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
MODULATOR Najvažniji deo GCxGC sistema Modulatori sa ventilima, termalni i kriogeni Imaju tri glavne funkcije: akumuliranje, refokusiranje i oslobadjanje uzorka
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
Autoinjector Auto injector with 15 sample position. Sample volume 1.5ml/2ml. Variable injection GC GC oven temperature Heat-up rate (1) GC cooling rate Temperature control Column flow rate Gas control Pressure Columns x 2 Temp range: amb. + 4 C to 450 C (in 1 C steps) Max. 100 C/min, in 0.01 C steps (230 V specifications) Cooling from 450 C to 50 C in 3.5 minutes or less 8 or more temperature control zones Can accommodate column flow rates up to 15 ml/min. The carrier gas can be controlled in constant linear velocity mode. 0.000 to 970kPa RTX-1, 30 x 0.25 x 0.25 and BPX-50 1 m, 0.15 mm, 0.15 μm
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) minimum Quadrupole 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 temperature Independently 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 generator At 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 The fatty acid methyl ester profile of Brachybacterium sp. CH-KOV3 a) GC MS; b) 2D GCxGC MS. 23 Djurić et al., Int J Biol Macromol 2017;104:311-21. Izrael-Živković et al., Journal of Molecular Catalysis. B, Enzymatic 2017; in press
Analiza degradacije kraft lignina Lama et al., ACS Sustainable Chemistry & Engineering 2017;5:2415-20
Degradation of grape pomace
PCB
Tianeptin- antidepresiv Hipotalamus miša