Quadrupole Ion Trap Mass Spectrometry

by March, Raymond E.; Todd, John F.

• ISBN13: 9780471488880
• ISBN10: 0471488887
• Edition: 2nd
• Format: Hardcover
• Copyright: 2005-08-23
• Publisher: Wiley-Interscience

Summary

A definitive reference, completely updated Published in 1989, the First Edition of this book, originally entitled Quadrupole Storage Mass Spectrometry, quickly became the definitive reference in analytical laboratories worldwide. Revised to reflect scientific and technological advances and new applications in the field, the Second Edition includes new chapters covering: * New ion trap instruments of high sensitivity * Peptide analysis by liquid chromatography/ion trap tandem mass spectrometry * Analytical aspects of ion trap mass spectrometry combined with gas chromatography * Simulation of ion trajectories in the ion trap One additional chapter discusses the Rosetta mission, a "comet chaser" that was sent on a ten-year journey in 2004 to study the comet Churyumov-Gerasimenko using, among other instruments, a GC/MS system incorporating a specially designed ion trap mass spectrometer. This comprehensive reference also includes discussions of the history of the quadrupole ion trap, the theory of quadrupole mass spectrometry, the dynamics of ion-trapping chemistry in the quadrupole ion trap, the cylindrical ion trap, miniature traps, and linear ion traps. Complete with conclusions and references, this primer effectively encapsulates the body of knowledge on quadrupole ion trap mass spectrometry. With its concise descriptions of the theory of ion motion and the principles of operation, Quadrupole Ion Trap Mass Spectrometry, Second Edition is ideal for new users of quadrupole devices, as well as for scientists, researchers, and graduate and post-doctoral students working in analytical laboratories.

Author Biography

RAYMOND E. MARCH, PHD, DSc, coauthor of the First Edition, is Professor Emeritus in the Department of Chemistry at Trent University in Peterborough, Ontario, Canada.

JOHN F. J. TODD, PHD, is Emeritus Professor of Mass Spectroscopy at the University of Kent in the United Kingdom.

Table of Contents

Preface	xiii
Preface to First Edition	xix
Nomenclature	xxv
A Historical Review of the Early Development of the Quadrupole Ion Trap	1	(33)
Introduction	1	(1)
Principles of Operation	2	(4)
Utilization of the Quadrupole Ion Trap	6	(11)
Early Mass-Selective Modes of Operation	6	(1)
Mass-Selective Detection	6	(4)
Mass-Selective Storage	10	(2)
Ion Loss Processes	12	(1)
Unstable Trajectories	13	(1)
Interactions	13	(3)
Nonlinear Resonances	16	(1)
Self-Emptying	17	(1)
The Low-Pressure QUISTOR-Quadrupole Combination	17	(3)
Early Studies of the Theoretical Aspects of Low-Pressure Ion Trap Operation	20	(1)
Research Activities with the Quadrupole Ion Trap	21	(2)
Mass-Selective Axial Ejection	23	(2)
Conclusion	25	(9)
References	25	(9)
Theory of Quadrupole Instruments	34	(39)
Prelude	35	(1)
Introduction	35	(1)
Theory of Quadrupolar Devices	36	(31)
The Quadrupole Mass Filter (QMF)	38	(1)
QMF with Round Rods	39	(1)
The Structure of the QMF	39	(1)
Quadrupolar Potential	40	(2)
The Mathieu Equation	42	(1)
Regions of Stability of the QMF	43	(4)
Mass Selectivity of the QMF	47	(3)
The Quadrupole Ion Trap (QIT)	50	(1)
The Structure of the QIT	50	(2)
Electrode Surfaces	52	(3)
Quadrupolar Potential	55	(3)
An Alternative Approach to QIT Theory	58	(1)
Regions of Ion Trajectory Stability	58	(1)
Secular Frequencies	59	(5)
Calculations	64	(1)
qz and LMCO	64	(1)
βz	65	(1)
ωz	65	(1)
Mass Range	65	(1)
The Complete Solution to the Mathieu Equation	65	(2)
Secular Frequencies	67	(1)
Conclusions	67	(6)
Appendix	68	(3)
References	71	(2)
Dynamics of Ion Trapping	73	(60)
Introduction	74	(1)
The Pseudopotential Well Model	74	(17)
Specimen Calculation of the Pseudopotential Well Depth Dz	79	(1)
Some Applications of the Pseudopotential Well Model	79	(1)
Estimation of the Effects of Space Charge	80	(8)
Ion Kinetic Energies	88	(3)
Higher Order Field Components and Nonlinear Resonances	91	(21)
Historical Background	91	(2)
Fundamental Aspects of Nonlinear Resonances	93	(1)
Multipole Fields	93	(7)
Experimental Observations of Effects Arising from Nonlinear Resonances in the Quadrupole Ion Trap Mass Spectrometer	100	(4)
Nonlinear Field Effects in Quadrupole Mass Spectrometers and Linear Ion Traps	104	(1)
Mass Shifts	105	(7)
Motion of Trapped Ions	112	(13)
Collision Processes: Collisional Cooling	113	(2)
Collision Processes: Trapping Injected Ions	115	(2)
Resonant Excitation	117	(1)
Resonant Excitation: Ion Ejection	118	(2)
Resonant Excitation: Collision-Activated Decomposition	120	(2)
Collision Energies	122	(2)
Boundary-Activated Dissociation (BAD)	124	(1)
Surface-Induced Dissociation	125	(1)
Conclusion	125	(8)
References	125	(8)
Simulation of Ion Trajectories in the Quadrupole Ion Trap	133	(28)
Introduction	134	(2)
Recent Applications of Simulations	136	(1)
Theoretical Background	136	(22)
Numerical Integration of the Mathieu Equation	137	(1)
Calculation of Electrostatic Fields	138	(1)
Direct Method	139	(1)
Matrix Field Interpolation	139	(2)
Computer Simulation Programs	141	(1)
ITSIM	141	(1)
ISIS	141	(1)
SIMION	141	(1)
Dialogue and Operating Platform	142	(1)
Electrode Design	143	(2)
Scan Functions and User Programs	145	(1)
Ion Definition	146	(2)
Calculation of an Ion Trajectory	148	(1)
Data Collection and Display	149	(1)
Collision Models	150	(1)
Comparison of Simulators	151	(1)
Single-Ion Trajectories in a Collision-Free System	152	(3)
Collisional Cooling	155	(1)
Ion Injection	156	(2)
Conclusions	158	(3)
References	159	(2)
Linear Quadrupole Ion Trap Mass Spectrometer	161	(27)
Introduction	162	(2)
History	163	(1)
Mass Discrimination	163	(1)
Variable Retarding Field	163	(1)
Spectroscopic Studies	164	(1)
Resonant Ejection	164	(1)
Linear Ion Trap	164	(11)
Thermo Finnigan Linear Ion Trap	164	(1)
Advantages of a Linear Ion Trap	165	(1)
Description of the Thermo Finnigan Linear Ion Trap	165	(1)
MDS SCIEX Linear Ion Trap	166	(1)
Description of the MDS SCIEX Linear Ion Trap	166	(1)
Ion Trapping in Collision Cell Qc	167	(1)
Mass-Selective Axial Ion Ejection	168	(1)
Ion Accumulation in Q0	168	(1)
CID by Variation in Precursor Ion Axial Kinetic Energy	169	(1)
Ion Trapping in RF-Only Quadrupole Mass Filter Q2	169	(1)
Ion Confinement Theory	169	(1)
Ion Trap Capacities	170	(1)
Characteristics of Linear Ion Trap Operation	171	(1)
Trapping Efficiency	171	(1)
Mass Discrimination	172	(1)
Ion Isolation	172	(1)
Ion Activation	172	(1)
Tandem Mass Spectrometry	172	(1)
Spectral Space Charge Limit	172	(1)
Ion Ejection	172	(1)
Enhanced Mass Resolution	173	(1)
Sensitivity	173	(1)
Low-Pressure Linear Ion Trap, Q2	173	(2)
Rectilinear Ion Trap	175	(4)
RIT Structure	176	(1)
Optimization of the RIT Geometry	176	(1)
Stability Diagram	177	(2)
RIT Performance	179	(1)
Stacked-Ring Set	179	(5)
Electrostatic Ion Guide	181	(1)
Ion Tunnel	181	(1)
Transmission Efficiency	181	(1)
Charge State Discrimination	182	(2)
Conclusions	184	(4)
Appendix	185	(1)
References	185	(3)
Cylindrical Ion Trap Mass Spectrometer	188	(23)
Introduction	189	(1)
Initial Studies of a Cylindrical Ion Trap	189	(3)
Operation of a CIT	189	(2)
Further Development of the CIT	191	(1)
Miniature Ion-Trapping Devices	191	(1)
Stored-Ion Spectroscopy	191	(1)
Readily Machined Ion Traps	191	(1)
Miniature Cylindrical Ion Traps (Mini-CITs)	192	(9)
Driving Force	193	(1)
Miniaturization	193	(1)
Portable Miniature CIT	194	(1)
Vacuum System	195	(1)
Ionization Source	195	(1)
Detector System	195	(1)
Waveform Generation	196	(1)
Control Software	196	(2)
Mini-CIT System Performance	198	(1)
Mass Calibration	198	(1)
Tandem Mass Spectrometry	199	(2)
Limit of Detection and Mass Resolution	201	(1)
Membrane Introduction Mass Spectrometry	201	(2)
Miniature Cylindrical Ion Trap Array	203	(1)
Field Applications of Mini-CITs	204	(2)
Micro Ion Traps	206	(1)
Single-Ion Study	206	(1)
Optimization of Micro Ion Traps	206	(1)
Conclusions	207	(4)
References	208	(3)
Gas Chromatography/Mass Spectrometry	211	(39)
Introduction	212	(1)
Gas Chromatography	213	(17)
Gas Chromatography/Mass Spectrometry	213	(1)
Information Theory	213	(1)
Informing Power in Mass Spectrometry	214	(1)
Informing Power in Tandem Mass Spectrometry	214	(1)
The State of the GC Market	215	(1)
Carrier Gas	215	(1)
The ITD Instrument	216	(1)
Mass Analysis by Mass-Selective Instability	217	(1)
Mode of Operation	217	(2)
A Remarkable Achievement	219	(1)
Ion Trap Mass Spectrometer, ITMS	220	(1)
SATURN Model I Ion Trap Detector	220	(1)
SATURN Model 4000 GC/MS System	220	(2)
Ion Creation	222	(1)
Ion Ejection	222	(3)
Chemical Ionization	225	(1)
Chemical Ionization Mass Spectral Mode	225	(3)
Chemical Ionization with Specific Reagent Ions	228	(1)
Tandem Mass Spectrometry	229	(1)
Scan Function for Tandem Mass Spectrometry	230	(1)
Tandem Mass Spectrometric Determination of Dioxins and Furans	230	(6)
Tuning of the Mass Spectrometer	233	(1)
Ionization	233	(1)
Isolation of Mass-Selected Ion Species	234	(1)
Resonant Excitation of Isolated Ion Species	235	(1)
Analytical RF Ramp	236	(1)
Comparison of Three Mass Spectrometric Methods	236	(9)
Instruments	237	(1)
Operational Conditions	237	(1)
Product Ions Monitored	238	(1)
Calibration	239	(1)
Resonant Excitation	239	(2)
Comparisons of Performances	241	(1)
Ion Signals at Low Concentration	241	(1)
Real Samples	241	(1)
Ionization Cross Sections	241	(4)
Conclusions	245	(5)
References	246	(4)
Ion Trap Mass Spectrometry/Liquid Chromatography	250	(41)
Introduction	251	(1)
Electrospray Ionization	252	(1)
Commercial Instrument Manufacturers	252	(2)
Commercial Instrument Development	253	(1)
Commercial Instrumentation	254	(1)
Early Exploration of ESI Combined with a QIT	254	(2)
Instrument Configuration	255	(1)
Axial Modulation and Mass Range Extension	256	(1)
Electrospray Mass Spectrum	256	(8)
Charge State and Molecular Weight	257	(1)
Computer Algorithms	258	(1)
Ion Trap Extended Mass Range Operation	258	(3)
Ion/Molecule Reactions	261	(1)
MSn of Peptides and Proteins	261	(2)
Positive Ion MS/MS and MSn Studies	263	(1)
Recent Applications of ESI Combined with a QIT	264	(6)
Major Nonlinear Resonances for Hexapole and Octopole	264	(2)
Ejection by a Dipole Field	266	(1)
Ejection by a Hexapole Field	267	(1)
Octopole Field	267	(1)
Modified Hyperbolic Angle Ion Traps	268	(2)
Combined Hexapole and Octopole Fields	270	(1)
The HCT Ion Trap	270	(8)
Ion Ejection	272	(1)
Ion Trap Capacity	272	(1)
Mass Resolution at High Scan Speeds	272	(2)
Sensitivity for a Protein Digest	274	(1)
De Novo Peptide Sequencing	275	(2)
Protein Identification	277	(1)
MOWSE Score	277	(1)
Expectation Value	277	(1)
De Novo Peptide Sequencing of Thirteen Proteins	278	(1)
Multidimensional Liquid Chromatography	278	(1)
Digital Ion Trap	278	(9)
Introduction	280	(1)
Concept of the DIT	280	(1)
Stability Parameters	281	(1)
Field Adjustment	282	(1)
Trapping Ability	282	(1)
Mass Resolution	282	(1)
Pseudopotential Well Depth	283	(1)
Forward and Reverse Mass Scans	284	(3)
Summation of the Digital Ion Trap Development	287	(1)
Conclusions	287	(4)
References	287	(4)
An Ion Trap Too Far? The Rosetta Mission to Characterize a Comet	291	(18)
Introduction	291	(1)
The Rosetta Mission	292	(3)
The MODULUS Ptolemy Experiment	295	(14)
Stable Isotope Ratio Measurements for Light Elements	296	(1)
The Ion Trap Mass Spectrometer as the Instrument of Choice	296	(5)
Sample Processing and Isotope Ratio Measurements	301	(1)
Ion Trap Operation	301	(2)
Sample Processing and Analysis	303	(3)
Operational Sequence at Cometary Encounter	306	(1)
Summary and Conclusions	307	(1)
Acknowledgment	307	(1)
References	307	(2)
Author Index	309	(8)
Subject Index	317

Excerpts

"This comprehensive reference includes discussions of the history of the quadrupole ion trap, the theory of quadrupole mass spectrometry, the dynamics of ion-trapping chemistry in the quadrupole ion trap, the cylindrical ion trap, miniature traps, and linear ion traps. Complete with conclusions and references, this primer effectively encapsulates the body of knowledge on quadrupole ion trap mass spectrometry." "With its concise descriptions of the theory of ion motion and the principles of operation, Quadrupole Ion Trap Mass Spectrometry, Second Edition is ideal for new users of quadrupole devices, as well as for scientists, researchers, and graduate and post-doctoral students working in analytical laboratories."--BOOK JACKET.