1 / 28

Pr. Jean-Louis Habib Jiwan UCL – Département de chimie habib@chim.ucl.ac.be

Les détecteurs de masse : une révolution en chromatographie 2ème partie : chromatographie et spectrométrie de masse. Pr. Jean-Louis Habib Jiwan UCL – Département de chimie habib@chim.ucl.ac.be. Couplings. EI CI. GC. On line. ESI APCI APPI. LC. Off line. MALDI. LC. DESI. TLC.

quynh
Download Presentation

Pr. Jean-Louis Habib Jiwan UCL – Département de chimie habib@chim.ucl.ac.be

An Image/Link below is provided (as is) to download presentation Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author. Content is provided to you AS IS for your information and personal use only. Download presentation by click this link. While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server. During download, if you can't get a presentation, the file might be deleted by the publisher.

E N D

Presentation Transcript

  1. Les détecteurs de masse : une révolution en chromatographie 2ème partie : chromatographie et spectrométrie de masse Pr. Jean-Louis Habib Jiwan UCL – Département de chimie habib@chim.ucl.ac.be

  2. Couplings EI CI GC On line ESI APCI APPI LC Off line MALDI LC DESI TLC Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  3. Couplings : MALDI - LC LC Source : documentation Applied Biosystem MALDI - MS Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  4. On line couplings : acquisition modes TIC ? SRM RIC SIM MRM Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  5. Acquisition modes and data treatment intensity ● ● ● ● ● ● ● ● ● ● ● ● ● ● time Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  6. Acquisition modes and data treatment : pesticide mixture LC analysis of a pesticide mixture Source : B Ardrey « Liquid Chromatography-Mass Spectrometry. An Introduction », Wiley 2003 Micromass data Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  7. Acquisition modes and data treatment : pesticide mixture Background mass spectrum obtained for this pesticide mixture analysis RIC Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  8. Acquisition modes and data treatment : pesticide mixture Component eluting after 4.65 min Background substraction Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  9. Acquisition modes and data treatment : pesticide mixture Component eluting after 5.05 min Background substraction Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  10. Acquisition modes and data treatment : pesticide mixture Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  11. Acquisition modes and data treatment : GC-MS / SCAN GC – MS of urine sample after trimethylsilylation Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  12. Acquisition modes and data treatment : GC-MS / SCAN Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  13. Acquisition modes and data treatment : Deconvolution GC – MS of hydrocarbon mixtures Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  14. Acquisition modes and data treatment : METOCLOPRAMIDE Solid-state radiolysis of METOCLOPRAMIDE LC-MS analysis APCI mode  C14H22N3O2Cl Chemical mass 299.8 Exact mass 299.1400 Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  15. Acquisition modes : detection of target compounds SCAN, SIM or SRM ? SIM = Single Ion Monitoring SRM = Single Reaction Monitoring Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  16. Full Scan Precursor ion scan m/z 68 Neutral loss scan 42 Da Acquisition modes and data treatment : Atrazine analysis LC-MS of Atrazine and its degradation products [N=C-NH-C=N+H]+ m/z = 68 CH3-CH=CH2 MW = 42 Source : RJ Steen et al, J Chromato A 2001, 915, 129 Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  17. Acquisition modes : SIM or SRM GC-MS of heptafluorobutyryl derivative of Methtryptoline SIM 362 m/z SRM 362 → 179 m/z RA Yost Adv Mass Spectrom 1985, 10B, 1479 Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  18. FT ICR ORBITRAP TOF LC ION TRAP Ion source Acquisition modes : Advanced methods on hybrid instruments Chromatographic separation MSn capabilities HRMS Accurate mass capabilities Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  19. Acquisition modes : Advanced methods on hybrid instruments Naloxone Naltrexone 6-beta-naltrexol Buprenorphine MS1 [M+H]+ Expected 342.1705 MS2 [342-H2O]+ Expected 324.1600 MS3 [324-C4H6]+ Expected 270.1113 LCMS – IT - TOF Source : documentation Shimadzu Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  20. LC - MS : quantitative analysis - glucosamine D-Glucosamine chlorhydrate (C6H11O5NH2) . HCl MW 215.6 83.1% of free base D-Glucosamine sulfate (C6H11O5NH2)2 . H2SO4 . 2KCl MW 605.5 59.2% of free base HPLC Methods Difficulties : ► no chromophore ► highly polar ► positively charged at pH 7 Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  21. LC - MS : quantitative analysis - glucosamine HPLC Methods HILIC CH3CN / H2O (0.01% HCOOH) Mass spectrometry ESI mode  Ion Trap : MS2 162 m/z (LCQ : LOD 25 ng/ml LOQ 50 ng/ml) Triple Quad : MS2 neutral loss of 96 uma (TSQ : LOD 0.5 ng/ml LOQ 1 ng/ml) Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  22. LC - MS : quantitative analysis - glucosamine LCQ results Tablets X : 298 mg/g (expected 443) Liquid Y : 0.7 mg/g Gel Z : 0.8 mg/g Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  23. TLC – MS : DESI Invention of Graham Cooks Science 2004, 306, 471 Source : Documentation from Prosolia Inc Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  24. TLC – MS : DESI Source : G. Van Berkel et al, Anal. Chem. 2005, 77, 1207 Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  25. TLC – MS : Rhodamines 6G : R1,R2,R4 = CH2CH3; R3,R5 = H; R6, R7 = CH3 SRM m/z 443 → 415 B : R1, R6, R7 = H; R2, R3, R4, R5 = CH2CH3 SRM m/z 443 → 415 123 : R1 = CH3, R2,R3,R4,R5,R6,R7 = H SRM m/z 345 → 285 TLC: RP C2 Eluent : 80/20 MeOH/H2O 200 mM Ammonium acetate DESI solvent : MeOH Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  26. TLC – MS : Rhodamines Source : G. Van Berkel et al, Anal. Chem. 2005, 77, 7183 Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  27. TLC – MS : extra strengthExcedrin extract Caffeine [M+H]+ = 195 m/z [M+Na]+ = 217 m/Z Acetaminophen [M+H]+ = 152 m/z [M+Na]+ = 174 m/z Aspirin [M+Na]+ = 203 m/z [M+2Na-H]+ = 225 m/z TLC : NP eluent ACOEt/ACOH 99/1 DESI solvent : MeOH Full scan m/z 60 -300 Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

  28. Acknowledgments UCL, SC, CHIM, Mass Spec. Lab. Pr. Em. Ed de Hoffmann, A. Spôte, R. Rozenberg, R. Libert, L. Pesché UCL, MD, FARM, CHAM Pr. B. Tilquin, A. Maquille UCL, Saint-Luc Pr. Fr. Van Hoof, Pr. Ph. De Nayer €€€ : UCL FSR and COSIF Pr. Jean-Louis Habib Jiwan UCL – Département de chimie IPL mai 2007

More Related