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Mass Spectrometry MS Interpretation General Interpretation Strategies

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Aims and Objectives

Aims and Objectives Aims
• Introduces students to the principles of mass spectral interpretation. • Present fundamental concepts regarding mass spectral interpretation

Objectives
At the end of this Section you should be able to: • List and explain the main characteristics of the mass spectrum • Explain how mass spectrometric data can be used for structure analysis • Explain why is important to optimise ESI/APCI parameters

Content
Introduction Mass to Charge Ratio Mass Resolution Doublet Method Resolution of Single Peak High Mass Resolution Mass Accuracy High Mass Accuracy Mass Range Multiply Charged Ions Spectral Features Isotopic abundances High Mass Region –Brominated Sample The Nitrogen Rule Interpretation Strategy Logical Losses Illogical losses Fragmentation in API Rings and Insaturations Number of Carbons Cleavages –Ion Abundance Cleavages –Simple Mechanisms Electrospray Ionisation ESI Considerations APCI Considerations APPI Considerations LC-MS Structural Information Modes MS/MS Overview MS/MS Experiments Product Ion Scanning Overview Application Precursor Ion Scanning Overview Application Constant Neutral Loss Scanning Overview Application Single/Multiple Reaction Monitoring Overview Application MS/MS Quantitative Considerations References 3 4 5 6 7 8 9 9 10 11 13 14 21 23 24 24 25 25 26 27 29 30 32 33 35 36 37 38 39 40 40 41 42 42 43 44 44 45 46 46 47 48 49

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Introduction Mass Spectrometry is a wide-ranging analytical technique. It relates to the production and subsequent separation and identification of charged species that are produced by a variety of ionisation methods. The importance of learning how to identify mass spectra

References: 1. Pure & Appl. Chem., 1999, 71, 1594-1607. 2. G. Zerbi and G. H. Benyon. IUPAC Symbolism and nomenclature for MS. Org. Mass Spectrom. 12, (1977), 115-118. 3. Terrence A. Lee. “A Beginner’s Guide to Mass Spectral Interpretation.” John Wiley and Sons 1998, 1-20. 4. J. T. Watson. “Introduction to Mass Spectrmetry.” Chapter 2. Lippincott-Raven, Pa, USA, (1997), 16. 5. James Barker. “Mass Spectrometry” John Wiley and Sons 1999, 117-147. 6. E. De Hoffmann, J. Charette, and V. Stroobant. “Mass Spectrometry –Principles and Applications.” John Wiley and Sons 1996, 39-48. 7. F. W. McLafferty. “Interpretation of Mass Spectra.” 3rd Edition. University Science Books: Mill Valley, (1980), 15. 8. M. E. Bier and J. E. Schwartz in “Electrospray Ionisation Mass Spectrometry.” R. B. Cole [ed.], John Wiley and Sons Inc, (1997), 263. 9. E. Sheehan and S. Mitrovich in “A Global View of LC/MS”, 1st edition, (Appendix D), Global Publishing, PA, USA, (1998), 106. 10. J. Yergy, D. Heller, G. Hansen, R. J. Cotter, C. Fenselau. “Isotopic Distributions in MS of Large Molecules.” Anal. Chem. 55, (1983), 353-356. 11. Ross Willoughby, Ed Sheehan, Sam Mitrovich. “A Global View of LC/MS” Global View Publishing. 1998, 297-324 12. http://www.sisweb.com/referenc/source/exactmaa.htm 13. Reg Davis, Martin Frearson. “Mass Spectrometry” John Wiley and Sons 1990, 15-22 14. Susana Grimalt, Óscar J. Pozo, Jose M. Marín, Juan V. Sancho, and Félix Hernández. “Evaluation of Different Quantitative Approaches for the Determination of Noneasily Ionizable Molecules by Different Atmospheric Pressure Interfaces Used in Liquid Chromatography Tandem Mass Spectrometry: Abamectin as Case of Study.” J. Am. Soc Mass Spectrom. 2005, 16, 1619–1630. © Crawford Scientific www.chromacademy.com 49 15. 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Cole. “Formation and Decompositions of Chloride Adduct Ions, [M + Cl]-, in Negative Ion Electrospray Ionization Mass Spectrometry” J Am Soc Mass Spectrom. 11, (2000), 932–941. 20. Christophe Guimbaud, Thorsten Bartels-Rausch, Markus Ammann. “An atmospheric pressure chemical ionization mass spectrometer (APCI-MS) combined with a chromatographic technique to measure the adsorption enthalpy of acetone on ice.” International Journal of Mass Spectrometry. 226, (2003) 279–290. 21. G. A. Eiceman, J. F. Bergloff, J. E. Rodriguez, W. Munro, and Z. Karpas. “Atmospheric Pressure Chemical Ionization of Fluorinated Phenols in Atmospheric Pressure Chemical Ionization Mass Spectrometry, Tandem Mass Spectrometry, and Ion Mobility Spectrometry” J Am Soc Mass Spectrom 1999, 10, 1157–1165. 22. Beata M. Kolakowski, J. 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