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CHEMISTRY OF IONS IN THE GAS PHASE: FULLERENES AND ATOMIC CLUSTERS. Olivera Ne šković Vinča Institute of Nuclear Sciences. A simple definition of a Mass Spectrometer. A Mass Spectrometer is an analytical instrument that can separate charged molecules according to their mass–to–charge ratio. - PowerPoint PPT Presentation
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CHEMISTRY OF IONS IN THE GAS PHASE: FULLERENES AND
ATOMIC CLUSTERS
Olivera Nešković
Vinča Institute of Nuclear Sciences
A simple definition of a Mass A simple definition of a Mass SpectrometerSpectrometer
• A Mass Spectrometer is an analytical instrument A Mass Spectrometer is an analytical instrument that can separate charged molecules according that can separate charged molecules according to theirto their mass–to–charge ratio.mass–to–charge ratio.
• Mass spectrometer can answer the questions Mass spectrometer can answer the questions “what is in the sample” (qualitative structural “what is in the sample” (qualitative structural information) and “how much is present” information) and “how much is present” (quantitative determination) for a very wide (quantitative determination) for a very wide range of samples at high sensitivityrange of samples at high sensitivity
Investigator(s) Contribution Nobel Prize
Thomson 1897 discovery of the electron, first mass spectrometer
1906 in Physics
Dempster 1918 Electron ionization and magnetic focusing
Aston 1919 atomic weights using MS and isotopes study
1922 in Chemistry
Stephens 1946 Time-of-flight mass analysis
Hipple, Sommer, and Thomas
1949 Ion cyclotron resonance
Johnson and Nier 1953 Double-focusing instruments
Paul and Steinwedel
1953 Quadrupole analyzers 1989 in Physics
Beynon 1956 High-resolution MS
Mass
Spectrometry
Mass
Spectrometry
Mass S
pectrometry
Mass S
pectrometry
VINCAAdvanced
MassSpectrometry
FacilityPictureGallery
FULLERENES
DERIVATIZED (FUNCTIONALIZED) FULLERENES
CARBON NANOTUBES
FUNCTIONALIZED NANOTUBES
• Li@C60, Li@C70, Li2@C70 and Li3@C70 • Fullerenol C60(OH)16, C60(OH)22• Fullerene bisadduct derivative C60C15H29N3O4 • Carbon nanotubes as Maldi matrix• Decorated carbon nanotubes by silver clusters• Endo and exo fullerenes by 99mTc• Carbon nanotubes derocated by DNA• Sequencing DNA by carbon nanotubes
The personal review (the limiting range of topics):
• Prof. Dr. T.D. Märk, Institut für Ionenphysik, Innsbruck, Austria
• Prof. Dr. Chava Lifshictz, The Hebrew University of Jerusalem, Israel
• Prof. Dr. Lev Sidorov, Moscow State University, Russia
• Prof. Dr. Thomas Drewello, University of Warwick, UK
• Prof. Dr. Maurizio Prato, University of Trieste, Italy
Camera
Pumping Pumping
Timed ion selector
Reflector
Lineardetector
Extractiongrids
Reflectordetector
Laser
Sample plate
Components of a Mass Spectrometer
INLET ION SOURCE MASS FILTER DETECTOR
Sample plate
HPLCGCSolids probe
MALDI
API/ElectrosprayIonSprayEI, CI
TOF
QuadrupoleIon TrapMagnetic SectorFTMS
“Hybrid”
Microchannel PlateElectron Multiplier
Laser flash produces matrix (M) neutrals, positive, negative ions and sample neutrals.
M M*, MH+, (M-H)-
Sample molecules (A) are ionised by gas phase proton transfer
MH++A AH++M(M-H)-+A AH-+M
Ion Source: MALDI (Matrix Assisted Laser Desorption Ionisation)
+
+
+
+
+Ions of same mass, different velocities
++
Delayed Extraction (DE)
1: Laser fired. Formed ions detach from plate in the absence of an electric field.
0 kV
0 nsec
4: Slow ions catch up with faster ones at the detector.
+20 kV+
+++
3: Field applied. Gradient accelerates slow ions more than fast ones.
+20 kV ++
+
2: Expansion of the ion cloud in the absence of an electric field.
0 kV
150 nsec
++ +
Detector
The electrical field applied within the reflector produces an ion mirror effect directing the ions towards a second detector
Mass Filter: Reflector TOF
Improvement in resolution by • Increasing the effective flight length of the tube• Re-focusing of analogous ions having slight different energy due to initial spread in the ion source
2,4,6-trihydroxy acetophenone (THAP)
-cyano-4-hydroxycinnamic acid2,5-dihydroxybenzoic acid (2,5-DHB)
Dithranol trans-3-indoleacrylic acid
Sinapinic acid (3,5-Dimethoxy-4-hydroxy cinnamic acid)
2-(4-hydroxyphenylazo)-benzoic acid (HABA)
3-hydroxypicolinic acid (3-HPA)
COOH
OH
N N
OH O OH
HO
CH3O
CH3O
CH CHCOOH
COOH
OHN
OH
OHHO
COCH3
HO
CH C(CN)COOH
C C
COOH
N
H
H
OH
HO
COOH
Carbon ClustersPeptide (0.1-10 pmol/l)
Protein (0.1-10 pmol/ l)
Oligonucleotide (10-100 pmol/ l)
Polymer (10-4M)
MALDI-TOF Matrices
Isotopic Resolution
• What benefit is high resolution• Improved identification of peptides• Indication of potential modification• Greater degree of mass accuracy
• Resolution is defined as :
Mass / (peak width at half peak height)
High Resolution - Too much data?Monoisotopic resolution of Insulin
C12 : 5730.61
C13
2 x C13
In compounds with more than 100 carbon atoms the height of the 13C isotope peak exceeds the height of the 12C peak
MALDI TOF mass spectrum of the fullerenol C60(OH)16 containing sample using DCTB as a
matrix and the corresponding negative-ion results
MALDI TOF mass spectrum of the novel fullerene bisadduct derivative C60C15H29N3O4. M+ and [M-H]+ positive ions , m/z=
1035.56 and 1036.48, were detected using CHCA and DCTB matrices
Silver clusters on carbon nanotubes
Figure 1. TEM images of Ag/polymer MWCNT, (a) in the atmosphere of Ar, (b) in the
500 520 540 560 580 600
Mass (m /z)
8.6E +4
0102030405060708090
100
% In
tens
ity
<<A5_20090401_O3>> 4700 Reflector Spec #1=>SM3[BP = 502.9, 85908]
502.
8875
504.
8934
575.
6540
538.
0265
540.
0317
573.
6571
577.
6596
511.
7487
513.
7502
500.
8856
548.
8847
546.
8802
539.
0295
506.
9008
536.
0130
503.
8916
541.
0361
571.
6611
509.
7503
515.
7507
579.
6620
592.
8669
550.
8857
576.
6692
544.
8741
501.
8875
574.
6693
528.
8879
530.
8863
590.
8674
547.
8834
584.
0289
517.
2814
542.
5086
526.
8900
594.
8686
519.
2823
512.
7545
582.
0224
537.
7695
524.
9095
533.
7408
558.
8225
507.
9090
586.
0416
535.
2653
556.
8302
522.
0139
578.
2431
500.
0455
597.
1603
572.
6711
560.
8234
554.
0315
570.
8796
566.
0222
568.
0260
500 520 540 560 580 600
Mass (m /z)
5.9E +4
0102030405060708090
100
% In
tens
ity
<<A4_20090401_O2>> 4700 Reflector Spec #1[BP = 610.8, 83871]50
4.88
17
502.
8788
575.
6449
538.
0115
540.
0176
548.
8660
573.
6461
546.
8654
577.
6464
592.
8387
511.
7328
500.
8739
513.
7347
506.
8859
550.
8667
539.
0154
503.
8807
541.
0216
590.
8397
594.
8358
535.
9985
571.
6459
509.
7336
579.
6465
515.
7372
501.
8754
544.
8619
576.
6519
547.
8666
584.
0125
530.
8639
517.
2804
582.
0063
574.
6469
519.
2761
507.
8861
528.
8698
543.
0383
532.
8652
586.
0269
526.
8759
512.
7377
558.
8168
560.
8096
522.
0126
500 520 540 560 580 600
Mass (m /z)
9.1E +4
0102030405060708090
100
% In
tens
ity
<<A2_20090401_O1>> 4700 Reflector Spec #1[BP = 610.8, 98238]
504.
8709
502.
8666
537.
9944
540.
0009
548.
8569
575.
6302
546.
8552
506.
8752
573.
6307
511.
7164
500.
8580
513.
7162
577.
6312
538.
9969
592.
8418
550.
8581
541.
0039
503.
8677
535.
9811
505.
8734
583.
9943
590.
8431
594.
8422
530.
8552
509.
7170
547.
8573
581.
9841
544.
8486
515.
7169
501.
8599
528.
8582
571.
6323
586.
0027
579.
6296
507.
8778
532.
8577
576.
6354
543.
0150
526.
8577
551.
8629
534.
7233
574.
6387
512.
7198
524.
8610
540.
1561
517.
2502
538.
1509
519.
2477
536.
7193
597.
1165
573.
1227
521.
9890
567.
9949
565.
9926
553.
9944
Mass spectrum of silver clusters
Using carbon nanotubes to inducemicronuclei and double strand breaks of
the DNA in human cellsJelena Cveticanin, Gordana Joksic, Andreja Leskovac,
Sandra Petrovic, Ana Valenta Sobot and Olivera Neskovic1Vinca Institute of Nuclear Sciences, PO Box 522, Belgrade, Serbia
Figure 1 Figure 2
Figure 1: Implication of functionalized CNTS in the human lymphocyte cell
Figure 2: STM picture of functionalized CNTS by sequence of DNA
Hipervalent molecules
LinI, n=2-6Knudsen efusion mass spectromety
LiI with C70Experimental and theoretical investigation of
new hypervalent molecules LinF (n = 2–4)