Mass Spectrometry for Chemists and Biochemists

by Robert A. W. Johnstone , Malcolm E. Rose

• ISBN13: 9780521424974
• ISBN10: 0521424976
• Edition: 2nd
• Format: Paperback
• Copyright: 1996-10-28
• Publisher: Cambridge University Press

Summary

This book describes the full range of mass spectrometry techniques and applications. This versatile technique is in ubiquitous use in universities and industry laboratories because of its ability to identify and quantify materials quickly and, if necessary, in minute amounts, and solve analytical problems in a huge variety of fields. The authors adopt an instructional approach and make use of recent examples to illustrate important points. This second edition includes new methods and applications that have developed in the last ten years. Powerful methods combining mass spectrometry with newer separation techniques, the increased use of computers, and analysis of once difficult polar and large-mass compounds such as proteins using new ionisation methods are all discussed. Requiring no previous knowledge of mass spectrometry, this is an ideal teaching text at both undergraduate and postgraduate level, and will also be of considerable interest to research workers.

Table of Contents

Introduction	xiii
Acknowledgments	xvii
Table of quantities	xviii
List of abbreviations	xx
The mass spectrum	1	(21)
Formation of ions	1	(1)
Formation of the mass spectrum following electron ionization	1	(8)
Multiply charged ions	9	(1)
Isotopes	10	(4)
Metastable ions	14	(1)
Elemental compositions of ions	15	(2)
Appearance of the mass spectrum	17	(1)
Formation of the mass spectrum following ionization by other methods	18	(4)
Instrument design	22	(38)
Introduction	22	(1)
Inlet systems	23	(4)
Ion sources	27	(10)
Analysers (separation of ions)	37	(18)
Detection and recording of spectra	55	(3)
A total system	58	(2)
Methods of ionization	60	(53)
Introduction	60	(4)
Electron ionization	64	(2)
Chemical ionization	66	(12)
Negative-ion chemical ionization	78	(4)
Pulsed positive-ion/negative-ion chemical ionization	82	(1)
Modified electron and chemical ionization	82	(3)
Field ionization	85	(4)
Field desorption	89	(2)
Spraying and ion evaporation	91	(9)
High-speed particles	100	(8)
Lasers	108	(2)
Plasma desorption	110	(3)
Computers in mass spectrometry: data systems	113	(29)
Introduction	113	(1)
Data acquisition and mass calibration	114	(7)
Control of the mass spectrometer	121	(2)
Data processing	123	(18)
Data display units	141	(1)
Combined chromatography and mass spectrometry	142	(41)
Introduction	142	(2)
Gas chromatography / mass spectrometry	144	(14)
Liquid chromatography / mass spectrometry	158	(8)
Some applications of liquid chromatography / mass spectrometry	166	(6)
Capillary electrophresis / mass spectrometry	172	(4)
Supercritical fluid chromatography / mass spectrometry	176	(4)
Thin-layer chromatography / mass spectrometry	180	(3)
Uses of derivatization	183	(22)
Introduction	183	(3)
Imparting volatility and thermal stability	186	(2)
Modelling the molecule for analysis	188	(15)
Inorganic compounds	203	(2)
Quantitative mass spectrometry	205	(27)
Introduction and principles	205	(3)
Calibration and internal standards	208	(5)
Selected ion monitoring	213	(6)
Applications based on gas chromatography / mass spectrometry	219	(5)
Applications based on direct inlet	224	(3)
Applications based on liquid chromatography / mass spectrometry	227	(1)
Selected reaction monitoring	228	(4)
Metastable ions and mass spectrometry / mass spectrometry	232	(57)
The origins of metastable ions	232	(4)
The usefulness of metastable ions	236	(2)
Metastable ions in conventional mass spectrometers	238	(18)
Metastable ions in mass spectrometers of reversed geometry	256	(3)
Triple quadrupole analysers	259	(1)
Triple-focussing magnetic-sector mass spectrometers	260	(1)
Activation of normal ions	261	(9)
Mass spectrometry / mass spectrometry (tandem MS)	270	(11)
Summary and miscellany of MS/MS experiments	281	(8)
Theory of mass spectrometry	289	(36)
Introduction	289	(2)
Energy states resulting from electron ionization at low gas pressures	291	(7)
Energy states resulting from ionization at higher gas pressures	298	(2)
Energy states resulting from ionization in condensed (liquid) media	300	(1)
Energy states resulting from collisional and other activation	301	(2)
Formation of ions	303	(7)
Theories of fragmentation rates	310	(3)
Thermochemical arguments	313	(2)
Ion lifetimes	315	(1)
Qualitative theories	316	(9)
Structure elucidation	325	(72)
Classifications of mass spectra	325	(4)
Examination of the mass spectrum	329	(8)
Modification of mass spectra through instrumental parameters	337	(7)
Postulation of ion structures	344	(2)
Fragmentation of hydrocarbons	346	(7)
Primary fragmentations of aliphatic heteroatomic compounds	353	(20)
Primary fragmentations of aromatic heteroatomic compounds	373	(9)
Subsequent decomposition of primary fragment ions	382	(5)
Rearrangement accompanying fragmentation	387	(6)
Fragmentation following other methods of ionization	393	(2)
A suggested scheme for interpretation of mass spectra	395	(2)
Examples of structure elucidation by mass spectrometry	397	(30)
Introduction	397	(4)
Example A	401	(5)
Example B	406	(2)
Example C	408	(3)
Example D	411	(2)
Example E	413	(2)
Example F	415	(3)
Example G	418	(2)
Example H	420	(7)
Further discussion of selected topics	427	(51)
Ionization and appearance energies	427	(4)
Isotope analysis and labelling	431	(13)
Ion cyclotron resonance spectroscopy	444	(11)
Pyrolysis / mass spectrometry and pyrolysis / chromatography / mass spectrometry	455	(18)
Further literature on mass spectrometry	473	(5)
References	478	(18)
Index	496