11 12308

C4-O12 12269

C6-F13 13203

C7-N14 14310

N14-C15 14700

C15-C16 15530

C16-N17 14670

N17-C18 14661

C18-C19 15528

C19-N14 14701

N1-C2 13703

C2-C3 14123

C3-C4 14229

C4-C4a 14585

C4a-C5 14303

C5-C6 14214

C6-C7 14567

C7-C8 14189

C8-C8a 14311

N1-C20 14762

C20-C21 15436

C21-C22 15157

C22-C20 15449

C3-C9 15069

C9-O10 13502

C9-O11 12250

C4-O12 13096

C6-F13 13167

C7-N14 14102

N14-C15 14754

C15-C16 15534

C16-N17 14645

N17-C18 14636

C18-C19 15533

C19-N14 14746

-00314

00413

-00679

-00434

00134

-00096

00126

-00005

00030

00228

00015

-00029

00029

00130

-00069

-00058

00827

-00036

-00208

00054

00004

-00025

-00025

00005

00045















+) cations transfer


+ molecules with



N

O O

O HF

NN

- CO2

N

O

F

NN

N

O O

O HF

N

H

C2 H

4 N

H H

H+

[M+H]+ = 332

RI = 100

H+

mz = 288RI = 52

H+

mz= 290RI = 17

- H2 O

N

O O

F

NN

H

H+

mz = 314RI = 6

445

The

proton


Ciprofloxacin










745kJmol-1

and 904 kJmol-1



kJmol-1


















15 e V

70 e V

mz

16

100

14

5

5

5

9

19

8

7

34

-

17

100

17

5

7

6

12

22

11

10

29

4

362

361[M]+bull

317[M-CO2]+bull

276

273

254

247


232

231

71(C4H9N)+bull

56










eV(801 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

O21

-0299

0201

-0261

0338

-0099

-0028

0112

0092

0079

0051

-0227

-0292

0181

-0209

0322

-0062

-0005

014

0081

0104

0057

-0252

0007

-002

0052

-0016

0037

0023

0028

-0011

0025

0006

-0025

C22

C24

C23

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

015

0091

0016

0416

-0295

-0366

-0297

-0167

-0395

0142

0144

-0429

0143

0142

0194

0155

0088

0011

0402

-0291

-0332

-0244

-0141

-0081

01

0133

-0434

0135

0108

0188

0005

-0003

-0005

-0014

0004

0034

0053

0026

0314

-0042

-0011

-0005

-0008

-0034

-0006




















) The difference



) gives the



(020

eV)

Scheme 7 Main



N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

M

= 361mz = 317

C4H9N

N

O

N

O

HF

CH3

mz = 246

RI= 100 RI= 17

RI = 20

++

H-Rearangment

+

mz = 71RI = 29

+

mz

CH2

N

H2C

CH2

CH3

NH2C

H2C

CH2

CH2

H




Neutral molecule


Molecular ion


∆ L

N1-C2 13975

C2-C3 13719

C3-C4 14898

C4-C4a 15017

C4a-C5 14187

C5-C6 14314

C6-C7 14450

C7-C8 14368

C8-C8a 14446

C8a-N1 14153

C8-O21 13588

O21-C22 14028

C22-C24 15634

C24-N1 14823

C24-C23 15475

C3-C9 14961

C9-O10 13569

C9-O11 12301

C4-O12 12276

C6-F13 13223

C7-N14 14236

N14-C15 14675

C15-C16 15526

C16-N17 14676

N17-C19 14678

C19-C20 15524

C19-N14 14680

N17-C18 14632

N1-C2 14088

C2-C3 13706

C3-C4 14890

C4-C4a 15094

C4a-C5 14207

C5-C6 14253

C6-C7 14713

C7-C8 14520

C8-C8a 14459

C8a-N1 14031

C8-O21 13472

O21-C22 14140

C22-C24 15611

C24-N1 14852

C24-C23 15482

C3-C9 15018

C9-O10 13532

C9-O11 12275

C4-O12 12239

C6-F13 13164

C7-N14 13877

N14-C15 14978

C15-C16 15561

C16-N17 14620

N17-C19 14630

C19-C20 15521

C19-N14 14955

N17-C18 14730

00113

-00013

-00008

00077

00020

-00061

00263

00152

00013

-00122

-00116

00112

-00023

00029

00007

00057

-00037

-00026

-00037

-00059

-00359

00303

00035

-00056

-00048

-00003

00275

00098















and 19 respectively







N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

mz = 318

RI= 14

H+

[M+H]+

mz = 362

RI = 100

N

O

N

NH3C

O

O

OH

F

CH3

H+

- H2 O

mz = 344RI = 5

- C2 H

4 N

N

O

O

O

OH

F

CH3

H+

N

CH3

mz= 320RI = 31

H+








atoms of the ring



908 kJmol-1



kJmol-1



CHAPTER (5)

CONCLUSIONS


[M]+bull



for Levofloxacin







spectra indicated













REFERNCES














New York NY (1969)



















pp142(1998)







Soc3(2006)


















Chemistry (2004)















24714(2003)













(1999)


867105(2008)






241359(2005)






153 37(1996)





1216 794(2009)



250 370(2006)





Chem46 363( 2005)


B 530186(1990)


759(2005)





(1993)




هقدهت هي



للحصىل على


2213





زشق السبع









جبهعخ ثب

كليخ العلم










[M-C2H4N]+ and [M-

CO2-C2H4N]+









[MH-CO2]+bull


+
















هي قجر













12 Aim of the Work






15 as well as 70 eV


technique






techniques






(ΔHf (M)+bull

)




investigation

CHAPTER (2)



Ionization






is formed


e-

[M] [M] +bull

+ 2 e-



can dissociate to




ion [F] +

[M]+bull

[F]+ + [N]


Also [M]+bull


and neutral


[M]+bull

[F]+bull





may


Io

ni

za

ti

on

E

ne

rg

y

(27)

Th

e

ion

izat

ion

ene

rgy

(IE

)

so

met

ime

s

call

ed

(les

s

cor

rect

ly)

the

ion

izat















principle(28-29)








showed


law of the form

σ (E) = C (E-Eo)n-1

(4)









which is formed

by the reaction

M+e- M

+bull + 2e

- (5)


IE[M]+bull

= ∆Hf[M]+bull

- ∆Hf[M] (6)

Where ∆Hf[M]+bull





[M]+bull

[F]+

+ [N]bull (7)



AE[F]+ = IE [F] +D[F-N] + Eexc (8)





(∆Eth) = ∆Hf[F]+ + ∆Hf[N] - ∆Hf[M] (9)





∆Hf[F]+ = IE[F] +∆Hf[F] (11)


Stevenson(32)



work of Audier(33)






molecular ion


spectra










is defined by



[A ndash B] +bull

A+ + B

bull (12)

odd even odd

[A ndash B] +bull

Abull + B

+ (13)

odd odd even

The fragment ion A+

or B+









Ionization






















CH4+ e- CH4

+bull CH3

+CH2

+ CH

++ 2e (14)

CH4+bull

+ CH4 CH5+ + CH3

bull (15)

CH3+ + CH4 C2H5

+ + H2 (16)


+




210 Proton Affinity





[BH]+ + M B+[M+H]

+ (17)




M + CH5+

[M+H]+ + CH4 (18)

M + H+ MH

+ (19)


+] = - PA

PA = - ∆Hordm































segments













CHAPTER (3)







software

31 Apparatus




positive ion mode










32 Materials






reagent gas




eV











CHAPTER (4)


41 Results











techniques














in


















literature

42 Discussion













Molecule

R1

R2

Norfloxacin

Pefloxacin

Ciprofloxacin

Levofloxacin

ethyl

ethyl

cyclopropyl


piperazinyl

4-methyl-piprazinyl

piperazinyl

4-methyl-piprazinyl









compounds




NN

N

F

CH3

O O

OH

PEFLOXACIN

H3C

NN

HN

F

O O

OH

CIPROFLOXACIN

NN

N

F

O O

OH

LEVOFLOXACIN

O

CH3H3C





compounds











chapter 2)







mz 320









15 e V

70 e V

mz

11

60

7

52

14

100

5

9

68

2

4

7

8

7

2

2

2

2

-

-

-

-

-

-

-

-

-

8

12

70

9

59

16

100

9

13

88

5

9

4

11

13

6

6

6

6

7

6

6

7

6

6

8

7

14

15

320

319 [M]+middot

278

277 [M-C2H4N]+

276

275 [M-CO2]+

245

234

233[M-CO2-C2H4N]+

219

218

217

204

203

190

189

176

175

161

95

85

83

81

73

71

69

57

56







The

removal

of an

electron

from an

organic

molecule

often

leads to

change in

its

relative










) (using




423

Fragm

entatio

n of

Norflo

xacin

using

EI

techniq

ue

Most

previous


(214850-51) where


However the present









respectively


[M-CO2]+bull



Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C9

O10

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0309

0199

-0264

0338

-0119

-0015

0102

0082

-0050

0096

0160

13002

0417

-0295

-0367

-0298

-0169

-0395

0127

0095

-0320

0095

0127

-0287

0175

-0202

0314

-0078

0000

0137

0173

-0145

0190

0149

-0004

0399

-0291

-0324

-0230

-0128

-0168

0082

0103

-0339

0105

0078

0022

-0024

0062

-0024

0041

0015

0035

0091

-0095

0094

-0011

-0006

-0018

0004

0043

0068

0041

0227

-0045

0008

-0019

0010

-0049







fragment (odd-




CO2]+bull



bull radical








+ ion through


(Scheme 1)




C3H7N (Scheme 1)


for



and ∆Hf(M)


) (Table





and



N

O O

O HF

NN

M

= 319

- CO2

N

O

F

NN

= 275

C2 H

4 N

= 277

N

O O

O HF

RI = 70 RI = 100

RI = 59

H

N

O

HF

RI = 88

C2H

4N

- CO2

= 233

NN

+ +

- C3 H

7 N

N

O

HF

N

mz mz

mz

mz = 218

RI = 9

mz

HH rearrangement

rearrangement

+

si m

pl e

cl e

av

ag

e



Table

5

Calcul

ated

∆Hf(M

)∆Hf(

M)+bull

an

d IE

values

for the

four

6-

fluoro

quinol

one

molec

ules

using

MND

O method

Neutral molecule




∆ L

N1-C2 14007

C2-C3 13700

C3-C4 14881

C4-C4a 15012

C4a-C5 14185

C5-C6 14294

C6-C7 14433

C7-C8 14203

C8-C8a 14304

C8a-N1 14204

N1-C20 14830

C20-C21 15379

C3-C9 14950

C9-O10 13571

C9-O11 12304

C4-O12 12275

C6-F13 13223

C7-N14 14306

N14-C15 14706

C15-C16 15517

C16-N17 14676

N17-C18 14677

C18-C19 15514 C19-N14 14706

N1-C2 14167

C2-C3 13650

C3-C4 14863

C4-C4a 15080

C4a-C5 14118

C5-C6 14299

C6-C7 14807

C7-C8 14391

C8-C8a 14142

C8a-N1 13980

N1-C20 14934

C20-C21 15374

C3-C9 15028

C9-O10 13527

C9-O11 12268

C4-O12 12237

C6-F13 13126

C7-N14 13740

N14-C15 14962

C15-C16 15615

C16-N17 14567

N17-C18 14571

C18-C19 15558 C19-N14 14935

00160

-00050

-00018

00068

-00067

00005

00374

00188

-00162

-00224

00104

-00005

00078

-00044

-00036

-00038

-00097

-00566

00256

00098

-00109

-00106

00044

00229

IE

eV k J mol-1

∆Hf(M)+bull

k J mol-1

∆Hf(M)

k J mol-1

Molecule




) and



CO2]+bull









81 782 305 -485

Norfloxacin

8 772 314 -464

Pefloxacin

88 849 485 -368

Ciprofloxacin

83 801 142 -631

Levofloxacin




-1) The


-1)


kJmol-1


ion

by 106 kJmol-1























mz RI[] mz RI[]

mz RI[] mz RI[]

97 17 163 8 218 15 236 32 237 6 250 6 252 5 258 7 264 9 270 8 272 5 274 6 275 9 276 60 277 23 278 55 279 13 290 10 292 9 302 8 304 20 306 12 316 5 318 10 320[M+H]

+ 100 321 18 334[M+CH3]

+ 14 348[M+C2H5]

+ 20

289 6 290 31 291 9 292 12 316 10 317 5 318 27 319 6 332 6 333 6 334[M+H]

+ 100 335 19 346 6 348[M+CH3]

+ 5 362[M+C2H5]

+ 21

276 10 287 8 288 52 289 14 290 17 302 5 304 5 314 6 316 18 317 9 318 38 319 9 320 14 330 5 332[M+H]

+ 100 333 18 334 6 346[M+CH3]

+ 17 360[M+C2H5]

+ 23 361 6

130 7 318 14 319 9 320 31 321 7 344 5 346 6 348 7 360 9 361 9 362[M+H]

+ 100 363 20 376[M+CH3]

+ 5 390[M+C2H5]

+ 19















(59)





authors( 214860)



technique




in scheme 2




+

ion



+ and






N

O O

O HF

NHN

[M+H]+ = 320

- CO2

N

O

F

NHN

mz = 276

mz = 278

N

O O

O HF

RI = 100 RI = 60

RI = 55

H

C2 H

4 N

N

H+ H+

H+

N

O O

F

NHN

H+

- H2 O

mz = 302RI = 8

rearrangment
























kJmol-1






species



method

431

Mass

spectr

a of

Peflox

acin

under

EI technique

PA (M) kJmol

-1

∆Hf(M+H)+

kJmol-1

Protonated Site

∆Hf(M) kcalmol

-1

Molecule

904

749

142

297

O12H

N1H

-116

Norfloxacin

916

753

151

314

O12H

N1H

-111

Pefloxacin

904

745

255

418

O12H

N1H

-88

Ciprofloxacin

908

715

2

192

O12H

N1H

-149

Levofloxacin












Table 8




15 eV

70 eV

mz

10

55

3

21

100

4

6

16

10

10

6

10

30

26

7

4

12

61

3

18

100

4

6

14

11

7

4

6

20

15

6

4

334

333 [M]+middot

291

290

289 [M-CO2]+

245

219

218 [M-CO2-C4H9N]+

203 [M-CO2-C4H9N-CH3]+

96

81

79

71 [C4H9N]+bull

70

57

56







800 eV (772 kJ mole-1





Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

-0307

0198

-0262

-0297

0178

-0206

0010

-0020

0056

C4

C4a

C5

C6

C7

C8

C8a

C21

C22

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

0337

-0119

-0016

0103

0081

-0050

0095

0162

-0002

04135

-0301

-0357

-0300

-0169

-0391

0128

0143

-0428

0144

0128

0193

0318

-0082

0000

0124

0218

-0171

0190

0151

-0003

0401

-0293

-0328

-0228

-0124

-0164

0114

0124

-0418

0126

0114

0183

-0019

0037

0016

0021

0137

-0121

0095

-0011

-0001

-0014

0008

0029

0072

0045

0227

-0014

-0019

0010

-0018

-0014

-0010







ion by the







ion at mz 218 with


CO2- C4H9N]+bull





[C4H9N]+bull



On the other



at mz=71 RI=20 in

compariso

n with

Norfloxaci

n the

absence of

ndashCH3

group lead

to produce

the

fragment

[M-

C2H4N]+

ion at mz

= 277

RI=59

Scheme 3 Main

fragmentat

ion

pathways

of

Pefloxacin

at 70 eV

N

O O

O HF

NN

M

=333

- CO2

N

O

F

NN

mz =289

C4 H

9 N

RI = 61 RI = 100

H

N

O

HF

NH2C

RI = 14

mz = 218

H3C

N

O

H

CH2

F

NH2C

mz =203RI = 11

+ +

+

+


mz

- CH

3

H2C

N

CH2

CH2H3C

N

H2CCH2

CH2

H2C

H

r ea r

ang

men

t

C4H9N +

N

O

F

NH2C

O

O H



The

appearance

energy (AE)

of the

fragment

[M-CO2]+bull

ion at

mz=289 is

calculated

(using the

heats of

formation of

∆Hf(M)

molecule

∆Hf (CO2)

and ∆Hf [M-

CO2]+bull

)and

is found to

be equal to

830 eV(801

kJmol-1

)

The

difference

between the

value for

AE [M-CO2]+bull












-1)

Neutral molecule


Molecular ion


∆ L

N1-C2 14016

C2-C3 13689

C3-C4 14885

C4-C4a 15009

C4a-C5 14182

C5-C6 14295

C6-C7 14435

C7-C8 14208

C8-C8a 14299

C8a-N1 14220

N1-C21 14819

C21-C22 15379

C3-C9 14953

C9-O10 13581

C9-O11 12293

C4-O12 12274

C6-F13 13223

C7-N14 14312

N14-C15 14704

C15-C16 15521

C16-N17 14676

N17-C19 14677

C19-C20 15526

C20-N14 14699

N17-C18 14640

N1-C2 14180

C2-C3 13665

C3-C4 14877

C4-C4a 15072

C4a-C5 14101

C5-C6 14324

C6-C7 14928

C7-C8 14547

C8-C8a 14088

C8a-N1 13994

N1-C21 14922

C21-C22 15372

C3-C9 15008

C9-O10 13534

C9-O11 12273

C4-O12 12226

C6-F13 13114

C7-N14 13624

N14-C15 15031

C15-C16 15508

C16-N17 14609

N17-C19 14600

C19-C20 15504

C20-N14 15020

N17-C18 14739

00164

-00024

-00008

00063

-00081

00029

00493

00339

-00211

-00226

00103

-00007

00055

-00047

-00020

-00048

-00109

-00688

00327

-00013

-00067

-00077

-00022

00321

00099


kJmol-1


to 68 kJmol-1







100)







+


+



molecule



[M+C2H5- CO2]+bull

ion

N

O O

O HF

NN

=334

- CO2

N

O

F

NN

mz =290

RI = 100 RI = 31

HH+

[M+H]+

N

O

CF

NN

H+

O

mz = 316

RI = 10

- H2 O

- C2 H

4 N

N

O O

O HF

H+

N

mz = 292

RI = 12

H+

H3C

mz















kJmol-1



-







It is









15 eV

70 eV

mz

11

62

11

67

18

100

11

68

5

7

9

4

4

5

6

6

8

19

14

74

13

71

19

100

11

69

5

8

9

4

5

5

5

6

9

20

332

331 [M]+

290

289 [M-C2H4N]+

288

287 [M-CO2]+

246

245 [M-CO2-C2H4N]+

231

230

229

218

215

204

202

201

57

56










eV(849 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

(e)

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C22

O10

C9

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0277 0206

-0266 0339

-0117 -0021 0133 0076

-0075 0100 0035

-0053 -0057 -0295 0418

-0370 -0295 -0159 -0387 0128 0098

-0312 0096 0127

-0125 0233

-0179 0206

-0085 -0029 0147 0157

-0059 0116

-0042 -0026 -0034 -0285 0380

-0297 0064

-0137 -0419 0133 0099

-0324 0100 0138

0152 0027 0087

-0133 0032

-0008 0014 0081 0016 0016

-0077 0027 0023 0010

-0038 0073 0359 0022

-0032 0005 0001

-0012 0004 0011
















at mz 287 with






ion indicates





















N

O O

O HF

NN

M

= 331

- CO2

N

O

F

NN

= 287

C2 H

4 N

N

O O

O HF

N

RI = 74

RI = 100

RI = 71

H

N

O

HF

RI = 69

C2 H

4 N

- CO2

+ +

H H

H rearengment

N

H rearengm

ent

mz 56RI = 20

mz

mz

mz = 245

mz = 289

H2C

NCH2

CH2




Neutral molecule


Molecular ion


∆ L




CO2)+bull








(050 eV)This














N1-C2 14017

C2-C3 1371

C3-C4 14908

C4-C4a 15019

C4a-C5 14169

C5-C6 1431

C6-C7 14441

C7-C8 14194

C8-C8a 14281

N1-C20 14534

C20-C21 15421

C21-C22 15186

C22-C20 15420

C3-C9 14939

C9-O10 13571

C9-O11 12308

C4-O12 12269

C6-F13 13203

C7-N14 14310

N14-C15 14700

C15-C16 15530

C16-N17 14670

N17-C18 14661

C18-C19 15528

C19-N14 14701

N1-C2 13703

C2-C3 14123

C3-C4 14229

C4-C4a 14585

C4a-C5 14303

C5-C6 14214

C6-C7 14567

C7-C8 14189

C8-C8a 14311

N1-C20 14762

C20-C21 15436

C21-C22 15157

C22-C20 15449

C3-C9 15069

C9-O10 13502

C9-O11 12250

C4-O12 13096

C6-F13 13167

C7-N14 14102

N14-C15 14754

C15-C16 15534

C16-N17 14645

N17-C18 14636

C18-C19 15533

C19-N14 14746

-00314

00413

-00679

-00434

00134

-00096

00126

-00005

00030

00228

00015

-00029

00029

00130

-00069

-00058

00827

-00036

-00208

00054

00004

-00025

-00025

00005

00045















+) cations transfer


+ molecules with



N

O O

O HF

NN

- CO2

N

O

F

NN

N

O O

O HF

N

H

C2 H

4 N

H H

H+

[M+H]+ = 332

RI = 100

H+

mz = 288RI = 52

H+

mz= 290RI = 17

- H2 O

N

O O

F

NN

H

H+

mz = 314RI = 6

445

The

proton


Ciprofloxacin










745kJmol-1

and 904 kJmol-1



kJmol-1


















15 e V

70 e V

mz

16

100

14

5

5

5

9

19

8

7

34

-

17

100

17

5

7

6

12

22

11

10

29

4

362

361[M]+bull

317[M-CO2]+bull

276

273

254

247


232

231

71(C4H9N)+bull

56










eV(801 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

O21

-0299

0201

-0261

0338

-0099

-0028

0112

0092

0079

0051

-0227

-0292

0181

-0209

0322

-0062

-0005

014

0081

0104

0057

-0252

0007

-002

0052

-0016

0037

0023

0028

-0011

0025

0006

-0025

C22

C24

C23

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

015

0091

0016

0416

-0295

-0366

-0297

-0167

-0395

0142

0144

-0429

0143

0142

0194

0155

0088

0011

0402

-0291

-0332

-0244

-0141

-0081

01

0133

-0434

0135

0108

0188

0005

-0003

-0005

-0014

0004

0034

0053

0026

0314

-0042

-0011

-0005

-0008

-0034

-0006




















) The difference



) gives the



(020

eV)

Scheme 7 Main



N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

M

= 361mz = 317

C4H9N

N

O

N

O

HF

CH3

mz = 246

RI= 100 RI= 17

RI = 20

++

H-Rearangment

+

mz = 71RI = 29

+

mz

CH2

N

H2C

CH2

CH3

NH2C

H2C

CH2

CH2

H




Neutral molecule


Molecular ion


∆ L

N1-C2 13975

C2-C3 13719

C3-C4 14898

C4-C4a 15017

C4a-C5 14187

C5-C6 14314

C6-C7 14450

C7-C8 14368

C8-C8a 14446

C8a-N1 14153

C8-O21 13588

O21-C22 14028

C22-C24 15634

C24-N1 14823

C24-C23 15475

C3-C9 14961

C9-O10 13569

C9-O11 12301

C4-O12 12276

C6-F13 13223

C7-N14 14236

N14-C15 14675

C15-C16 15526

C16-N17 14676

N17-C19 14678

C19-C20 15524

C19-N14 14680

N17-C18 14632

N1-C2 14088

C2-C3 13706

C3-C4 14890

C4-C4a 15094

C4a-C5 14207

C5-C6 14253

C6-C7 14713

C7-C8 14520

C8-C8a 14459

C8a-N1 14031

C8-O21 13472

O21-C22 14140

C22-C24 15611

C24-N1 14852

C24-C23 15482

C3-C9 15018

C9-O10 13532

C9-O11 12275

C4-O12 12239

C6-F13 13164

C7-N14 13877

N14-C15 14978

C15-C16 15561

C16-N17 14620

N17-C19 14630

C19-C20 15521

C19-N14 14955

N17-C18 14730

00113

-00013

-00008

00077

00020

-00061

00263

00152

00013

-00122

-00116

00112

-00023

00029

00007

00057

-00037

-00026

-00037

-00059

-00359

00303

00035

-00056

-00048

-00003

00275

00098















and 19 respectively







N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

mz = 318

RI= 14

H+

[M+H]+

mz = 362

RI = 100

N

O

N

NH3C

O

O

OH

F

CH3

H+

- H2 O

mz = 344RI = 5

- C2 H

4 N

N

O

O

O

OH

F

CH3

H+

N

CH3

mz= 320RI = 31

H+








atoms of the ring



908 kJmol-1



kJmol-1



CHAPTER (5)

CONCLUSIONS


[M]+bull



for Levofloxacin







spectra indicated













REFERNCES














New York NY (1969)



















pp142(1998)







Soc3(2006)


















Chemistry (2004)















24714(2003)













(1999)


867105(2008)






241359(2005)






153 37(1996)





1216 794(2009)



250 370(2006)





Chem46 363( 2005)


B 530186(1990)


759(2005)





(1993)




هقدهت هي



للحصىل على


2213





زشق السبع









جبهعخ ثب

كليخ العلم










[M-C2H4N]+ and [M-

CO2-C2H4N]+









[MH-CO2]+bull


+
















هي قجر


















(ΔHf (M)+bull

)




investigation

CHAPTER (2)



Ionization






is formed


e-

[M] [M] +bull

+ 2 e-



can dissociate to




ion [F] +

[M]+bull

[F]+ + [N]


Also [M]+bull


and neutral


[M]+bull

[F]+bull





may


Io

ni

za

ti

on

E

ne

rg

y

(27)

Th

e

ion

izat

ion

ene

rgy

(IE

)

so

met

ime

s

call

ed

(les

s

cor

rect

ly)

the

ion

izat















principle(28-29)








showed


law of the form

σ (E) = C (E-Eo)n-1

(4)









which is formed

by the reaction

M+e- M

+bull + 2e

- (5)


IE[M]+bull

= ∆Hf[M]+bull

- ∆Hf[M] (6)

Where ∆Hf[M]+bull





[M]+bull

[F]+

+ [N]bull (7)



AE[F]+ = IE [F] +D[F-N] + Eexc (8)





(∆Eth) = ∆Hf[F]+ + ∆Hf[N] - ∆Hf[M] (9)





∆Hf[F]+ = IE[F] +∆Hf[F] (11)


Stevenson(32)



work of Audier(33)






molecular ion


spectra










is defined by



[A ndash B] +bull

A+ + B

bull (12)

odd even odd

[A ndash B] +bull

Abull + B

+ (13)

odd odd even

The fragment ion A+

or B+









Ionization






















CH4+ e- CH4

+bull CH3

+CH2

+ CH

++ 2e (14)

CH4+bull

+ CH4 CH5+ + CH3

bull (15)

CH3+ + CH4 C2H5

+ + H2 (16)


+




210 Proton Affinity





[BH]+ + M B+[M+H]

+ (17)




M + CH5+

[M+H]+ + CH4 (18)

M + H+ MH

+ (19)


+] = - PA

PA = - ∆Hordm































segments













CHAPTER (3)







software

31 Apparatus




positive ion mode










32 Materials






reagent gas




eV











CHAPTER (4)


41 Results











techniques














in


















literature

42 Discussion













Molecule

R1

R2

Norfloxacin

Pefloxacin

Ciprofloxacin

Levofloxacin

ethyl

ethyl

cyclopropyl


piperazinyl

4-methyl-piprazinyl

piperazinyl

4-methyl-piprazinyl









compounds




NN

N

F

CH3

O O

OH

PEFLOXACIN

H3C

NN

HN

F

O O

OH

CIPROFLOXACIN

NN

N

F

O O

OH

LEVOFLOXACIN

O

CH3H3C





compounds











chapter 2)







mz 320









15 e V

70 e V

mz

11

60

7

52

14

100

5

9

68

2

4

7

8

7

2

2

2

2

-

-

-

-

-

-

-

-

-

8

12

70

9

59

16

100

9

13

88

5

9

4

11

13

6

6

6

6

7

6

6

7

6

6

8

7

14

15

320

319 [M]+middot

278

277 [M-C2H4N]+

276

275 [M-CO2]+

245

234

233[M-CO2-C2H4N]+

219

218

217

204

203

190

189

176

175

161

95

85

83

81

73

71

69

57

56







The

removal

of an

electron

from an

organic

molecule

often

leads to

change in

its

relative










) (using




423

Fragm

entatio

n of

Norflo

xacin

using

EI

techniq

ue

Most

previous


(214850-51) where


However the present









respectively


[M-CO2]+bull



Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C9

O10

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0309

0199

-0264

0338

-0119

-0015

0102

0082

-0050

0096

0160

13002

0417

-0295

-0367

-0298

-0169

-0395

0127

0095

-0320

0095

0127

-0287

0175

-0202

0314

-0078

0000

0137

0173

-0145

0190

0149

-0004

0399

-0291

-0324

-0230

-0128

-0168

0082

0103

-0339

0105

0078

0022

-0024

0062

-0024

0041

0015

0035

0091

-0095

0094

-0011

-0006

-0018

0004

0043

0068

0041

0227

-0045

0008

-0019

0010

-0049







fragment (odd-




CO2]+bull



bull radical








+ ion through


(Scheme 1)




C3H7N (Scheme 1)


for



and ∆Hf(M)


) (Table





and



N

O O

O HF

NN

M

= 319

- CO2

N

O

F

NN

= 275

C2 H

4 N

= 277

N

O O

O HF

RI = 70 RI = 100

RI = 59

H

N

O

HF

RI = 88

C2H

4N

- CO2

= 233

NN

+ +

- C3 H

7 N

N

O

HF

N

mz mz

mz

mz = 218

RI = 9

mz

HH rearrangement

rearrangement

+

si m

pl e

cl e

av

ag

e



Table

5

Calcul

ated

∆Hf(M

)∆Hf(

M)+bull

an

d IE

values

for the

four

6-

fluoro

quinol

one

molec

ules

using

MND

O method

Neutral molecule




∆ L

N1-C2 14007

C2-C3 13700

C3-C4 14881

C4-C4a 15012

C4a-C5 14185

C5-C6 14294

C6-C7 14433

C7-C8 14203

C8-C8a 14304

C8a-N1 14204

N1-C20 14830

C20-C21 15379

C3-C9 14950

C9-O10 13571

C9-O11 12304

C4-O12 12275

C6-F13 13223

C7-N14 14306

N14-C15 14706

C15-C16 15517

C16-N17 14676

N17-C18 14677

C18-C19 15514 C19-N14 14706

N1-C2 14167

C2-C3 13650

C3-C4 14863

C4-C4a 15080

C4a-C5 14118

C5-C6 14299

C6-C7 14807

C7-C8 14391

C8-C8a 14142

C8a-N1 13980

N1-C20 14934

C20-C21 15374

C3-C9 15028

C9-O10 13527

C9-O11 12268

C4-O12 12237

C6-F13 13126

C7-N14 13740

N14-C15 14962

C15-C16 15615

C16-N17 14567

N17-C18 14571

C18-C19 15558 C19-N14 14935

00160

-00050

-00018

00068

-00067

00005

00374

00188

-00162

-00224

00104

-00005

00078

-00044

-00036

-00038

-00097

-00566

00256

00098

-00109

-00106

00044

00229

IE

eV k J mol-1

∆Hf(M)+bull

k J mol-1

∆Hf(M)

k J mol-1

Molecule




) and



CO2]+bull









81 782 305 -485

Norfloxacin

8 772 314 -464

Pefloxacin

88 849 485 -368

Ciprofloxacin

83 801 142 -631

Levofloxacin




-1) The


-1)


kJmol-1


ion

by 106 kJmol-1























mz RI[] mz RI[]

mz RI[] mz RI[]

97 17 163 8 218 15 236 32 237 6 250 6 252 5 258 7 264 9 270 8 272 5 274 6 275 9 276 60 277 23 278 55 279 13 290 10 292 9 302 8 304 20 306 12 316 5 318 10 320[M+H]

+ 100 321 18 334[M+CH3]

+ 14 348[M+C2H5]

+ 20

289 6 290 31 291 9 292 12 316 10 317 5 318 27 319 6 332 6 333 6 334[M+H]

+ 100 335 19 346 6 348[M+CH3]

+ 5 362[M+C2H5]

+ 21

276 10 287 8 288 52 289 14 290 17 302 5 304 5 314 6 316 18 317 9 318 38 319 9 320 14 330 5 332[M+H]

+ 100 333 18 334 6 346[M+CH3]

+ 17 360[M+C2H5]

+ 23 361 6

130 7 318 14 319 9 320 31 321 7 344 5 346 6 348 7 360 9 361 9 362[M+H]

+ 100 363 20 376[M+CH3]

+ 5 390[M+C2H5]

+ 19















(59)





authors( 214860)



technique




in scheme 2




+

ion



+ and






N

O O

O HF

NHN

[M+H]+ = 320

- CO2

N

O

F

NHN

mz = 276

mz = 278

N

O O

O HF

RI = 100 RI = 60

RI = 55

H

C2 H

4 N

N

H+ H+

H+

N

O O

F

NHN

H+

- H2 O

mz = 302RI = 8

rearrangment
























kJmol-1






species



method

431

Mass

spectr

a of

Peflox

acin

under

EI technique

PA (M) kJmol

-1

∆Hf(M+H)+

kJmol-1

Protonated Site

∆Hf(M) kcalmol

-1

Molecule

904

749

142

297

O12H

N1H

-116

Norfloxacin

916

753

151

314

O12H

N1H

-111

Pefloxacin

904

745

255

418

O12H

N1H

-88

Ciprofloxacin

908

715

2

192

O12H

N1H

-149

Levofloxacin












Table 8




15 eV

70 eV

mz

10

55

3

21

100

4

6

16

10

10

6

10

30

26

7

4

12

61

3

18

100

4

6

14

11

7

4

6

20

15

6

4

334

333 [M]+middot

291

290

289 [M-CO2]+

245

219

218 [M-CO2-C4H9N]+

203 [M-CO2-C4H9N-CH3]+

96

81

79

71 [C4H9N]+bull

70

57

56







800 eV (772 kJ mole-1





Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

-0307

0198

-0262

-0297

0178

-0206

0010

-0020

0056

C4

C4a

C5

C6

C7

C8

C8a

C21

C22

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

0337

-0119

-0016

0103

0081

-0050

0095

0162

-0002

04135

-0301

-0357

-0300

-0169

-0391

0128

0143

-0428

0144

0128

0193

0318

-0082

0000

0124

0218

-0171

0190

0151

-0003

0401

-0293

-0328

-0228

-0124

-0164

0114

0124

-0418

0126

0114

0183

-0019

0037

0016

0021

0137

-0121

0095

-0011

-0001

-0014

0008

0029

0072

0045

0227

-0014

-0019

0010

-0018

-0014

-0010







ion by the







ion at mz 218 with


CO2- C4H9N]+bull





[C4H9N]+bull



On the other



at mz=71 RI=20 in

compariso

n with

Norfloxaci

n the

absence of

ndashCH3

group lead

to produce

the

fragment

[M-

C2H4N]+

ion at mz

= 277

RI=59

Scheme 3 Main

fragmentat

ion

pathways

of

Pefloxacin

at 70 eV

N

O O

O HF

NN

M

=333

- CO2

N

O

F

NN

mz =289

C4 H

9 N

RI = 61 RI = 100

H

N

O

HF

NH2C

RI = 14

mz = 218

H3C

N

O

H

CH2

F

NH2C

mz =203RI = 11

+ +

+

+


mz

- CH

3

H2C

N

CH2

CH2H3C

N

H2CCH2

CH2

H2C

H

r ea r

ang

men

t

C4H9N +

N

O

F

NH2C

O

O H



The

appearance

energy (AE)

of the

fragment

[M-CO2]+bull

ion at

mz=289 is

calculated

(using the

heats of

formation of

∆Hf(M)

molecule

∆Hf (CO2)

and ∆Hf [M-

CO2]+bull

)and

is found to

be equal to

830 eV(801

kJmol-1

)

The

difference

between the

value for

AE [M-CO2]+bull












-1)

Neutral molecule


Molecular ion


∆ L

N1-C2 14016

C2-C3 13689

C3-C4 14885

C4-C4a 15009

C4a-C5 14182

C5-C6 14295

C6-C7 14435

C7-C8 14208

C8-C8a 14299

C8a-N1 14220

N1-C21 14819

C21-C22 15379

C3-C9 14953

C9-O10 13581

C9-O11 12293

C4-O12 12274

C6-F13 13223

C7-N14 14312

N14-C15 14704

C15-C16 15521

C16-N17 14676

N17-C19 14677

C19-C20 15526

C20-N14 14699

N17-C18 14640

N1-C2 14180

C2-C3 13665

C3-C4 14877

C4-C4a 15072

C4a-C5 14101

C5-C6 14324

C6-C7 14928

C7-C8 14547

C8-C8a 14088

C8a-N1 13994

N1-C21 14922

C21-C22 15372

C3-C9 15008

C9-O10 13534

C9-O11 12273

C4-O12 12226

C6-F13 13114

C7-N14 13624

N14-C15 15031

C15-C16 15508

C16-N17 14609

N17-C19 14600

C19-C20 15504

C20-N14 15020

N17-C18 14739

00164

-00024

-00008

00063

-00081

00029

00493

00339

-00211

-00226

00103

-00007

00055

-00047

-00020

-00048

-00109

-00688

00327

-00013

-00067

-00077

-00022

00321

00099


kJmol-1


to 68 kJmol-1







100)







+


+



molecule



[M+C2H5- CO2]+bull

ion

N

O O

O HF

NN

=334

- CO2

N

O

F

NN

mz =290

RI = 100 RI = 31

HH+

[M+H]+

N

O

CF

NN

H+

O

mz = 316

RI = 10

- H2 O

- C2 H

4 N

N

O O

O HF

H+

N

mz = 292

RI = 12

H+

H3C

mz















kJmol-1



-







It is









15 eV

70 eV

mz

11

62

11

67

18

100

11

68

5

7

9

4

4

5

6

6

8

19

14

74

13

71

19

100

11

69

5

8

9

4

5

5

5

6

9

20

332

331 [M]+

290

289 [M-C2H4N]+

288

287 [M-CO2]+

246

245 [M-CO2-C2H4N]+

231

230

229

218

215

204

202

201

57

56










eV(849 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

(e)

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C22

O10

C9

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0277 0206

-0266 0339

-0117 -0021 0133 0076

-0075 0100 0035

-0053 -0057 -0295 0418

-0370 -0295 -0159 -0387 0128 0098

-0312 0096 0127

-0125 0233

-0179 0206

-0085 -0029 0147 0157

-0059 0116

-0042 -0026 -0034 -0285 0380

-0297 0064

-0137 -0419 0133 0099

-0324 0100 0138

0152 0027 0087

-0133 0032

-0008 0014 0081 0016 0016

-0077 0027 0023 0010

-0038 0073 0359 0022

-0032 0005 0001

-0012 0004 0011
















at mz 287 with






ion indicates





















N

O O

O HF

NN

M

= 331

- CO2

N

O

F

NN

= 287

C2 H

4 N

N

O O

O HF

N

RI = 74

RI = 100

RI = 71

H

N

O

HF

RI = 69

C2 H

4 N

- CO2

+ +

H H

H rearengment

N

H rearengm

ent

mz 56RI = 20

mz

mz

mz = 245

mz = 289

H2C

NCH2

CH2




Neutral molecule


Molecular ion


∆ L




CO2)+bull








(050 eV)This














N1-C2 14017

C2-C3 1371

C3-C4 14908

C4-C4a 15019

C4a-C5 14169

C5-C6 1431

C6-C7 14441

C7-C8 14194

C8-C8a 14281

N1-C20 14534

C20-C21 15421

C21-C22 15186

C22-C20 15420

C3-C9 14939

C9-O10 13571

C9-O11 12308

C4-O12 12269

C6-F13 13203

C7-N14 14310

N14-C15 14700

C15-C16 15530

C16-N17 14670

N17-C18 14661

C18-C19 15528

C19-N14 14701

N1-C2 13703

C2-C3 14123

C3-C4 14229

C4-C4a 14585

C4a-C5 14303

C5-C6 14214

C6-C7 14567

C7-C8 14189

C8-C8a 14311

N1-C20 14762

C20-C21 15436

C21-C22 15157

C22-C20 15449

C3-C9 15069

C9-O10 13502

C9-O11 12250

C4-O12 13096

C6-F13 13167

C7-N14 14102

N14-C15 14754

C15-C16 15534

C16-N17 14645

N17-C18 14636

C18-C19 15533

C19-N14 14746

-00314

00413

-00679

-00434

00134

-00096

00126

-00005

00030

00228

00015

-00029

00029

00130

-00069

-00058

00827

-00036

-00208

00054

00004

-00025

-00025

00005

00045















+) cations transfer


+ molecules with



N

O O

O HF

NN

- CO2

N

O

F

NN

N

O O

O HF

N

H

C2 H

4 N

H H

H+

[M+H]+ = 332

RI = 100

H+

mz = 288RI = 52

H+

mz= 290RI = 17

- H2 O

N

O O

F

NN

H

H+

mz = 314RI = 6

445

The

proton


Ciprofloxacin










745kJmol-1

and 904 kJmol-1



kJmol-1


















15 e V

70 e V

mz

16

100

14

5

5

5

9

19

8

7

34

-

17

100

17

5

7

6

12

22

11

10

29

4

362

361[M]+bull

317[M-CO2]+bull

276

273

254

247


232

231

71(C4H9N)+bull

56










eV(801 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

O21

-0299

0201

-0261

0338

-0099

-0028

0112

0092

0079

0051

-0227

-0292

0181

-0209

0322

-0062

-0005

014

0081

0104

0057

-0252

0007

-002

0052

-0016

0037

0023

0028

-0011

0025

0006

-0025

C22

C24

C23

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

015

0091

0016

0416

-0295

-0366

-0297

-0167

-0395

0142

0144

-0429

0143

0142

0194

0155

0088

0011

0402

-0291

-0332

-0244

-0141

-0081

01

0133

-0434

0135

0108

0188

0005

-0003

-0005

-0014

0004

0034

0053

0026

0314

-0042

-0011

-0005

-0008

-0034

-0006




















) The difference



) gives the



(020

eV)

Scheme 7 Main



N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

M

= 361mz = 317

C4H9N

N

O

N

O

HF

CH3

mz = 246

RI= 100 RI= 17

RI = 20

++

H-Rearangment

+

mz = 71RI = 29

+

mz

CH2

N

H2C

CH2

CH3

NH2C

H2C

CH2

CH2

H




Neutral molecule


Molecular ion


∆ L

N1-C2 13975

C2-C3 13719

C3-C4 14898

C4-C4a 15017

C4a-C5 14187

C5-C6 14314

C6-C7 14450

C7-C8 14368

C8-C8a 14446

C8a-N1 14153

C8-O21 13588

O21-C22 14028

C22-C24 15634

C24-N1 14823

C24-C23 15475

C3-C9 14961

C9-O10 13569

C9-O11 12301

C4-O12 12276

C6-F13 13223

C7-N14 14236

N14-C15 14675

C15-C16 15526

C16-N17 14676

N17-C19 14678

C19-C20 15524

C19-N14 14680

N17-C18 14632

N1-C2 14088

C2-C3 13706

C3-C4 14890

C4-C4a 15094

C4a-C5 14207

C5-C6 14253

C6-C7 14713

C7-C8 14520

C8-C8a 14459

C8a-N1 14031

C8-O21 13472

O21-C22 14140

C22-C24 15611

C24-N1 14852

C24-C23 15482

C3-C9 15018

C9-O10 13532

C9-O11 12275

C4-O12 12239

C6-F13 13164

C7-N14 13877

N14-C15 14978

C15-C16 15561

C16-N17 14620

N17-C19 14630

C19-C20 15521

C19-N14 14955

N17-C18 14730

00113

-00013

-00008

00077

00020

-00061

00263

00152

00013

-00122

-00116

00112

-00023

00029

00007

00057

-00037

-00026

-00037

-00059

-00359

00303

00035

-00056

-00048

-00003

00275

00098















and 19 respectively







N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

mz = 318

RI= 14

H+

[M+H]+

mz = 362

RI = 100

N

O

N

NH3C

O

O

OH

F

CH3

H+

- H2 O

mz = 344RI = 5

- C2 H

4 N

N

O

O

O

OH

F

CH3

H+

N

CH3

mz= 320RI = 31

H+








atoms of the ring



908 kJmol-1



kJmol-1



CHAPTER (5)

CONCLUSIONS


[M]+bull



for Levofloxacin







spectra indicated













REFERNCES














New York NY (1969)



















pp142(1998)







Soc3(2006)


















Chemistry (2004)















24714(2003)













(1999)


867105(2008)






241359(2005)






153 37(1996)





1216 794(2009)



250 370(2006)





Chem46 363( 2005)


B 530186(1990)


759(2005)





(1993)




هقدهت هي



للحصىل على


2213





زشق السبع









جبهعخ ثب

كليخ العلم










[M-C2H4N]+ and [M-

CO2-C2H4N]+









[MH-CO2]+bull


+
















هي قجر













CHAPTER (2)



Ionization






is formed


e-

[M] [M] +bull

+ 2 e-



can dissociate to




ion [F] +

[M]+bull

[F]+ + [N]


Also [M]+bull


and neutral


[M]+bull

[F]+bull





may


Io

ni

za

ti

on

E

ne

rg

y

(27)

Th

e

ion

izat

ion

ene

rgy

(IE

)

so

met

ime

s

call

ed

(les

s

cor

rect

ly)

the

ion

izat















principle(28-29)








showed


law of the form

σ (E) = C (E-Eo)n-1

(4)









which is formed

by the reaction

M+e- M

+bull + 2e

- (5)


IE[M]+bull

= ∆Hf[M]+bull

- ∆Hf[M] (6)

Where ∆Hf[M]+bull





[M]+bull

[F]+

+ [N]bull (7)



AE[F]+ = IE [F] +D[F-N] + Eexc (8)





(∆Eth) = ∆Hf[F]+ + ∆Hf[N] - ∆Hf[M] (9)





∆Hf[F]+ = IE[F] +∆Hf[F] (11)


Stevenson(32)



work of Audier(33)






molecular ion


spectra










is defined by



[A ndash B] +bull

A+ + B

bull (12)

odd even odd

[A ndash B] +bull

Abull + B

+ (13)

odd odd even

The fragment ion A+

or B+









Ionization






















CH4+ e- CH4

+bull CH3

+CH2

+ CH

++ 2e (14)

CH4+bull

+ CH4 CH5+ + CH3

bull (15)

CH3+ + CH4 C2H5

+ + H2 (16)


+




210 Proton Affinity





[BH]+ + M B+[M+H]

+ (17)




M + CH5+

[M+H]+ + CH4 (18)

M + H+ MH

+ (19)


+] = - PA

PA = - ∆Hordm































segments













CHAPTER (3)







software

31 Apparatus




positive ion mode










32 Materials






reagent gas




eV











CHAPTER (4)


41 Results











techniques














in


















literature

42 Discussion













Molecule

R1

R2

Norfloxacin

Pefloxacin

Ciprofloxacin

Levofloxacin

ethyl

ethyl

cyclopropyl


piperazinyl

4-methyl-piprazinyl

piperazinyl

4-methyl-piprazinyl









compounds




NN

N

F

CH3

O O

OH

PEFLOXACIN

H3C

NN

HN

F

O O

OH

CIPROFLOXACIN

NN

N

F

O O

OH

LEVOFLOXACIN

O

CH3H3C





compounds











chapter 2)







mz 320









15 e V

70 e V

mz

11

60

7

52

14

100

5

9

68

2

4

7

8

7

2

2

2

2

-

-

-

-

-

-

-

-

-

8

12

70

9

59

16

100

9

13

88

5

9

4

11

13

6

6

6

6

7

6

6

7

6

6

8

7

14

15

320

319 [M]+middot

278

277 [M-C2H4N]+

276

275 [M-CO2]+

245

234

233[M-CO2-C2H4N]+

219

218

217

204

203

190

189

176

175

161

95

85

83

81

73

71

69

57

56







The

removal

of an

electron

from an

organic

molecule

often

leads to

change in

its

relative










) (using




423

Fragm

entatio

n of

Norflo

xacin

using

EI

techniq

ue

Most

previous


(214850-51) where


However the present









respectively


[M-CO2]+bull



Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C9

O10

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0309

0199

-0264

0338

-0119

-0015

0102

0082

-0050

0096

0160

13002

0417

-0295

-0367

-0298

-0169

-0395

0127

0095

-0320

0095

0127

-0287

0175

-0202

0314

-0078

0000

0137

0173

-0145

0190

0149

-0004

0399

-0291

-0324

-0230

-0128

-0168

0082

0103

-0339

0105

0078

0022

-0024

0062

-0024

0041

0015

0035

0091

-0095

0094

-0011

-0006

-0018

0004

0043

0068

0041

0227

-0045

0008

-0019

0010

-0049







fragment (odd-




CO2]+bull



bull radical








+ ion through


(Scheme 1)




C3H7N (Scheme 1)


for



and ∆Hf(M)


) (Table





and



N

O O

O HF

NN

M

= 319

- CO2

N

O

F

NN

= 275

C2 H

4 N

= 277

N

O O

O HF

RI = 70 RI = 100

RI = 59

H

N

O

HF

RI = 88

C2H

4N

- CO2

= 233

NN

+ +

- C3 H

7 N

N

O

HF

N

mz mz

mz

mz = 218

RI = 9

mz

HH rearrangement

rearrangement

+

si m

pl e

cl e

av

ag

e



Table

5

Calcul

ated

∆Hf(M

)∆Hf(

M)+bull

an

d IE

values

for the

four

6-

fluoro

quinol

one

molec

ules

using

MND

O method

Neutral molecule




∆ L

N1-C2 14007

C2-C3 13700

C3-C4 14881

C4-C4a 15012

C4a-C5 14185

C5-C6 14294

C6-C7 14433

C7-C8 14203

C8-C8a 14304

C8a-N1 14204

N1-C20 14830

C20-C21 15379

C3-C9 14950

C9-O10 13571

C9-O11 12304

C4-O12 12275

C6-F13 13223

C7-N14 14306

N14-C15 14706

C15-C16 15517

C16-N17 14676

N17-C18 14677

C18-C19 15514 C19-N14 14706

N1-C2 14167

C2-C3 13650

C3-C4 14863

C4-C4a 15080

C4a-C5 14118

C5-C6 14299

C6-C7 14807

C7-C8 14391

C8-C8a 14142

C8a-N1 13980

N1-C20 14934

C20-C21 15374

C3-C9 15028

C9-O10 13527

C9-O11 12268

C4-O12 12237

C6-F13 13126

C7-N14 13740

N14-C15 14962

C15-C16 15615

C16-N17 14567

N17-C18 14571

C18-C19 15558 C19-N14 14935

00160

-00050

-00018

00068

-00067

00005

00374

00188

-00162

-00224

00104

-00005

00078

-00044

-00036

-00038

-00097

-00566

00256

00098

-00109

-00106

00044

00229

IE

eV k J mol-1

∆Hf(M)+bull

k J mol-1

∆Hf(M)

k J mol-1

Molecule




) and



CO2]+bull









81 782 305 -485

Norfloxacin

8 772 314 -464

Pefloxacin

88 849 485 -368

Ciprofloxacin

83 801 142 -631

Levofloxacin




-1) The


-1)


kJmol-1


ion

by 106 kJmol-1























mz RI[] mz RI[]

mz RI[] mz RI[]

97 17 163 8 218 15 236 32 237 6 250 6 252 5 258 7 264 9 270 8 272 5 274 6 275 9 276 60 277 23 278 55 279 13 290 10 292 9 302 8 304 20 306 12 316 5 318 10 320[M+H]

+ 100 321 18 334[M+CH3]

+ 14 348[M+C2H5]

+ 20

289 6 290 31 291 9 292 12 316 10 317 5 318 27 319 6 332 6 333 6 334[M+H]

+ 100 335 19 346 6 348[M+CH3]

+ 5 362[M+C2H5]

+ 21

276 10 287 8 288 52 289 14 290 17 302 5 304 5 314 6 316 18 317 9 318 38 319 9 320 14 330 5 332[M+H]

+ 100 333 18 334 6 346[M+CH3]

+ 17 360[M+C2H5]

+ 23 361 6

130 7 318 14 319 9 320 31 321 7 344 5 346 6 348 7 360 9 361 9 362[M+H]

+ 100 363 20 376[M+CH3]

+ 5 390[M+C2H5]

+ 19















(59)





authors( 214860)



technique




in scheme 2




+

ion



+ and






N

O O

O HF

NHN

[M+H]+ = 320

- CO2

N

O

F

NHN

mz = 276

mz = 278

N

O O

O HF

RI = 100 RI = 60

RI = 55

H

C2 H

4 N

N

H+ H+

H+

N

O O

F

NHN

H+

- H2 O

mz = 302RI = 8

rearrangment
























kJmol-1






species



method

431

Mass

spectr

a of

Peflox

acin

under

EI technique

PA (M) kJmol

-1

∆Hf(M+H)+

kJmol-1

Protonated Site

∆Hf(M) kcalmol

-1

Molecule

904

749

142

297

O12H

N1H

-116

Norfloxacin

916

753

151

314

O12H

N1H

-111

Pefloxacin

904

745

255

418

O12H

N1H

-88

Ciprofloxacin

908

715

2

192

O12H

N1H

-149

Levofloxacin












Table 8




15 eV

70 eV

mz

10

55

3

21

100

4

6

16

10

10

6

10

30

26

7

4

12

61

3

18

100

4

6

14

11

7

4

6

20

15

6

4

334

333 [M]+middot

291

290

289 [M-CO2]+

245

219

218 [M-CO2-C4H9N]+

203 [M-CO2-C4H9N-CH3]+

96

81

79

71 [C4H9N]+bull

70

57

56







800 eV (772 kJ mole-1





Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

-0307

0198

-0262

-0297

0178

-0206

0010

-0020

0056

C4

C4a

C5

C6

C7

C8

C8a

C21

C22

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

0337

-0119

-0016

0103

0081

-0050

0095

0162

-0002

04135

-0301

-0357

-0300

-0169

-0391

0128

0143

-0428

0144

0128

0193

0318

-0082

0000

0124

0218

-0171

0190

0151

-0003

0401

-0293

-0328

-0228

-0124

-0164

0114

0124

-0418

0126

0114

0183

-0019

0037

0016

0021

0137

-0121

0095

-0011

-0001

-0014

0008

0029

0072

0045

0227

-0014

-0019

0010

-0018

-0014

-0010







ion by the







ion at mz 218 with


CO2- C4H9N]+bull





[C4H9N]+bull



On the other



at mz=71 RI=20 in

compariso

n with

Norfloxaci

n the

absence of

ndashCH3

group lead

to produce

the

fragment

[M-

C2H4N]+

ion at mz

= 277

RI=59

Scheme 3 Main

fragmentat

ion

pathways

of

Pefloxacin

at 70 eV

N

O O

O HF

NN

M

=333

- CO2

N

O

F

NN

mz =289

C4 H

9 N

RI = 61 RI = 100

H

N

O

HF

NH2C

RI = 14

mz = 218

H3C

N

O

H

CH2

F

NH2C

mz =203RI = 11

+ +

+

+


mz

- CH

3

H2C

N

CH2

CH2H3C

N

H2CCH2

CH2

H2C

H

r ea r

ang

men

t

C4H9N +

N

O

F

NH2C

O

O H



The

appearance

energy (AE)

of the

fragment

[M-CO2]+bull

ion at

mz=289 is

calculated

(using the

heats of

formation of

∆Hf(M)

molecule

∆Hf (CO2)

and ∆Hf [M-

CO2]+bull

)and

is found to

be equal to

830 eV(801

kJmol-1

)

The

difference

between the

value for

AE [M-CO2]+bull












-1)

Neutral molecule


Molecular ion


∆ L

N1-C2 14016

C2-C3 13689

C3-C4 14885

C4-C4a 15009

C4a-C5 14182

C5-C6 14295

C6-C7 14435

C7-C8 14208

C8-C8a 14299

C8a-N1 14220

N1-C21 14819

C21-C22 15379

C3-C9 14953

C9-O10 13581

C9-O11 12293

C4-O12 12274

C6-F13 13223

C7-N14 14312

N14-C15 14704

C15-C16 15521

C16-N17 14676

N17-C19 14677

C19-C20 15526

C20-N14 14699

N17-C18 14640

N1-C2 14180

C2-C3 13665

C3-C4 14877

C4-C4a 15072

C4a-C5 14101

C5-C6 14324

C6-C7 14928

C7-C8 14547

C8-C8a 14088

C8a-N1 13994

N1-C21 14922

C21-C22 15372

C3-C9 15008

C9-O10 13534

C9-O11 12273

C4-O12 12226

C6-F13 13114

C7-N14 13624

N14-C15 15031

C15-C16 15508

C16-N17 14609

N17-C19 14600

C19-C20 15504

C20-N14 15020

N17-C18 14739

00164

-00024

-00008

00063

-00081

00029

00493

00339

-00211

-00226

00103

-00007

00055

-00047

-00020

-00048

-00109

-00688

00327

-00013

-00067

-00077

-00022

00321

00099


kJmol-1


to 68 kJmol-1







100)







+


+



molecule



[M+C2H5- CO2]+bull

ion

N

O O

O HF

NN

=334

- CO2

N

O

F

NN

mz =290

RI = 100 RI = 31

HH+

[M+H]+

N

O

CF

NN

H+

O

mz = 316

RI = 10

- H2 O

- C2 H

4 N

N

O O

O HF

H+

N

mz = 292

RI = 12

H+

H3C

mz















kJmol-1



-







It is









15 eV

70 eV

mz

11

62

11

67

18

100

11

68

5

7

9

4

4

5

6

6

8

19

14

74

13

71

19

100

11

69

5

8

9

4

5

5

5

6

9

20

332

331 [M]+

290

289 [M-C2H4N]+

288

287 [M-CO2]+

246

245 [M-CO2-C2H4N]+

231

230

229

218

215

204

202

201

57

56










eV(849 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

(e)

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C22

O10

C9

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0277 0206

-0266 0339

-0117 -0021 0133 0076

-0075 0100 0035

-0053 -0057 -0295 0418

-0370 -0295 -0159 -0387 0128 0098

-0312 0096 0127

-0125 0233

-0179 0206

-0085 -0029 0147 0157

-0059 0116

-0042 -0026 -0034 -0285 0380

-0297 0064

-0137 -0419 0133 0099

-0324 0100 0138

0152 0027 0087

-0133 0032

-0008 0014 0081 0016 0016

-0077 0027 0023 0010

-0038 0073 0359 0022

-0032 0005 0001

-0012 0004 0011
















at mz 287 with






ion indicates





















N

O O

O HF

NN

M

= 331

- CO2

N

O

F

NN

= 287

C2 H

4 N

N

O O

O HF

N

RI = 74

RI = 100

RI = 71

H

N

O

HF

RI = 69

C2 H

4 N

- CO2

+ +

H H

H rearengment

N

H rearengm

ent

mz 56RI = 20

mz

mz

mz = 245

mz = 289

H2C

NCH2

CH2




Neutral molecule


Molecular ion


∆ L




CO2)+bull








(050 eV)This














N1-C2 14017

C2-C3 1371

C3-C4 14908

C4-C4a 15019

C4a-C5 14169

C5-C6 1431

C6-C7 14441

C7-C8 14194

C8-C8a 14281

N1-C20 14534

C20-C21 15421

C21-C22 15186

C22-C20 15420

C3-C9 14939

C9-O10 13571

C9-O11 12308

C4-O12 12269

C6-F13 13203

C7-N14 14310

N14-C15 14700

C15-C16 15530

C16-N17 14670

N17-C18 14661

C18-C19 15528

C19-N14 14701

N1-C2 13703

C2-C3 14123

C3-C4 14229

C4-C4a 14585

C4a-C5 14303

C5-C6 14214

C6-C7 14567

C7-C8 14189

C8-C8a 14311

N1-C20 14762

C20-C21 15436

C21-C22 15157

C22-C20 15449

C3-C9 15069

C9-O10 13502

C9-O11 12250

C4-O12 13096

C6-F13 13167

C7-N14 14102

N14-C15 14754

C15-C16 15534

C16-N17 14645

N17-C18 14636

C18-C19 15533

C19-N14 14746

-00314

00413

-00679

-00434

00134

-00096

00126

-00005

00030

00228

00015

-00029

00029

00130

-00069

-00058

00827

-00036

-00208

00054

00004

-00025

-00025

00005

00045















+) cations transfer


+ molecules with



N

O O

O HF

NN

- CO2

N

O

F

NN

N

O O

O HF

N

H

C2 H

4 N

H H

H+

[M+H]+ = 332

RI = 100

H+

mz = 288RI = 52

H+

mz= 290RI = 17

- H2 O

N

O O

F

NN

H

H+

mz = 314RI = 6

445

The

proton


Ciprofloxacin










745kJmol-1

and 904 kJmol-1



kJmol-1


















15 e V

70 e V

mz

16

100

14

5

5

5

9

19

8

7

34

-

17

100

17

5

7

6

12

22

11

10

29

4

362

361[M]+bull

317[M-CO2]+bull

276

273

254

247


232

231

71(C4H9N)+bull

56










eV(801 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

O21

-0299

0201

-0261

0338

-0099

-0028

0112

0092

0079

0051

-0227

-0292

0181

-0209

0322

-0062

-0005

014

0081

0104

0057

-0252

0007

-002

0052

-0016

0037

0023

0028

-0011

0025

0006

-0025

C22

C24

C23

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

015

0091

0016

0416

-0295

-0366

-0297

-0167

-0395

0142

0144

-0429

0143

0142

0194

0155

0088

0011

0402

-0291

-0332

-0244

-0141

-0081

01

0133

-0434

0135

0108

0188

0005

-0003

-0005

-0014

0004

0034

0053

0026

0314

-0042

-0011

-0005

-0008

-0034

-0006




















) The difference



) gives the



(020

eV)

Scheme 7 Main



N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

M

= 361mz = 317

C4H9N

N

O

N

O

HF

CH3

mz = 246

RI= 100 RI= 17

RI = 20

++

H-Rearangment

+

mz = 71RI = 29

+

mz

CH2

N

H2C

CH2

CH3

NH2C

H2C

CH2

CH2

H




Neutral molecule


Molecular ion


∆ L

N1-C2 13975

C2-C3 13719

C3-C4 14898

C4-C4a 15017

C4a-C5 14187

C5-C6 14314

C6-C7 14450

C7-C8 14368

C8-C8a 14446

C8a-N1 14153

C8-O21 13588

O21-C22 14028

C22-C24 15634

C24-N1 14823

C24-C23 15475

C3-C9 14961

C9-O10 13569

C9-O11 12301

C4-O12 12276

C6-F13 13223

C7-N14 14236

N14-C15 14675

C15-C16 15526

C16-N17 14676

N17-C19 14678

C19-C20 15524

C19-N14 14680

N17-C18 14632

N1-C2 14088

C2-C3 13706

C3-C4 14890

C4-C4a 15094

C4a-C5 14207

C5-C6 14253

C6-C7 14713

C7-C8 14520

C8-C8a 14459

C8a-N1 14031

C8-O21 13472

O21-C22 14140

C22-C24 15611

C24-N1 14852

C24-C23 15482

C3-C9 15018

C9-O10 13532

C9-O11 12275

C4-O12 12239

C6-F13 13164

C7-N14 13877

N14-C15 14978

C15-C16 15561

C16-N17 14620

N17-C19 14630

C19-C20 15521

C19-N14 14955

N17-C18 14730

00113

-00013

-00008

00077

00020

-00061

00263

00152

00013

-00122

-00116

00112

-00023

00029

00007

00057

-00037

-00026

-00037

-00059

-00359

00303

00035

-00056

-00048

-00003

00275

00098















and 19 respectively







N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

mz = 318

RI= 14

H+

[M+H]+

mz = 362

RI = 100

N

O

N

NH3C

O

O

OH

F

CH3

H+

- H2 O

mz = 344RI = 5

- C2 H

4 N

N

O

O

O

OH

F

CH3

H+

N

CH3

mz= 320RI = 31

H+








atoms of the ring



908 kJmol-1



kJmol-1



CHAPTER (5)

CONCLUSIONS


[M]+bull



for Levofloxacin







spectra indicated













REFERNCES














New York NY (1969)



















pp142(1998)







Soc3(2006)


















Chemistry (2004)















24714(2003)













(1999)


867105(2008)






241359(2005)






153 37(1996)





1216 794(2009)



250 370(2006)





Chem46 363( 2005)


B 530186(1990)


759(2005)





(1993)




هقدهت هي



للحصىل على


2213





زشق السبع









جبهعخ ثب

كليخ العلم










[M-C2H4N]+ and [M-

CO2-C2H4N]+









[MH-CO2]+bull


+
















هي قجر













Io

ni

za

ti

on

E

ne

rg

y

(27)

Th

e

ion

izat

ion

ene

rgy

(IE

)

so

met

ime

s

call

ed

(les

s

cor

rect

ly)

the

ion

izat















principle(28-29)








showed


law of the form

σ (E) = C (E-Eo)n-1

(4)









which is formed

by the reaction

M+e- M

+bull + 2e

- (5)


IE[M]+bull

= ∆Hf[M]+bull

- ∆Hf[M] (6)

Where ∆Hf[M]+bull





[M]+bull

[F]+

+ [N]bull (7)



AE[F]+ = IE [F] +D[F-N] + Eexc (8)





(∆Eth) = ∆Hf[F]+ + ∆Hf[N] - ∆Hf[M] (9)





∆Hf[F]+ = IE[F] +∆Hf[F] (11)


Stevenson(32)



work of Audier(33)






molecular ion


spectra










is defined by



[A ndash B] +bull

A+ + B

bull (12)

odd even odd

[A ndash B] +bull

Abull + B

+ (13)

odd odd even

The fragment ion A+

or B+









Ionization






















CH4+ e- CH4

+bull CH3

+CH2

+ CH

++ 2e (14)

CH4+bull

+ CH4 CH5+ + CH3

bull (15)

CH3+ + CH4 C2H5

+ + H2 (16)


+




210 Proton Affinity





[BH]+ + M B+[M+H]

+ (17)




M + CH5+

[M+H]+ + CH4 (18)

M + H+ MH

+ (19)


+] = - PA

PA = - ∆Hordm































segments













CHAPTER (3)







software

31 Apparatus




positive ion mode










32 Materials






reagent gas




eV











CHAPTER (4)


41 Results











techniques














in


















literature

42 Discussion













Molecule

R1

R2

Norfloxacin

Pefloxacin

Ciprofloxacin

Levofloxacin

ethyl

ethyl

cyclopropyl


piperazinyl

4-methyl-piprazinyl

piperazinyl

4-methyl-piprazinyl









compounds




NN

N

F

CH3

O O

OH

PEFLOXACIN

H3C

NN

HN

F

O O

OH

CIPROFLOXACIN

NN

N

F

O O

OH

LEVOFLOXACIN

O

CH3H3C





compounds











chapter 2)







mz 320









15 e V

70 e V

mz

11

60

7

52

14

100

5

9

68

2

4

7

8

7

2

2

2

2

-

-

-

-

-

-

-

-

-

8

12

70

9

59

16

100

9

13

88

5

9

4

11

13

6

6

6

6

7

6

6

7

6

6

8

7

14

15

320

319 [M]+middot

278

277 [M-C2H4N]+

276

275 [M-CO2]+

245

234

233[M-CO2-C2H4N]+

219

218

217

204

203

190

189

176

175

161

95

85

83

81

73

71

69

57

56







The

removal

of an

electron

from an

organic

molecule

often

leads to

change in

its

relative










) (using




423

Fragm

entatio

n of

Norflo

xacin

using

EI

techniq

ue

Most

previous


(214850-51) where


However the present









respectively


[M-CO2]+bull



Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C9

O10

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0309

0199

-0264

0338

-0119

-0015

0102

0082

-0050

0096

0160

13002

0417

-0295

-0367

-0298

-0169

-0395

0127

0095

-0320

0095

0127

-0287

0175

-0202

0314

-0078

0000

0137

0173

-0145

0190

0149

-0004

0399

-0291

-0324

-0230

-0128

-0168

0082

0103

-0339

0105

0078

0022

-0024

0062

-0024

0041

0015

0035

0091

-0095

0094

-0011

-0006

-0018

0004

0043

0068

0041

0227

-0045

0008

-0019

0010

-0049







fragment (odd-




CO2]+bull



bull radical








+ ion through


(Scheme 1)




C3H7N (Scheme 1)


for



and ∆Hf(M)


) (Table





and



N

O O

O HF

NN

M

= 319

- CO2

N

O

F

NN

= 275

C2 H

4 N

= 277

N

O O

O HF

RI = 70 RI = 100

RI = 59

H

N

O

HF

RI = 88

C2H

4N

- CO2

= 233

NN

+ +

- C3 H

7 N

N

O

HF

N

mz mz

mz

mz = 218

RI = 9

mz

HH rearrangement

rearrangement

+

si m

pl e

cl e

av

ag

e



Table

5

Calcul

ated

∆Hf(M

)∆Hf(

M)+bull

an

d IE

values

for the

four

6-

fluoro

quinol

one

molec

ules

using

MND

O method

Neutral molecule




∆ L

N1-C2 14007

C2-C3 13700

C3-C4 14881

C4-C4a 15012

C4a-C5 14185

C5-C6 14294

C6-C7 14433

C7-C8 14203

C8-C8a 14304

C8a-N1 14204

N1-C20 14830

C20-C21 15379

C3-C9 14950

C9-O10 13571

C9-O11 12304

C4-O12 12275

C6-F13 13223

C7-N14 14306

N14-C15 14706

C15-C16 15517

C16-N17 14676

N17-C18 14677

C18-C19 15514 C19-N14 14706

N1-C2 14167

C2-C3 13650

C3-C4 14863

C4-C4a 15080

C4a-C5 14118

C5-C6 14299

C6-C7 14807

C7-C8 14391

C8-C8a 14142

C8a-N1 13980

N1-C20 14934

C20-C21 15374

C3-C9 15028

C9-O10 13527

C9-O11 12268

C4-O12 12237

C6-F13 13126

C7-N14 13740

N14-C15 14962

C15-C16 15615

C16-N17 14567

N17-C18 14571

C18-C19 15558 C19-N14 14935

00160

-00050

-00018

00068

-00067

00005

00374

00188

-00162

-00224

00104

-00005

00078

-00044

-00036

-00038

-00097

-00566

00256

00098

-00109

-00106

00044

00229

IE

eV k J mol-1

∆Hf(M)+bull

k J mol-1

∆Hf(M)

k J mol-1

Molecule




) and



CO2]+bull









81 782 305 -485

Norfloxacin

8 772 314 -464

Pefloxacin

88 849 485 -368

Ciprofloxacin

83 801 142 -631

Levofloxacin




-1) The


-1)


kJmol-1


ion

by 106 kJmol-1























mz RI[] mz RI[]

mz RI[] mz RI[]

97 17 163 8 218 15 236 32 237 6 250 6 252 5 258 7 264 9 270 8 272 5 274 6 275 9 276 60 277 23 278 55 279 13 290 10 292 9 302 8 304 20 306 12 316 5 318 10 320[M+H]

+ 100 321 18 334[M+CH3]

+ 14 348[M+C2H5]

+ 20

289 6 290 31 291 9 292 12 316 10 317 5 318 27 319 6 332 6 333 6 334[M+H]

+ 100 335 19 346 6 348[M+CH3]

+ 5 362[M+C2H5]

+ 21

276 10 287 8 288 52 289 14 290 17 302 5 304 5 314 6 316 18 317 9 318 38 319 9 320 14 330 5 332[M+H]

+ 100 333 18 334 6 346[M+CH3]

+ 17 360[M+C2H5]

+ 23 361 6

130 7 318 14 319 9 320 31 321 7 344 5 346 6 348 7 360 9 361 9 362[M+H]

+ 100 363 20 376[M+CH3]

+ 5 390[M+C2H5]

+ 19















(59)





authors( 214860)



technique




in scheme 2




+

ion



+ and






N

O O

O HF

NHN

[M+H]+ = 320

- CO2

N

O

F

NHN

mz = 276

mz = 278

N

O O

O HF

RI = 100 RI = 60

RI = 55

H

C2 H

4 N

N

H+ H+

H+

N

O O

F

NHN

H+

- H2 O

mz = 302RI = 8

rearrangment
























kJmol-1






species



method

431

Mass

spectr

a of

Peflox

acin

under

EI technique

PA (M) kJmol

-1

∆Hf(M+H)+

kJmol-1

Protonated Site

∆Hf(M) kcalmol

-1

Molecule

904

749

142

297

O12H

N1H

-116

Norfloxacin

916

753

151

314

O12H

N1H

-111

Pefloxacin

904

745

255

418

O12H

N1H

-88

Ciprofloxacin

908

715

2

192

O12H

N1H

-149

Levofloxacin












Table 8




15 eV

70 eV

mz

10

55

3

21

100

4

6

16

10

10

6

10

30

26

7

4

12

61

3

18

100

4

6

14

11

7

4

6

20

15

6

4

334

333 [M]+middot

291

290

289 [M-CO2]+

245

219

218 [M-CO2-C4H9N]+

203 [M-CO2-C4H9N-CH3]+

96

81

79

71 [C4H9N]+bull

70

57

56







800 eV (772 kJ mole-1





Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

-0307

0198

-0262

-0297

0178

-0206

0010

-0020

0056

C4

C4a

C5

C6

C7

C8

C8a

C21

C22

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

0337

-0119

-0016

0103

0081

-0050

0095

0162

-0002

04135

-0301

-0357

-0300

-0169

-0391

0128

0143

-0428

0144

0128

0193

0318

-0082

0000

0124

0218

-0171

0190

0151

-0003

0401

-0293

-0328

-0228

-0124

-0164

0114

0124

-0418

0126

0114

0183

-0019

0037

0016

0021

0137

-0121

0095

-0011

-0001

-0014

0008

0029

0072

0045

0227

-0014

-0019

0010

-0018

-0014

-0010







ion by the







ion at mz 218 with


CO2- C4H9N]+bull





[C4H9N]+bull



On the other



at mz=71 RI=20 in

compariso

n with

Norfloxaci

n the

absence of

ndashCH3

group lead

to produce

the

fragment

[M-

C2H4N]+

ion at mz

= 277

RI=59

Scheme 3 Main

fragmentat

ion

pathways

of

Pefloxacin

at 70 eV

N

O O

O HF

NN

M

=333

- CO2

N

O

F

NN

mz =289

C4 H

9 N

RI = 61 RI = 100

H

N

O

HF

NH2C

RI = 14

mz = 218

H3C

N

O

H

CH2

F

NH2C

mz =203RI = 11

+ +

+

+


mz

- CH

3

H2C

N

CH2

CH2H3C

N

H2CCH2

CH2

H2C

H

r ea r

ang

men

t

C4H9N +

N

O

F

NH2C

O

O H



The

appearance

energy (AE)

of the

fragment

[M-CO2]+bull

ion at

mz=289 is

calculated

(using the

heats of

formation of

∆Hf(M)

molecule

∆Hf (CO2)

and ∆Hf [M-

CO2]+bull

)and

is found to

be equal to

830 eV(801

kJmol-1

)

The

difference

between the

value for

AE [M-CO2]+bull












-1)

Neutral molecule


Molecular ion


∆ L

N1-C2 14016

C2-C3 13689

C3-C4 14885

C4-C4a 15009

C4a-C5 14182

C5-C6 14295

C6-C7 14435

C7-C8 14208

C8-C8a 14299

C8a-N1 14220

N1-C21 14819

C21-C22 15379

C3-C9 14953

C9-O10 13581

C9-O11 12293

C4-O12 12274

C6-F13 13223

C7-N14 14312

N14-C15 14704

C15-C16 15521

C16-N17 14676

N17-C19 14677

C19-C20 15526

C20-N14 14699

N17-C18 14640

N1-C2 14180

C2-C3 13665

C3-C4 14877

C4-C4a 15072

C4a-C5 14101

C5-C6 14324

C6-C7 14928

C7-C8 14547

C8-C8a 14088

C8a-N1 13994

N1-C21 14922

C21-C22 15372

C3-C9 15008

C9-O10 13534

C9-O11 12273

C4-O12 12226

C6-F13 13114

C7-N14 13624

N14-C15 15031

C15-C16 15508

C16-N17 14609

N17-C19 14600

C19-C20 15504

C20-N14 15020

N17-C18 14739

00164

-00024

-00008

00063

-00081

00029

00493

00339

-00211

-00226

00103

-00007

00055

-00047

-00020

-00048

-00109

-00688

00327

-00013

-00067

-00077

-00022

00321

00099


kJmol-1


to 68 kJmol-1







100)







+


+



molecule



[M+C2H5- CO2]+bull

ion

N

O O

O HF

NN

=334

- CO2

N

O

F

NN

mz =290

RI = 100 RI = 31

HH+

[M+H]+

N

O

CF

NN

H+

O

mz = 316

RI = 10

- H2 O

- C2 H

4 N

N

O O

O HF

H+

N

mz = 292

RI = 12

H+

H3C

mz















kJmol-1



-







It is









15 eV

70 eV

mz

11

62

11

67

18

100

11

68

5

7

9

4

4

5

6

6

8

19

14

74

13

71

19

100

11

69

5

8

9

4

5

5

5

6

9

20

332

331 [M]+

290

289 [M-C2H4N]+

288

287 [M-CO2]+

246

245 [M-CO2-C2H4N]+

231

230

229

218

215

204

202

201

57

56










eV(849 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

(e)

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C22

O10

C9

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0277 0206

-0266 0339

-0117 -0021 0133 0076

-0075 0100 0035

-0053 -0057 -0295 0418

-0370 -0295 -0159 -0387 0128 0098

-0312 0096 0127

-0125 0233

-0179 0206

-0085 -0029 0147 0157

-0059 0116

-0042 -0026 -0034 -0285 0380

-0297 0064

-0137 -0419 0133 0099

-0324 0100 0138

0152 0027 0087

-0133 0032

-0008 0014 0081 0016 0016

-0077 0027 0023 0010

-0038 0073 0359 0022

-0032 0005 0001

-0012 0004 0011
















at mz 287 with






ion indicates





















N

O O

O HF

NN

M

= 331

- CO2

N

O

F

NN

= 287

C2 H

4 N

N

O O

O HF

N

RI = 74

RI = 100

RI = 71

H

N

O

HF

RI = 69

C2 H

4 N

- CO2

+ +

H H

H rearengment

N

H rearengm

ent

mz 56RI = 20

mz

mz

mz = 245

mz = 289

H2C

NCH2

CH2




Neutral molecule


Molecular ion


∆ L




CO2)+bull








(050 eV)This














N1-C2 14017

C2-C3 1371

C3-C4 14908

C4-C4a 15019

C4a-C5 14169

C5-C6 1431

C6-C7 14441

C7-C8 14194

C8-C8a 14281

N1-C20 14534

C20-C21 15421

C21-C22 15186

C22-C20 15420

C3-C9 14939

C9-O10 13571

C9-O11 12308

C4-O12 12269

C6-F13 13203

C7-N14 14310

N14-C15 14700

C15-C16 15530

C16-N17 14670

N17-C18 14661

C18-C19 15528

C19-N14 14701

N1-C2 13703

C2-C3 14123

C3-C4 14229

C4-C4a 14585

C4a-C5 14303

C5-C6 14214

C6-C7 14567

C7-C8 14189

C8-C8a 14311

N1-C20 14762

C20-C21 15436

C21-C22 15157

C22-C20 15449

C3-C9 15069

C9-O10 13502

C9-O11 12250

C4-O12 13096

C6-F13 13167

C7-N14 14102

N14-C15 14754

C15-C16 15534

C16-N17 14645

N17-C18 14636

C18-C19 15533

C19-N14 14746

-00314

00413

-00679

-00434

00134

-00096

00126

-00005

00030

00228

00015

-00029

00029

00130

-00069

-00058

00827

-00036

-00208

00054

00004

-00025

-00025

00005

00045















+) cations transfer


+ molecules with



N

O O

O HF

NN

- CO2

N

O

F

NN

N

O O

O HF

N

H

C2 H

4 N

H H

H+

[M+H]+ = 332

RI = 100

H+

mz = 288RI = 52

H+

mz= 290RI = 17

- H2 O

N

O O

F

NN

H

H+

mz = 314RI = 6

445

The

proton


Ciprofloxacin










745kJmol-1

and 904 kJmol-1



kJmol-1


















15 e V

70 e V

mz

16

100

14

5

5

5

9

19

8

7

34

-

17

100

17

5

7

6

12

22

11

10

29

4

362

361[M]+bull

317[M-CO2]+bull

276

273

254

247


232

231

71(C4H9N)+bull

56










eV(801 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

O21

-0299

0201

-0261

0338

-0099

-0028

0112

0092

0079

0051

-0227

-0292

0181

-0209

0322

-0062

-0005

014

0081

0104

0057

-0252

0007

-002

0052

-0016

0037

0023

0028

-0011

0025

0006

-0025

C22

C24

C23

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

015

0091

0016

0416

-0295

-0366

-0297

-0167

-0395

0142

0144

-0429

0143

0142

0194

0155

0088

0011

0402

-0291

-0332

-0244

-0141

-0081

01

0133

-0434

0135

0108

0188

0005

-0003

-0005

-0014

0004

0034

0053

0026

0314

-0042

-0011

-0005

-0008

-0034

-0006




















) The difference



) gives the



(020

eV)

Scheme 7 Main



N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

M

= 361mz = 317

C4H9N

N

O

N

O

HF

CH3

mz = 246

RI= 100 RI= 17

RI = 20

++

H-Rearangment

+

mz = 71RI = 29

+

mz

CH2

N

H2C

CH2

CH3

NH2C

H2C

CH2

CH2

H




Neutral molecule


Molecular ion


∆ L

N1-C2 13975

C2-C3 13719

C3-C4 14898

C4-C4a 15017

C4a-C5 14187

C5-C6 14314

C6-C7 14450

C7-C8 14368

C8-C8a 14446

C8a-N1 14153

C8-O21 13588

O21-C22 14028

C22-C24 15634

C24-N1 14823

C24-C23 15475

C3-C9 14961

C9-O10 13569

C9-O11 12301

C4-O12 12276

C6-F13 13223

C7-N14 14236

N14-C15 14675

C15-C16 15526

C16-N17 14676

N17-C19 14678

C19-C20 15524

C19-N14 14680

N17-C18 14632

N1-C2 14088

C2-C3 13706

C3-C4 14890

C4-C4a 15094

C4a-C5 14207

C5-C6 14253

C6-C7 14713

C7-C8 14520

C8-C8a 14459

C8a-N1 14031

C8-O21 13472

O21-C22 14140

C22-C24 15611

C24-N1 14852

C24-C23 15482

C3-C9 15018

C9-O10 13532

C9-O11 12275

C4-O12 12239

C6-F13 13164

C7-N14 13877

N14-C15 14978

C15-C16 15561

C16-N17 14620

N17-C19 14630

C19-C20 15521

C19-N14 14955

N17-C18 14730

00113

-00013

-00008

00077

00020

-00061

00263

00152

00013

-00122

-00116

00112

-00023

00029

00007

00057

-00037

-00026

-00037

-00059

-00359

00303

00035

-00056

-00048

-00003

00275

00098















and 19 respectively







N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

mz = 318

RI= 14

H+

[M+H]+

mz = 362

RI = 100

N

O

N

NH3C

O

O

OH

F

CH3

H+

- H2 O

mz = 344RI = 5

- C2 H

4 N

N

O

O

O

OH

F

CH3

H+

N

CH3

mz= 320RI = 31

H+








atoms of the ring



908 kJmol-1



kJmol-1



CHAPTER (5)

CONCLUSIONS


[M]+bull



for Levofloxacin







spectra indicated













REFERNCES














New York NY (1969)



















pp142(1998)







Soc3(2006)


















Chemistry (2004)















24714(2003)













(1999)


867105(2008)






241359(2005)






153 37(1996)





1216 794(2009)



250 370(2006)





Chem46 363( 2005)


B 530186(1990)


759(2005)





(1993)




هقدهت هي



للحصىل على


2213





زشق السبع









جبهعخ ثب

كليخ العلم










[M-C2H4N]+ and [M-

CO2-C2H4N]+









[MH-CO2]+bull


+
















هي قجر

























principle(28-29)








showed


law of the form

σ (E) = C (E-Eo)n-1

(4)









which is formed

by the reaction

M+e- M

+bull + 2e

- (5)


IE[M]+bull

= ∆Hf[M]+bull

- ∆Hf[M] (6)

Where ∆Hf[M]+bull





[M]+bull

[F]+

+ [N]bull (7)



AE[F]+ = IE [F] +D[F-N] + Eexc (8)





(∆Eth) = ∆Hf[F]+ + ∆Hf[N] - ∆Hf[M] (9)





∆Hf[F]+ = IE[F] +∆Hf[F] (11)


Stevenson(32)



work of Audier(33)






molecular ion


spectra










is defined by



[A ndash B] +bull

A+ + B

bull (12)

odd even odd

[A ndash B] +bull

Abull + B

+ (13)

odd odd even

The fragment ion A+

or B+









Ionization






















CH4+ e- CH4

+bull CH3

+CH2

+ CH

++ 2e (14)

CH4+bull

+ CH4 CH5+ + CH3

bull (15)

CH3+ + CH4 C2H5

+ + H2 (16)


+




210 Proton Affinity





[BH]+ + M B+[M+H]

+ (17)




M + CH5+

[M+H]+ + CH4 (18)

M + H+ MH

+ (19)


+] = - PA

PA = - ∆Hordm































segments













CHAPTER (3)







software

31 Apparatus




positive ion mode










32 Materials






reagent gas




eV











CHAPTER (4)


41 Results











techniques














in


















literature

42 Discussion













Molecule

R1

R2

Norfloxacin

Pefloxacin

Ciprofloxacin

Levofloxacin

ethyl

ethyl

cyclopropyl


piperazinyl

4-methyl-piprazinyl

piperazinyl

4-methyl-piprazinyl









compounds




NN

N

F

CH3

O O

OH

PEFLOXACIN

H3C

NN

HN

F

O O

OH

CIPROFLOXACIN

NN

N

F

O O

OH

LEVOFLOXACIN

O

CH3H3C





compounds











chapter 2)







mz 320









15 e V

70 e V

mz

11

60

7

52

14

100

5

9

68

2

4

7

8

7

2

2

2

2

-

-

-

-

-

-

-

-

-

8

12

70

9

59

16

100

9

13

88

5

9

4

11

13

6

6

6

6

7

6

6

7

6

6

8

7

14

15

320

319 [M]+middot

278

277 [M-C2H4N]+

276

275 [M-CO2]+

245

234

233[M-CO2-C2H4N]+

219

218

217

204

203

190

189

176

175

161

95

85

83

81

73

71

69

57

56







The

removal

of an

electron

from an

organic

molecule

often

leads to

change in

its

relative










) (using




423

Fragm

entatio

n of

Norflo

xacin

using

EI

techniq

ue

Most

previous


(214850-51) where


However the present









respectively


[M-CO2]+bull



Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C9

O10

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0309

0199

-0264

0338

-0119

-0015

0102

0082

-0050

0096

0160

13002

0417

-0295

-0367

-0298

-0169

-0395

0127

0095

-0320

0095

0127

-0287

0175

-0202

0314

-0078

0000

0137

0173

-0145

0190

0149

-0004

0399

-0291

-0324

-0230

-0128

-0168

0082

0103

-0339

0105

0078

0022

-0024

0062

-0024

0041

0015

0035

0091

-0095

0094

-0011

-0006

-0018

0004

0043

0068

0041

0227

-0045

0008

-0019

0010

-0049







fragment (odd-




CO2]+bull



bull radical








+ ion through


(Scheme 1)




C3H7N (Scheme 1)


for



and ∆Hf(M)


) (Table





and



N

O O

O HF

NN

M

= 319

- CO2

N

O

F

NN

= 275

C2 H

4 N

= 277

N

O O

O HF

RI = 70 RI = 100

RI = 59

H

N

O

HF

RI = 88

C2H

4N

- CO2

= 233

NN

+ +

- C3 H

7 N

N

O

HF

N

mz mz

mz

mz = 218

RI = 9

mz

HH rearrangement

rearrangement

+

si m

pl e

cl e

av

ag

e



Table

5

Calcul

ated

∆Hf(M

)∆Hf(

M)+bull

an

d IE

values

for the

four

6-

fluoro

quinol

one

molec

ules

using

MND

O method

Neutral molecule




∆ L

N1-C2 14007

C2-C3 13700

C3-C4 14881

C4-C4a 15012

C4a-C5 14185

C5-C6 14294

C6-C7 14433

C7-C8 14203

C8-C8a 14304

C8a-N1 14204

N1-C20 14830

C20-C21 15379

C3-C9 14950

C9-O10 13571

C9-O11 12304

C4-O12 12275

C6-F13 13223

C7-N14 14306

N14-C15 14706

C15-C16 15517

C16-N17 14676

N17-C18 14677

C18-C19 15514 C19-N14 14706

N1-C2 14167

C2-C3 13650

C3-C4 14863

C4-C4a 15080

C4a-C5 14118

C5-C6 14299

C6-C7 14807

C7-C8 14391

C8-C8a 14142

C8a-N1 13980

N1-C20 14934

C20-C21 15374

C3-C9 15028

C9-O10 13527

C9-O11 12268

C4-O12 12237

C6-F13 13126

C7-N14 13740

N14-C15 14962

C15-C16 15615

C16-N17 14567

N17-C18 14571

C18-C19 15558 C19-N14 14935

00160

-00050

-00018

00068

-00067

00005

00374

00188

-00162

-00224

00104

-00005

00078

-00044

-00036

-00038

-00097

-00566

00256

00098

-00109

-00106

00044

00229

IE

eV k J mol-1

∆Hf(M)+bull

k J mol-1

∆Hf(M)

k J mol-1

Molecule




) and



CO2]+bull









81 782 305 -485

Norfloxacin

8 772 314 -464

Pefloxacin

88 849 485 -368

Ciprofloxacin

83 801 142 -631

Levofloxacin




-1) The


-1)


kJmol-1


ion

by 106 kJmol-1























mz RI[] mz RI[]

mz RI[] mz RI[]

97 17 163 8 218 15 236 32 237 6 250 6 252 5 258 7 264 9 270 8 272 5 274 6 275 9 276 60 277 23 278 55 279 13 290 10 292 9 302 8 304 20 306 12 316 5 318 10 320[M+H]

+ 100 321 18 334[M+CH3]

+ 14 348[M+C2H5]

+ 20

289 6 290 31 291 9 292 12 316 10 317 5 318 27 319 6 332 6 333 6 334[M+H]

+ 100 335 19 346 6 348[M+CH3]

+ 5 362[M+C2H5]

+ 21

276 10 287 8 288 52 289 14 290 17 302 5 304 5 314 6 316 18 317 9 318 38 319 9 320 14 330 5 332[M+H]

+ 100 333 18 334 6 346[M+CH3]

+ 17 360[M+C2H5]

+ 23 361 6

130 7 318 14 319 9 320 31 321 7 344 5 346 6 348 7 360 9 361 9 362[M+H]

+ 100 363 20 376[M+CH3]

+ 5 390[M+C2H5]

+ 19















(59)





authors( 214860)



technique




in scheme 2




+

ion



+ and






N

O O

O HF

NHN

[M+H]+ = 320

- CO2

N

O

F

NHN

mz = 276

mz = 278

N

O O

O HF

RI = 100 RI = 60

RI = 55

H

C2 H

4 N

N

H+ H+

H+

N

O O

F

NHN

H+

- H2 O

mz = 302RI = 8

rearrangment
























kJmol-1






species



method

431

Mass

spectr

a of

Peflox

acin

under

EI technique

PA (M) kJmol

-1

∆Hf(M+H)+

kJmol-1

Protonated Site

∆Hf(M) kcalmol

-1

Molecule

904

749

142

297

O12H

N1H

-116

Norfloxacin

916

753

151

314

O12H

N1H

-111

Pefloxacin

904

745

255

418

O12H

N1H

-88

Ciprofloxacin

908

715

2

192

O12H

N1H

-149

Levofloxacin












Table 8




15 eV

70 eV

mz

10

55

3

21

100

4

6

16

10

10

6

10

30

26

7

4

12

61

3

18

100

4

6

14

11

7

4

6

20

15

6

4

334

333 [M]+middot

291

290

289 [M-CO2]+

245

219

218 [M-CO2-C4H9N]+

203 [M-CO2-C4H9N-CH3]+

96

81

79

71 [C4H9N]+bull

70

57

56







800 eV (772 kJ mole-1





Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

-0307

0198

-0262

-0297

0178

-0206

0010

-0020

0056

C4

C4a

C5

C6

C7

C8

C8a

C21

C22

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

0337

-0119

-0016

0103

0081

-0050

0095

0162

-0002

04135

-0301

-0357

-0300

-0169

-0391

0128

0143

-0428

0144

0128

0193

0318

-0082

0000

0124

0218

-0171

0190

0151

-0003

0401

-0293

-0328

-0228

-0124

-0164

0114

0124

-0418

0126

0114

0183

-0019

0037

0016

0021

0137

-0121

0095

-0011

-0001

-0014

0008

0029

0072

0045

0227

-0014

-0019

0010

-0018

-0014

-0010







ion by the







ion at mz 218 with


CO2- C4H9N]+bull





[C4H9N]+bull



On the other



at mz=71 RI=20 in

compariso

n with

Norfloxaci

n the

absence of

ndashCH3

group lead

to produce

the

fragment

[M-

C2H4N]+

ion at mz

= 277

RI=59

Scheme 3 Main

fragmentat

ion

pathways

of

Pefloxacin

at 70 eV

N

O O

O HF

NN

M

=333

- CO2

N

O

F

NN

mz =289

C4 H

9 N

RI = 61 RI = 100

H

N

O

HF

NH2C

RI = 14

mz = 218

H3C

N

O

H

CH2

F

NH2C

mz =203RI = 11

+ +

+

+


mz

- CH

3

H2C

N

CH2

CH2H3C

N

H2CCH2

CH2

H2C

H

r ea r

ang

men

t

C4H9N +

N

O

F

NH2C

O

O H



The

appearance

energy (AE)

of the

fragment

[M-CO2]+bull

ion at

mz=289 is

calculated

(using the

heats of

formation of

∆Hf(M)

molecule

∆Hf (CO2)

and ∆Hf [M-

CO2]+bull

)and

is found to

be equal to

830 eV(801

kJmol-1

)

The

difference

between the

value for

AE [M-CO2]+bull












-1)

Neutral molecule


Molecular ion


∆ L

N1-C2 14016

C2-C3 13689

C3-C4 14885

C4-C4a 15009

C4a-C5 14182

C5-C6 14295

C6-C7 14435

C7-C8 14208

C8-C8a 14299

C8a-N1 14220

N1-C21 14819

C21-C22 15379

C3-C9 14953

C9-O10 13581

C9-O11 12293

C4-O12 12274

C6-F13 13223

C7-N14 14312

N14-C15 14704

C15-C16 15521

C16-N17 14676

N17-C19 14677

C19-C20 15526

C20-N14 14699

N17-C18 14640

N1-C2 14180

C2-C3 13665

C3-C4 14877

C4-C4a 15072

C4a-C5 14101

C5-C6 14324

C6-C7 14928

C7-C8 14547

C8-C8a 14088

C8a-N1 13994

N1-C21 14922

C21-C22 15372

C3-C9 15008

C9-O10 13534

C9-O11 12273

C4-O12 12226

C6-F13 13114

C7-N14 13624

N14-C15 15031

C15-C16 15508

C16-N17 14609

N17-C19 14600

C19-C20 15504

C20-N14 15020

N17-C18 14739

00164

-00024

-00008

00063

-00081

00029

00493

00339

-00211

-00226

00103

-00007

00055

-00047

-00020

-00048

-00109

-00688

00327

-00013

-00067

-00077

-00022

00321

00099


kJmol-1


to 68 kJmol-1







100)







+


+



molecule



[M+C2H5- CO2]+bull

ion

N

O O

O HF

NN

=334

- CO2

N

O

F

NN

mz =290

RI = 100 RI = 31

HH+

[M+H]+

N

O

CF

NN

H+

O

mz = 316

RI = 10

- H2 O

- C2 H

4 N

N

O O

O HF

H+

N

mz = 292

RI = 12

H+

H3C

mz















kJmol-1



-







It is









15 eV

70 eV

mz

11

62

11

67

18

100

11

68

5

7

9

4

4

5

6

6

8

19

14

74

13

71

19

100

11

69

5

8

9

4

5

5

5

6

9

20

332

331 [M]+

290

289 [M-C2H4N]+

288

287 [M-CO2]+

246

245 [M-CO2-C2H4N]+

231

230

229

218

215

204

202

201

57

56










eV(849 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

(e)

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

C20

C21

C22

O10

C9

O11

O12

F13

N14

C15

C16

N17

C18

C19

-0277 0206

-0266 0339

-0117 -0021 0133 0076

-0075 0100 0035

-0053 -0057 -0295 0418

-0370 -0295 -0159 -0387 0128 0098

-0312 0096 0127

-0125 0233

-0179 0206

-0085 -0029 0147 0157

-0059 0116

-0042 -0026 -0034 -0285 0380

-0297 0064

-0137 -0419 0133 0099

-0324 0100 0138

0152 0027 0087

-0133 0032

-0008 0014 0081 0016 0016

-0077 0027 0023 0010

-0038 0073 0359 0022

-0032 0005 0001

-0012 0004 0011
















at mz 287 with






ion indicates





















N

O O

O HF

NN

M

= 331

- CO2

N

O

F

NN

= 287

C2 H

4 N

N

O O

O HF

N

RI = 74

RI = 100

RI = 71

H

N

O

HF

RI = 69

C2 H

4 N

- CO2

+ +

H H

H rearengment

N

H rearengm

ent

mz 56RI = 20

mz

mz

mz = 245

mz = 289

H2C

NCH2

CH2




Neutral molecule


Molecular ion


∆ L




CO2)+bull








(050 eV)This














N1-C2 14017

C2-C3 1371

C3-C4 14908

C4-C4a 15019

C4a-C5 14169

C5-C6 1431

C6-C7 14441

C7-C8 14194

C8-C8a 14281

N1-C20 14534

C20-C21 15421

C21-C22 15186

C22-C20 15420

C3-C9 14939

C9-O10 13571

C9-O11 12308

C4-O12 12269

C6-F13 13203

C7-N14 14310

N14-C15 14700

C15-C16 15530

C16-N17 14670

N17-C18 14661

C18-C19 15528

C19-N14 14701

N1-C2 13703

C2-C3 14123

C3-C4 14229

C4-C4a 14585

C4a-C5 14303

C5-C6 14214

C6-C7 14567

C7-C8 14189

C8-C8a 14311

N1-C20 14762

C20-C21 15436

C21-C22 15157

C22-C20 15449

C3-C9 15069

C9-O10 13502

C9-O11 12250

C4-O12 13096

C6-F13 13167

C7-N14 14102

N14-C15 14754

C15-C16 15534

C16-N17 14645

N17-C18 14636

C18-C19 15533

C19-N14 14746

-00314

00413

-00679

-00434

00134

-00096

00126

-00005

00030

00228

00015

-00029

00029

00130

-00069

-00058

00827

-00036

-00208

00054

00004

-00025

-00025

00005

00045















+) cations transfer


+ molecules with



N

O O

O HF

NN

- CO2

N

O

F

NN

N

O O

O HF

N

H

C2 H

4 N

H H

H+

[M+H]+ = 332

RI = 100

H+

mz = 288RI = 52

H+

mz= 290RI = 17

- H2 O

N

O O

F

NN

H

H+

mz = 314RI = 6

445

The

proton


Ciprofloxacin










745kJmol-1

and 904 kJmol-1



kJmol-1


















15 e V

70 e V

mz

16

100

14

5

5

5

9

19

8

7

34

-

17

100

17

5

7

6

12

22

11

10

29

4

362

361[M]+bull

317[M-CO2]+bull

276

273

254

247


232

231

71(C4H9N)+bull

56










eV(801 kJmol-1






Atom

Neutral molecule

(e)

Charged molecule

(e)

∆

N1

C2

C3

C4

C4a

C5

C6

C7

C8

C8a

O21

-0299

0201

-0261

0338

-0099

-0028

0112

0092

0079

0051

-0227

-0292

0181

-0209

0322

-0062

-0005

014

0081

0104

0057

-0252

0007

-002

0052

-0016

0037

0023

0028

-0011

0025

0006

-0025

C22

C24

C23

C9

O10

O11

O12

F13

N14

C15

C16

N17

C19

C20

C18

015

0091

0016

0416

-0295

-0366

-0297

-0167

-0395

0142

0144

-0429

0143

0142

0194

0155

0088

0011

0402

-0291

-0332

-0244

-0141

-0081

01

0133

-0434

0135

0108

0188

0005

-0003

-0005

-0014

0004

0034

0053

0026

0314

-0042

-0011

-0005

-0008

-0034

-0006




















) The difference



) gives the



(020

eV)

Scheme 7 Main



N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

M

= 361mz = 317

C4H9N

N

O

N

O

HF

CH3

mz = 246

RI= 100 RI= 17

RI = 20

++

H-Rearangment

+

mz = 71RI = 29

+

mz

CH2

N

H2C

CH2

CH3

NH2C

H2C

CH2

CH2

H




Neutral molecule


Molecular ion


∆ L

N1-C2 13975

C2-C3 13719

C3-C4 14898

C4-C4a 15017

C4a-C5 14187

C5-C6 14314

C6-C7 14450

C7-C8 14368

C8-C8a 14446

C8a-N1 14153

C8-O21 13588

O21-C22 14028

C22-C24 15634

C24-N1 14823

C24-C23 15475

C3-C9 14961

C9-O10 13569

C9-O11 12301

C4-O12 12276

C6-F13 13223

C7-N14 14236

N14-C15 14675

C15-C16 15526

C16-N17 14676

N17-C19 14678

C19-C20 15524

C19-N14 14680

N17-C18 14632

N1-C2 14088

C2-C3 13706

C3-C4 14890

C4-C4a 15094

C4a-C5 14207

C5-C6 14253

C6-C7 14713

C7-C8 14520

C8-C8a 14459

C8a-N1 14031

C8-O21 13472

O21-C22 14140

C22-C24 15611

C24-N1 14852

C24-C23 15482

C3-C9 15018

C9-O10 13532

C9-O11 12275

C4-O12 12239

C6-F13 13164

C7-N14 13877

N14-C15 14978

C15-C16 15561

C16-N17 14620

N17-C19 14630

C19-C20 15521

C19-N14 14955

N17-C18 14730

00113

-00013

-00008

00077

00020

-00061

00263

00152

00013

-00122

-00116

00112

-00023

00029

00007

00057

-00037

-00026

-00037

-00059

-00359

00303

00035

-00056

-00048

-00003

00275

00098















and 19 respectively







N

O

N

NH3C

O

O

OH

F

CH3

CO2 N

O

N

NH3C

O

HF

CH3

mz = 318

RI= 14

H+

[M+H]+

mz = 362

RI = 100

N

O

N

NH3C

O

O

OH

F

CH3

H+

- H2 O

mz = 344RI = 5

- C2 H

4 N

N

O

O

O

OH

F

CH3

H+

N

CH3

mz= 320RI = 31

H+








atoms of the ring



908 kJmol-1



kJmol-1



CHAPTER (5)

CONCLUSIONS


[M]+bull



for Levofloxacin







spectra indicated













REFERNCES














New York NY (1969)



















pp142(1998)







Soc3(2006)


















Chemistry (2004)















24714(2003)













(1999)


867105(2008)






241359(2005)






153 37(1996)





1216 794(2009)



250 370(2006)





Chem46 363( 2005)


B 530186(1990)


759(2005)





(1993)




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للحصىل على


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زشق السبع









جبهعخ ثب

كليخ العلم










[M-C2H4N]+ and [M-

CO2-C2H4N]+









[MH-CO2]+bull


+
















هي قجر













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Benha University Physics department MASS ......ionization mass spectra of some 6-fluoroquinolones molecules, namely: Norfloxacin, Pefloxacin, Ciprofloxacin and Levofloxacin.While the