Radionica

Dan III

SVEOBUHVATNA DVODIMENZIONALNA GASNA

HROMATOGRAFIJA SA MASENIM

SPEKTROMETROM

(GCXGC-MS)

Marija Lješević,

Istraživač pripravnik, Institut za hemiju, tehnologiju i metalurgiju Univerziteta u Beogradu

U Beogradu, 23.11.2018.

GASNA HROMATOGRAFIJA

Tehnika za razdvajanje isparljivih jedinjenja

https://teaching.shu.ac.uk/hwb/chemistry/tutorials/chrom/gaschrm.htm

GC-MS

Ima veći kapacitet pikova u odnosu na ostale

hromatografske tehnike

Razdvaja 100-150 jedinjenja

U zavisnosti od načina jonizacije i vrste MS

detektora osetljivost od 1 pg-100 pg

GC-GC I GCXGC

Multidimenzional

na gasna

hromatografija

Heart-cut process

Sveobuhvatna

gasna

hromatografija

https://www.omicsonline.org/editor-pdf/Hadir_M_Maher_Shalaby.pdf

GC I GCXGC HROMATOGRAM AROMATIČNE

FRAKCIJE

• Kapacitet pikova- maksimalni teorijski broj

kompnenti koje mogu da se razdvoje na nekoj koloni pri

određenim uslovima

• GCxGC: kapacitet pikova prve kolone x kapacitet pikova druge

kolone

Phillips i saradnici- analiza naftnih derivata

GCXGC-MS

Ceo uzorak se razdvaja u obe kolone

https://www.shimadzu.com/an/gcms/gcgc-2.html

• Najvažniji deo GCxGC sistema

• Modulatori sa ventilima, termalni i kriogeni

•Imaju tri glavne funkcije: akumuliranje, refokusiranje i oslobadjanje

uzorka

MODULATOR

Adahchour et al. Trends in Analytical Chemistry (2006) 25:5, p 438

•Vreme modulacije-

Trajanje kompletnog ciklusa

modulacije, jednako je vremenu

koje prođe između dva

injektovanja u drugu kolonu.

•3-4 modulacije za 1 pik na

prvoj koloni (modulacija ne

bi trebalo da bude veća od

cetvrtine širine pika)

•Pikovi su veoma uski (50-

600 ms

Marriott, Shellie, Trends in Analycal

chemistry, 2002, 21, p 573.

Adahchour et al. Trends in Analytical Chemistry (2006) 25:5, p 438

Low scan times ( up to 100 ms)

Structured chromatograms

Adahcour et al, Trends in Analytical chemistry (2006), 25:5, p 438

GC

GC oven temperature Temp range: amb. + 4˚C to 450˚C (in 1 °C steps)

Heat-up rate (1) Max. 100 °C/min, in 0.01 °C steps (230 V specifications)

GC cooling rate Cooling from 450 °C to 50 °C in 3.5 minutes or less

Temperature control 8 or more temperature control zones

Column flow rate Can accommodate column flow rates up to 15 mL/min.

Gas control The carrier gas can be controlled in constant linear velocity mode.

Pressure 0.000 to 970kPa

Columns x 2 RTX-1, 30 x 0.25 x 0.25 and BPX-50 1 m, 0.15 mm, 0.15 μm

AutoinjectorAuto injector with 15 sample position. Sample volume

1.5ml/2ml. Variable injection

Mass Spectrometer

Mass range Satisfies m/z range of 1.5 to 1,090 Separator

Quadrupole with a pre-filter (equipped

with a low-noise electron multiplier with

overdrive lens)

Resolution (1) R ³ 2M (FWHM) minimumQuadrupole rod contamination

countermeasures

The analysis system is equipped with a

quadrupole mass filter with a pre-rod.

Resolution (2) 2,000 minimum (FWHM at m/z 614) Ionization voltage Configurable from 10 eV to 200 eV

Dynamic

range of the

electrical

system

The dynamic range is at least 1.6 x 10^7. Ion source temperatureIndependently heated up to 350 °C or

higher.

Sensitivity (EI

scan)1pg octafluoronaphtalene m/z 272, S/N > 1500 Scan speed

Maximum scan speed of at least 20,000

u/sec

Sensitivity (CI

scan)

100 fg octafluoronaphtalene m/z 272, S/N >

500 (For methane)Filament (1) A dual filament is used

Sensitivity

(NCI scan)

100 fg octafluoronaphtalene m/z 272, S/N >

500 (For methane)Modulator

Two stage loop modulator; cycle range

from 1000ms – 32000ms

Nitrogen generatorAt least 99.999% purity of given gases, flow rate 250,600 cc/min, deliver pressure 0-

80psi, inlet air requirements Minimum 35 l/min at 120-145psi

PRIMERI

Ukupni ugljovodonici nafte

BIOCHEMICAL PROFILING OF MICROORGANISMS USING COMPREHENSIVE GCxGC-MS

Djurić et al., Int J Biol Macromol 2017;104:311-21.Izrael-Živković et al., Journal of Molecular Catalysis. B, Enzymatic 2017; in press

The fatty acid methyl ester profile of

Brachybacterium sp. CH-KOV3 a) GC–MS;

b) 2D GCxGC–MS.

23

Lama et al., ACS Sustainable Chemistry & Engineering 2017;5:2415-20

Analiza degradacije kraft lignina

Degradation of grape pomace

PCB

Tianeptin- antidepresiv

Hipotalamus miša