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FUNDAMENTALS
AND
APPLICATIONS
OF FOURIER
TRANSFORM MASS
SPECTROMETRY
FUNDAMENTALS
AND
APPLICATIONS OF
FOURIER
TRANSFORM MASS
SPECTROMETRY
Edited by

BASEM KANAWATI
Analytical Biogeochemistry, Helmholtz Zentrum
M€
unchen, Neuherberg, Germany

PHILIPPE SCHMITT-KOPPLIN
Analytical Biogeochemistry, Helmholtz Zentrum
M€unchen, Neuherberg, Germany
Analytical Food Chemistry, Technical University of Munich,
Freising, Germany
Elsevier
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Contributors

Jeffery N. Agar
Department of Chemistry and Chemical Biology, Northeastern University, Boston, MA,
United States
Deborah V.A. de Aguiar
Chemistry Institute, Federal University of Goiás, Goi^ania, Brazil
Michaela Aichler
Research Unit Analytical Pathology, Helmholtz Zentrum M€
unchen, German Research
Center for Environmental Health, Neuherberg, Germany
Herve Alexandre
UMRPAM University of Burgundy/Agrosup Dijon, Institut Universitaire de la Vigne et du
Vin, Jules Guyot, Dijon, France
João Francisco Allochio Filho
Laboratory of Petroleology and Forensic Chemistry, Department of Chemistry, Federal
University of Espı́rito Santo, Vitória, Brazil
I. Jonathan Amster
Department of Chemistry, University of Georgia, Athens, GA, United States
Frederic Aubriet
Laboratory of Chemistry and Physics—Multi-Scale Approach of Complex Systems, FR 2843
Jean Barriol Institut, FR 3624 French High Field FT-ICR Mass Spectrometry Network,
Lorraine University, ICPM, Metz, France
Konstantin Ayzikov
Thermo Fisher Scientific, Bremen, Germany
Vincent Carre
Laboratory of Chemistry and Physics—Multi-Scale Approach of Complex Systems, FR 2843
Jean Barriol Institut, FR 3624 French High Field FT-ICR Mass Spectrometry Network,
Lorraine University, ICPM, Metz, France
Sebastian Dillinger
Fachbereich Chemie and Forschungszentrum OPTIMAS, Technical University
Kaiserslautern, Kaiserslautern, Germany
Jiana Duan
Department of Chemistry, University of Georgia, Athens, GA, United States
Michael L. Easterling
Bruker Daltonics Inc., Billerica, MA, United States
François Fenaille
Pharmacology and Immunoanalysis Unit (SPI), CEA, INRA, Paris-Saclay University,
Gif-sur-Yvette, France

xiii
xiv Contributors

Francisco Fernandez-Lima
Department of Chemistry and Biochemistry; Biomolecular Sciences Institute, Florida
International University, Miami, FL, United States
Federico Floris
Department of Chemistry, University of Warwick, Coventry, United Kingdom
Lena Gmelch
Comprehensive Foodomics Platform, Analytical Food Chemistry, Technical University
Munich, Freising, Germany
Michael Gonsior
University of Maryland Center for Environmental Science, Chesapeake Biological
Laboratory, Solomons, MD, United States
Marina Gotthardt
Comprehensive Foodomics Platform, Analytical Food Chemistry, Technical University
Munich, Freising, Germany
Regis D. Gougeon
UMRPAM University of Burgundy/Agrosup Dijon, Institut Universitaire de la Vigne et du
Vin, Jules Guyot, Dijon, France
Dmitry Grinfeld
Thermo Fisher Scientific, Bremen, Germany
Daniel Hemmler
Research Unit Analytical BioGeoChemistry, Helmholtz Zentrum M€ unchen, Neuherberg;
Comprehensive Foodomics Platform, Analytical Food Chemistry, Technical University
Munich, Freising, Germany
Jasmine Hertzog
Laboratory of Chemistry and Physics—Multi-Scale Approach of Complex Systems, FR 2843
Jean Barriol Institut, FR 3624 French High Field FT-ICR Mass Spectrometry Network,
Lorraine University, ICPM, Metz, France; Comprehensive Foodomics Platform, Analytical
Food Chemistry, Technical University Munich, Freising; Research Unit Analytical
BioGeoChemistry, Helmholtz Zentrum M€ unchen, Neuherberg, Germany
Christophe Junot
Pharmacology and Immunoanalysis Unit (SPI), CEA, INRA, Paris-Saclay University,
Gif-sur-Yvette, France
Basem Kanawati
Research Unit Analytical BioGeoChemistry, Helmholtz Zentrum M€
unchen, Neuherberg,
Germany
Yury I. Kostyukevich
Skolkovo Institute of Science and Technology Novaya St. Russian Federation, Russia
Sergey V. Kovalev
Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow, Russia
Anton N. Kozhinov
Spectroswiss, EPFL Innovation Park, Lausanne, Switzerland
 Contributors xv

Lisa Kreutzer
Research Unit Analytical Pathology; Research Unit of Radiation Cytogenetics & Research
Unit Analytical Pathology, Helmholtz Zentrum M€ unchen, German Research Center for
Environmental Health, Neuherberg, Germany
Valdemar Lacerda, Jr.
Laboratory of Petroleology and Forensic Chemistry, Department of Chemistry, Federal
University of Espı́rito Santo, Vitória, Brazil
Albert T. Lebedev
Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow, Russia
Youzhong Liu
UMRPAM University of Burgundy/Agrosup Dijon, Institut Universitaire de la Vigne et du
Vin, Jules Guyot, Dijon, France
Alexander Makarov
Thermo Fisher Scientific, Bremen, Germany
Franco Moritz
Research Unit Analytical BioGeoChemistry, Helmholtz Zentrum M€
unchen, Neuherberg,
Germany
Konstantin O. Nagornov
Spectroswiss, EPFL Innovation Park, Lausanne, Switzerland
Gereon Niedner-Schatteburg
Fachbereich Chemie and Forschungszentrum OPTIMAS, Technical University
Kaiserslautern, Kaiserslautern, Germany
Eugene N. Nikolaev
Skolkovo Institute of Science and Technology Novaya St. Russian Federation, Russia
Peter B. O’Connor
Department of Chemistry, University of Warwick, Coventry, United Kingdom
Igor Pereira
Chemistry Institute, Federal University of Goiás, Goi^ania, Brazil
Wanderson Romão
Laboratory of Petroleology and Forensic Chemistry, Department of Chemistry,
Federal University of Espı́rito Santo, Vitória; Federal Institute of Espı́rito Santo,
Vila Velha; National Institute of Forensic Science and Technology (INCT Forensic),
Vitória, Brazil
Chloe Roullier-Gall
UMRPAM University of Burgundy/Agrosup Dijon, Institut Universitaire de la Vigne et du
Vin, Jules Guyot, Dijon, France
Michael Rychlik
Comprehensive Foodomics Platform, Analytical Food Chemistry, Technical University
Munich, Freising, Germany; Centre for Nutrition and Food Sciences, Queensland Alliance
for Agriculture and Food Innovation (QAAFI), University of Queensland, Brisbane,
Australia
xvi Contributors

Philippe Schmitt-Kopplin
Research Unit Analytical BioGeoChemistry, Helmholtz Zentrum M€ unchen, Neuherberg;
Comprehensive Foodomics Platform, Analytical Food Chemistry, Technical University
Munich, Freising, Germany
J€
org-Peter Schnitzler
Helmholtz Zentrum M€ unchen, Institute of Biochemical Plant Pathology, Research Unit
Environmental Simulation, Neuherberg, Germany
Yury O. Tsybin
Spectroswiss, EPFL Innovation Park, Lausanne, Switzerland
Gessica Vasconselos
Chemistry Institute, Federal University of Goiás, Goi^ania, Brazil
Boniek G. Vaz
Chemistry Institute, Federal University of Goiás, Goi^ania, Brazil
Joelle Vinh
Laboratory of Biological Mass Spectrometry and Proteomics, CNRS USR 3149, ESPCI
Paris, PSL University, Paris; TGE FT-ICR CNRS, France
Gleb Vladimirov
Skolkovo Institute of Science and Technology Novaya St. Russian Federation, Russia
Axel Karl Walch
Research Unit Analytical Pathology, Helmholtz Zentrum M€
unchen, German Research
Center for Environmental Health, Neuherberg, Germany
Karl Peter Wanczek
Institute of Inorganic and Physical Chemistry, University of Bremen, Bremen, Germany
Foreword

This book provides a wide-ranging description of the current state of the art
in Fourier transform mass spectrometry. As described in several chapters,
beginning in late 1973 with the first FT ion cyclotron resonance mass spec-
trum (showing just a single CH+4 peak), the field has since exploded, with
installation of nearly 1000 FT-ICR MS plus several thousand orbitrap
instruments.
FT mass analyzers offer the highest mass resolution (e.g., baseline sepa-
ration of ions differing in mass by less than the mass of an electron) and mass
accuracy (mass error as low as a few ppb). Those figures of merit have
recently been improved by increased magnetic field strength (FT-ICR)
or smaller-size ion trap (orbitrap), as well as phase correction to double
the mass resolving power (FT-ICR and orbitrap), and frequency-multiple
detection for enhancement of FT-ICR mass resolving power by factors
of 2–4. Conversely, for a given mass resolving power, data acquisition
can be speeded up to achieve LC-MS without compromising chromato-
graphic resolution. Instrumentation improvements in ion injection, ion
trapping (dynamically harmonized ICR cell; “nadel” ICR cell, Cassini
quadrupolar cell), excitation, and detection continue to be guided by ion
trajectory simulations.
Multifaceted applications have been enabled by coupling FT mass ana-
lyzers with gas- and liquid-chromatography (collected fractions or on-line),
trapped ion mobility source, various ionization methods (e.g., electron
impact, laser desorption/ionization, MALDI, electrospray, photoioniza-
tion), various ion fragmentation methods (ion-neutral collisions, IR and
UV photodissociation, electron capture, electron transfer, surface-induced
dissociation). FTMS has had particularly high impact in proteomics
(MS/MS identification of protein amino acid sequences, including post-
translational (chemical) modifications not accessible from corresponding
DNA base sequences, and petroleomics (prediction of the properties and
behavior of petroleum and its products based on detailed organic composi-
tional analysis), and is expanding into various other “-omics” fields (food,
geochemistry, environment, forensics, carbohydrates, lipids, metabolism,
etc.) and in molecular imaging in biochemistry and medicine.
The chapters summarize the actual state of the art in the field as for exam-
ple two-dimensional FT-ICR MS/MS, which yields a single 2D spectrum

xvii
xviii Foreword

that connects each precursor ion with all of its product ions. Other chapters
describe gas-phase ion-molecule chemistry and low-temperature inorganic
clusters.
In summary, FTMS instruments now extend to virtually the full range of
mass analysis applications, thereby setting new “gold standards” which serve
to guide subsequence “targeted” analysis with lower-resolution instruments.

Alan G. Marshall
Robert O. Lawton Professor of Chemistry & Biochemistry
Founding Director and Chief Scientist,
Ion Cyclotron Resonance Program,
National High
Magnetic Field Laboratory
Florida State University
Tallahassee, FL, United States
Preface

The world of mass spectrometry is expanding rapidly in this century thanks

to many advances in physics, electronics, vacuum technology and mathe-
matical considerations, especially in the field of statistical data analysis and
engineering. Therefore a strong need emerged to write this book, which
addresses many aspects of technical fundamentals in the physics of mass
spectrometric FTMS analyzers and ion beam guides as well as diverse appli-
cations in many fields of natural and life science.
Here we give a brief account on the diverse topics which are included in
this comprehensive book:
Chapter 1 addresses the historical developments in the well-known Fou-
rier Transform Ion Cyclotron Resonance Mass Spectrometry FT-ICR-MS.
Chapter 1 does not only list the main historical developments of the
FT-ICR but also it dates back to the invention of ICR, prior to implemen-
tation of the effective Fourier Transform (FT) algorithm to speed up the
whole ICR experimental setup, by enabling the great technological transfer
from magnetic field scan to the rapid frequency chirp “all ions excitation”
for ICR detection.
Chapter 2 addresses technical fundamentals in the efficient Orbitrap mass
analyzer, showing its physical principle of operation, dealing with nonideal
orbitrap geometries and showing their possible calibration, and giving some
advances in signal processing which are steadily growing in the recent time.
The reader will find applications to this great mass analyzer not only in
Chapter 2 but also in Chapters 5, 11, 15, 16, 17 and 21, which discuss
advanced fundamentals, metabolomics, forensics, petroleomics, proteomics
and foodomics, respectively.
Advances in the new Paracell ICR mass analyzer can be found in
Chapters 3 and 4. In this respect, the reader will especially get advanced
knowledge on the physical developments of the Paracell, showing also with
sophisticated ion trajectory simulations on supercomputers with more
sophisticated ion trajectory simulators beyond SIMION the challenges that
could be overcome in ICR to reduce space-charge effects and coalescences
and also enhance both resolution and acquisition time.
Chapter 5 discusses mass resolving power characteristics in both Orbitrap
and ICR mass analyzers for achieving ultra-high resolution spectra in a broad
mass range. This discussion is assisted by robust and clear mathematical

xix
xx Preface

equations to facilitate understanding the differences in the resolution behav-

ior as a function of m/z. This chapter also addresses data reduction
approaches and also shows the possible conversion from raw (full) to line
shape (reduced profile) mass spectra with their pros and cons.
Extensive data processing strategies are discussed in Chapter 6, where
magnitude and absorption detection modes in FT-ICR are discussed in great
detail as well as many non-Fourier Transform techniques. Calibration, apo-
dization, denoising and batch processing as well as isotopic beat patterns are
also treated. Chapter 6 represents also different successful strategies and also
discusses advanced ICR control units for FT-ICR-MS automation to give
the reader some hands-on experience for achieving a full FTMS acquisition-
time investment.
Chapter 7 is dedicated for explaining all the fundamentals and also show-
ing many successful applications in the field of two dimensional FT-ICR-MS.
Data acquisition and processing as well as important denoising algorithms are
also discussed there which are specific to 2D-FT-ICR-MS.
Coupling of FTMS mass analyzers to ion mobility cells and to chromato-
graphic systems is discussed in Chapters 8 and 11, respectively. Chapter 9
shows many applications of FT-ICR-MS to medical imaging of cancer bio-
logical tissues and Chapter 10 shows diverse coupling of laser sources for
ionization to FT-ICR-MS with many discussed inorganic applications.
Many metabolomics applications can be found in both Chapter 11 for Orbi-
trap and Chapter 12 for FT-ICR-MS. The latter chapter shows also the
importance of mass difference networks for revealing not only the compo-
sitional elemental space in complex mixtures but also going in deep detail
beyond it (see details in Chapter 12). Environmental applications related
to aquatic and sediment chemistry can be found in Chapter 13, whereas deep
discussions for peptide sequencing can be found in both Chapters 14 and 17.
Forensic FTMS applications are given in Chapter 15, while many applica-
tions in the field of petroleomics exist in Chapter 16. Many challenges in
proteomics and proteoforms are greatly discussed in Chapter 19, which
shows the transition from the comprehensive description of exhaustive pro-
teome to functional proteomics by the use of FTMS. Both Chapters 18 and
19 shows diverse FT-ICR-MS applications into the gas phase ion chemistry,
done in several ICR cells, which serve as electronic reagent glass (electronic
reactor). Key physical chemistry thermodynamic and kinetic data could be
achieved in the past 40 years with FT-ICR-MS and they are discussed for
the case of inorganic elements and their substances as a review in Chapter 18,
focusing on nonmetal applications, while Chapter 19 discusses FT-ICR-MS
 Preface xxi

investigations of several inorganic metal cluster ions and also show the
advantage of cold ICR cell relative to traditional ambient temperature oper-
ation mode. The last three chapters, shows deep FT-ICR-MS investigations
in glycomics, foodomics and bio-oil analysis. With comprehensive treat-
ments of these divers topics of FTMS applications, the reader will get thor-
ough up to date knowledge (some of which are very practical), which can
help the reader to further run and overcome some scientific challenges while
running further FTMS applications. Despite the complex physical and
mathematical fundamentals of the FTMS mass analyzers, every effort has
been done from the editorial side to make every chapter as clear as possible
and therefore accessible to a large audience of scientific readers. We hope
that the reader will enjoy also reading these very interesting chapters.

The editors
Acknowledgments

The editors thank all book chapter contributors for their great efforts and
time spent to add up to date scientific knowledge from their great hands-
on expertise. We enjoyed cooperating together with many authors, who
provided excellent reviews and many explanations to our scientific queries
to make this book as clear as possible.
Basem Kanawati greatly thanks professor Karl Pater Wanczek for his
valuable comments and assistance, while preparing this book. He is the first
scientist, who introduced me in the past to advanced ICR-MS techniques,
with its diverse fundamental physical and chemical elements, ranging from
experimental physics studies and ion trajectory simulations in several ICR
cell designs to applications of this technique in studying many gas phase
ion-molecule reactions and ion energetics.
The editors also thank all Elsevier’s team members for witnessing and
greatly assisting the development of this extensive book. With their help,
we could all contribute to make the production of this comprehensive book
a reality.

xxiii
CHAPTER 1

Historical developments in Fourier

transform ion cyclotron resonance
mass spectrometry
Karl
*
Peter Wanczek*, Basem Kanawati†
Institute of Inorganic and Physical Chemistry, University of Bremen, Bremen, Germany
†
Research Unit Analytical BioGeoChemistry, Helmholtz Zentrum M€ unchen, Neuherberg, Germany

Contents
Introduction 4
Developments before 1970 5
1965 5
1966 6
1967 6
1968 7
1969 7
Developments from 1970 to 1980 7
1970 7
1971 8
1972 9
1973 9
1974 10
1975 11
1976 11
1977 12
1978 12
1979 12
1980 12
Developments from 1981 to 1990 13
Developments from 1991 to 2000 15
Developments from 2001 17
Conclusion 22
References 23

Fundamentals and Applications of Fourier Transform Mass Spectrometry © 2019 Elsevier Inc.
https://doi.org/10.1016/B978-0-12-814013-0.00001-6 All rights reserved.
4 Fundamentals and Applications of Fourier Transform Mass Spectrometry

Introduction
This review covers instrumentation and theory as well as applications, which
open new fields in scientific research. Therefore, the first decades will
occupy more space than the more recent years. The material is presented
in a chronological sequence of events to facilitate a historical point of view
through the discussion. The review is not intended to be comprehensive,
but a personal view of the authors of the most important developments
in the field.
Four different ion traps are known:
– Penning trap [1–3] (ion trapping by DC electrical fields and a homoge-
neous magnetic field), “ICR cells”
– Paul trap [4, 5] (ion trapping by RF electrical fields),
– Kingdon trap [6] (ion trapping by DC fields) and
– Combined trap [7] (a combination of the Paul and Penning trapping
principles).
Penning traps are covered as far as they are employed in ion cyclotron res-
onance (ICR) mass spectrometry and Fourier transform ion cyclotron—FT
ICR—mass spectrometry. Also covered are ICR drift cells employed in the
early times of the ICR technique. In the ICR drift cell ions drift on cycloidal
paths along the longitudinal axis, guided by magnetic and electric fields (see
text below).
In physics, precision measurements of atomic masses and fundamental
constants are performed with Penning traps. With ICR, elementary steps
of chemical reactions and ion-molecule reactions, which normally occur
at near-thermal energies, are studied. After the invention of the Fourier
transform technique, analytical applications dominate. The ICR method
developed independently from the physical applications until early 1980s
(cf. Ref. [8]: In this ICR volume, for the first time, physical applications
of Penning traps are described by G. Gr€aff from the Institute of Physics,
University of Mainz, in the chapter: “precision determination of cyclotron
frequencies of free electrons and ions,” pp. 318–325).
Several publications of general interest in ICR have been published. The
first book was written by Lehman and Bursey [9] in 1976. The book by
Marshall and Verdun [10] presents a detailed general introduction. Early
reviews in 1971 by Gray [11], by Beauchamp [12], by Futrell [13] and in
1973 by Hartmann et al. [14] covered the new methodology comprehen-
sively. Several reviews [15–18] of early ICR development were published,
and more recently [19, 20] Hartmann and Wanczek [8, 21] edited two
 Historical developments in FT ICR mass spectrometry 5

volumes in Lecture Notes in Chemistry on ICR Spectrometry in 1978 and

1982 which covered many aspects of the development of the field.
A recent contribution to the history of mass spectrometry is in “The
Encyclopedia of Mass Spectrometry,” Vol. 9, Part A [22]. The volume con-
tains a history of ICR by C.L. Wilkins [23] with many details.

Developments before 1970

In ICR, the ions were trapped in or drifted through an ICR cell at reduced
pressure and detected with the aid of image current [24], induced in the cell
plates by a coherent ion motion. The coherent motion is generated by exci-
tation of one of the characteristic ion frequencies. The method has many
similarities with NMR spectroscopy. The ions are present in the ICR cell
after detection. In general, only ions of one charge polarity can be trapped,
negative ions or positive ions.
The Omegatron of Sommer et al. [25] employed cyclotron resonance
excitation and charge detection of ions. The Omegatron was utilized
widely. Several improvements were introduced [26]. By the Hipple group
a further instrument was described, which employed the ion cyclotron
motion for focusing: The trochoidal mass Spectrometer [27]. Goudsmit
[28] described a Time-of-Flight mass spectrometer where the trajectory
of the ions is inside a magnetic field.
A very advanced instrument, the Mass “Synchrometer,” was built by
Smith and Damm [29]. High harmonics of the ion cyclotron frequency were
employed for mass determination with hitherto unparalleled accuracy. Cog-
geshall [30] first described the path of ions and electrons in nonuniform
crossed electric and magnetic fields. In 1962, Graham et al. [31, 32]
described an ICR instrument and discussed the determination of collision
cross sections. A detailed description of the ICR spectrometer followed [33].

1965
Llewellyn [34] of Varian Ass. filed a patent of an ICR spectrometer with drift
ICR cell and ion resonance detection with the aid of a marginal oscillator
(Pound box [35, 36]):
“A spectrometer is described which employs ion cyclotron resonance and energy
absorption in mass analysis. In an evacuated envelope ions are formed in the first
of two regions which are subjected to static magnetic and electric fields disposed at
right angles to each other and to the common axis of the two regions. The ions are
caused by the interaction of the fields to move with cycloidal motion into the
6 Fundamentals and Applications of Fourier Transform Mass Spectrometry

second region which is additionally subjected to an oscillating electric field in the

same direction as the static field. The ions in resonance with the oscillating field
absorb energy therefrom and separate from the nonresonant ions. The energy
absorbed by the resonant ions is then detected as a measure of the resonant ions.”
(Abstract of patent)

Furthermore, this ICR cell had a third region for total ion current measure-
ment. The spectrometer was produced and named “Syrotron.” The instru-
ment had a small mass range, below m/z ¼ 200 and a resolution of
m/Δm  1000. Because the early marginal oscillators operated at constant
frequency, the magnetic field had to be scanned for a mass spectrum. The
scan was slow. However, the instrument allowed to investigate ion-
molecule reactions, ion chemical reaction mechanisms at low pressure under
single collision conditions at (near)-thermal energies. The new technique
was easy to operate. As a consequence of this great development, a new field
of chemistry was opened. The first prototype instrument went to the
Baldeschwieler group at Stanford University, a chemistry group. Many
fundamental publications followed by this group, by former members of
the group who went to other places, and by “newcomers.” Most of these
publications opened new research fields for the first time.

1966
The Baldeschwieler group published a report on ion cyclotron double res-
onance for the study of the mechanisms of ion-molecule reactions with the
aid of kinetic energy dependence [37]. Ions are resonantly irradiated to
increase their kinetic energy. The mechanism of the ion-molecule reactions
of a mixture of CD4 and N2 was investigated. After electron impact ioniza-
tion, the mixture contained a small proportion of ions. Therefore, in the
ICR cell, all ion-molecule reactions are of pseudo-first order.

1967
A theory of collision-broadened ICR spectra was developed by Beauchamp
[38]. The Baldeschwieler [39] group published a detailed investigation of a
complicated ion chemical reaction system, generated from chloroethylene.
The enormous potential of the ICR method was shown for the first time.
Dunbar [40] studied the energy dependence of ion-molecule reactions.
A description of the instrument was given by Baldeschwieler et al. [41].
The authors stated: “the characteristics used in the observation and measure-
ment of ion molecule reactions are then:
1. The ion lifetimes extend to 100 ms.
2. The path lengths of the ions extend to 100 m.
 Historical developments in FT ICR mass spectrometry 7

3. The electric fields can be as small as 10 mV/cm.

4. Ions of specific charge to mass ratio can be accelerated by the application
of resonant radio frequency fields.” (p.113).

1968
New groups appeared. They all employ more or less laboratory-rebuilt, Syr-
otron ICR spectrometers. Bowers and Elleman from JET Propulsion Lab-
oratory and Beauchamp, now at California Institute of Technology, studied
the ion-molecule reactions of olefins [42]. Brauman and Blair [43], at Stan-
ford University, directly measured gas-phase acidities with proton transfer
reactions and double resonance experiments. Henis and coworkers from
Monsanto Company investigated the ion chemistry of methanol [44], and
described a detection scheme with electron energy modulation [45]. Kaplan
[46], later at the University of Cincinnati, identified collision-induced frag-
mentation with ion cyclotron double resonance ICDR. King and Elleman
[47] from Jet Propulsion Laboratory studied ion-molecule reactions of
hexafluoroethane.

1969
Clow and Futrell [48] from the University of Utah, observed charge
exchange by ICDR. Huntress and Beauchamp [49] adapted the ICR tech-
nique for Penning ionization. Benzene ionization by metastable N2 was
investigated. Isotopic exchange reactions of CH4-D2 and CD4-H2 mixtures
and the mechanism of self-induced labeling of methane by Tritium were
investigated by Inoue and Wexler [50] of Argonne National Laboratory.
O’Malley and Jennings [51] investigated the ion chemistry of acetylene. Jen-
nings and coworkers at the University of Sheffield, England were the first
research group outside the United States. The publications refs. [49] and
[51] appeared in the just established new “Journal of Mass Spectrometry
and Ion Physics.”

Developments from 1970 to 1980

From 1970 on besides many new research areas and new ICR groups, sev-
eral major improvements of the ICR technique were achieved.

1970
McIver [52] introduced the trapped ion analyzer ICR cell. Contrary to the
ICR drift cell, this cell has only a single region. The cell has trapping plates
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