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Direct Analysis in Real Time Mass Spectrometry

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Direct Analysis in Real Time Mass
Spectrometry

Principles and Practices of DART-MS

Edited by Yiyang Dong

Editor All books published by Wiley-VCH are
carefully produced. Nevertheless, authors,
Prof. Yiyang Dong editors, and publisher do not warrant the
Beijing University of Chemical information contained in these books,
Technology including this book, to be free of errors.
College of Life Science and Technology Readers are advised to keep in mind that
No.15 Beisanhuan East Road statements, data, illustrations, procedural
Chaoyang District details or other items may inadvertently
100029 Beijing be inaccurate.
China
Library of Congress Card No.: applied for

British Library Cataloguing-in-Publication

Data
A catalogue record for this book is
available from the British Library.

Bibliographic information published by

theDeutsche Nationalbibliothek
The Deutsche Nationalbibliothek
lists this publication in the Deutsche
Nationalbibliografie; detailed
bibliographic data are available on the
Internet at <http://dnb.d-nb.de>.

© 2018 Wiley-VCH Verlag GmbH & Co.

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translation into other languages). No part
of this book may be reproduced in any
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any other means – nor transmitted or
translated into a machine language
without written permission from the
publishers. Registered names, trademarks,
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specifically marked as such, are not to be
considered unprotected by law.

Print ISBN: 978-3-527-34184-9

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I dedicate this book to my beloved parents, Yuante Tung and Shuchen Hsu.
I am best endowed with your love, goodness, honesty, wisdom, endeavors, and
perseverance; for that, thank you so much.
 vii

Contents

Preface xv
About the Editor xvii

1 Introduction of Mass Spectrometry and Ambient Ionization

Techniques 1
Yiyang Dong, Jiahui Liu, and Tianyang Guo
1.1 Evolution of Analytical Chemistry and Its Challenges in the
Twenty-First Century 1
1.2 Historical Overview of Mass Spectrometry and Its Role in
Contemporary Analytical Chemistry 5
1.3 Desorption/Ionization in Mass Spectrometry 12
1.3.1 Electronic Ionization (EI) 13
1.3.2 Chemical Ionization (CI) 14
1.3.3 Fast Atom/Ion Bombardment Ionization (FAB) 15
1.3.4 Electrospray Ionization (ESI) 16
1.3.5 Matrix Assisted Laser Desorption/Ionization (MALDI) 18
1.3.6 Field Desorption (FD) or Field Ionization (FI) 19
1.3.7 Plasma Desorption (PD) (ICP, LTP, DART) 19
1.4 Ambient Ionization and Direct Analysis in Real Time 21
1.4.1 Ambient Ionization 21
1.4.2 Direct Analysis in Real Time 24
1.4.2.1 Mechanisms 24
1.4.2.2 Parameters 27
1.4.2.3 Devices 29
References 30

2 DART Mass Spectrometry: Principle and Ionization

Facilities 43
David Rondeau
2.1 Introduction 43
2.2 Metastable Gas Stream Formation 43
2.3 Ionization Mechanisms in Positive DART 45
2.3.1 Generation of Primary Ions by Ambient Air Ionization 46
2.3.2 Formation of the Protonated Molecules 50

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viii Contents

2.3.3 Formation of the Ammonium Adducts 54

2.3.4 Formation of the Radical Cations and Their Fragments 55
2.3.5 Matrix Effects in DART Due to Sample Solvents 59
2.4 Ionization Mechanisms in Negative DART 65
2.4.1 Generation of Primary Ions by Ambient Air Ionization 65
2.4.2 Formation of Deprotonated Molecules 68
2.4.3 Formation of Radical Anions 69
2.4.4 Formation of Anionic Adducts 70
2.5 Some Parameters Affecting the DART Mass Spectra 71
2.5.1 Substitution of Helium by Nitrogen or Argon 71
2.5.2 The Temperature of the Gas Stream 75
2.5.3 The Internal Energy of Ions in DART-MS 76
2.6 Conclusion 78
References 78

3 Sampling and Analyte Enrichment Strategies for DART-MS 81

Wen Ma, Xianjiang Li, and Huwei Liu
3.1 Dilution Strategy for Sticky Sample Analysis 81
3.2 Purification Strategy for Eliminating the Matrix Interference 82
3.2.1 Liquid Phase Extraction 82
3.2.2 Solid Phase Extraction (SPE) 86
3.2.3 Solid Phase Microextraction (SPME) 87
3.3 Derivatization Strategy to Decrease Polarity and Enhance
Volatility 89
3.4 Conclusions 91
References 91

4 Optimization of DART and Mass Spectrometric Parameters 97

Guohua Wu and Wushuang Li
4.1 Introduction 97
4.2 Effect of Working Gas Type, Gas Flow Rate, and
Its Temperature 98
4.2.1 Gas Type 98
4.2.2 Gas Flow Rate 99
4.2.3 The Working Gas Temperature of DART Ionization Source 100
4.3 Effects of Grid Electrode Voltage and Sampling Speed 102
4.3.1 Effect of Grid Electrode Voltage 102
4.3.2 Effect of Sampling Speed 103
4.4 Effect of the Sampling Mode 104
4.4.1 Sampling Methods 104
4.4.2 Position and Angle of the DART Ion Source 105
4.5 Effect of Ion Mode 106
4.6 Effect of Solvent Type and Reagents 108
4.7 Summary 109
References 109
 Contents ix

5 Interfacing DART to Extend Analytical Capabilities 115

Yiding Zhang, Shuting Xu, and Yu Bai
5.1 Introduction 115
5.2 Interfacing DART with Different Separation Techniques 116
5.2.1 Solid Samples 116
5.2.2 Gaseous Samples 118
5.2.3 Liquid Samples 119
5.2.3.1 Liquid Chromatography 119
5.2.3.2 Capillary Electrophoresis 123
5.3 Techniques of Interfacing DART with Other Analytical
Techniques 125
5.3.1 Surface Plasmon Resonance 125
5.3.2 Ion Mobility Spectrometry 126
5.4 Conclusion and Perspectives 129
References 129

6 Application of DART-MS in Foods and Agro-Products

Analysis 133
Canping Pan and Lei Wang
6.1 Introduction 133
6.2 Applications of DART-MS in Agriculture and Food Science 134
6.2.1 DART-MS in Pesticide Residue Analysis 134
6.2.1.1 Fast Screening Purposes 134
6.2.1.2 Screening Highly Hazardous Pesticides in Agrochemical
Formulations 140
6.2.1.3 Quantitative MRM Residue Method 147
6.2.2 Veterinary Drug Residue Detection 148
6.2.3 Fast Detection of Melamine in Milk 149
6.2.4 Detection of Mycotoxins in Cereals 150
6.2.5 Food Component Rapid Analysis 151
6.2.6 Contaminations in Food Contact Materials (FCMs) 156
6.3 Conclusion 156
References 157

7 Application of DART-MS for Industrial Chemical Analysis 163

Qiang Ma
7.1 Application on Household Items 163
7.1.1 Polydimethylsiloxane (PDMS) Analysis in Articles for Daily Use 163
7.1.2 Identification of Sulfides in Drywall 165
7.1.3 Phosphoric Acid Esters Screening in Aqueous Samples 168
7.2 Application on Food Packaging Safety and Quality Control 172
7.2.1 Identification of PDMS in Food Packaging Materials 172
7.2.2 Identification of Polymer Additives in Food and Food Packaging 175
7.2.3 Identification of Residue Primary Aromatic Amines (PAAs) in Food
Packaging Materials 176
7.3 Application on Pharmaceutical Products 177
7.3.1 Toxic Glycols Identification 177

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x Contents

7.3.2 Identification of Active Ingredients in Chinese Herbal Medicines 179

7.4 Application on Cosmetics Quality Control 182
7.4.1 Screening of Glucocorticoids Illegal Addition 182
7.5 Application on Other Industrial Chemical Fields 184
7.5.1 Ink Discrimination on Questioned Document 184
7.5.2 Ionic Liquids Identification 189
7.6 Conclusions 190
References 190

8 Application of Direct Analysis in Real Time Coupled to Mass

Spectrometry (DART-MS) for the Analysis of Environmental
Contaminants 193
Maxime C. Bridoux and Sébastien Schramm
8.1 Introduction 193
8.2 Screening and Quantitative Analysis of Pesticides 194
8.3 Flame Retardants DART-MS Analysis 204
8.3.1 Organophosphorus Flame Retardants (OPFRs) 204
8.3.2 Brominated Flame Retardants (BFRs) 207
8.4 Use of DART-MS for the Analysis of Personal Care Products
(PCPs) 210
8.4.1 Screening of Organic UV Filters in Water 210
8.4.2 Screening of Phthalic Acid Diesters 211
8.4.3 HPLC-DART-MS Analysis of Parabens 211
8.5 Use of DART-MS for the Analysis of Aerosols 212
8.5.1 Online DART for Aerosols Analysis 212
8.5.2 Offline DART Methods 213
8.5.3 Advantages and Limitations of DART-MS for Aerosols
Characterization 213
8.6 Miscellaneous Environmental Application of DART-MS 214
8.7 Conclusions 215
References 216

9 Application of DART-MS in Clinical and Pharmacological

Analysis 223
Yue Li
9.1 Introduction 223
9.2 Sample Preparation 224
9.3 Applications of DART-MS 225
9.3.1 Rapid Determination of Small Organic Compounds in Biological
Samples 225
9.3.1.1 Analysis of a Bitter Herbal Medicine Gentiana scabra Root
Extract 225
9.3.1.2 Simultaneous Determination of 3-Chlorotyrosine and 3-Nitrotyrosine
in Human Plasma 226
9.3.1.3 Rapid Screening for Methamphetamine,
3,4-Methylene-dioxymethamphetamine, and Their Metabolites in
Urine 227
 Contents xi

9.3.2 Newborn Screening for Phenylketonuria 227

9.3.3 DART-MS Analysis of Skin Metabolome Changes in Ultraviolet
B-Induced Mice 228
9.3.4 Application in Detection of Breast Cancer 231
9.3.5 Transmission Mode DART-MS for Fast Untargeted Metabolic
Fingerprinting 232
9.3.6 Applications of Confined DART Ion Source for Online In vivo Analysis
of Human Breath 233
9.3.6.1 Real-Time Analysis of Exhaled Breath 234
9.3.6.2 Real-Time Monitoring of Oral Anesthetic Drug 235
9.4 Challenges and Limitations 236
9.5 Recent Advancements 237
References 238

10 DART-MS Applications in Pharmaceuticals 241

Karina G. Putri, Qianwen Wu, and Young P. Jang
10.1 Pharmaceutical Analysis 241
10.2 Quality Assurance 243
10.3 Illegal Active Pharmaceutical Ingredients and Counterfeit Drugs 244
10.4 Drug Development 247
References 251

11 Application of DART-MS in Natural Phytochemical

Research 255
Vikas Bajpai, Awantika Singh, Brijesh Kumar, and Kunnath P. Madhusudanan
11.1 Introduction 255
11.2 Direct Analysis in Real Time (DART) Mass Spectrometry 256
11.3 DART-MS Parameter Optimization for Phytochemical Analysis 256
11.4 Applications of DART-MS in Phytochemical Research 257
11.4.1 Qualitative Phytochemical Analysis 257
11.4.2 Cell Culture Analysis 261
11.4.3 Analysis of Volatiles 261
11.4.4 Species Identification 262
11.4.5 Metabolic Profiling and Multivariate Analysis 263
11.4.6 Quantitative Analysis 274
11.5 Hyphenated DART-MS Techniques for Phytochemical Analysis 276
11.5.1 GC and HPLC-DART-MS 276
11.5.2 TLC/HPTLC-DART-MS 276
11.5.3 Capillary Electrophoresis-DART MS 277
11.5.4 DART-IMS-MS 277
11.5.5 Other Coupling Techniques 277
11.6 Improving Sensitivity of DART-MS for Phytochemical Analysis 278
11.6.1 Solvents and Gases 278
11.6.2 Matrix Suppression 279
11.7 DART -MS as Process Analytical Technology 279
11.8 Future Perspective 280
References 280

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xii Contents

12 Miscellaneous Applications of DART-MS 291

Yoshihito Okada
12.1 Introduction 291
12.2 Usefulness of Negative-Ion Mode 292
12.3 Application to Archeology and Conservation 293
12.4 Application by Using TLC 293
12.5 Application to Low Volatility, Chemical Warfare, and Homeland
Security 294
12.6 Pheromone Profiles from Live Animals in Parallel with Behavior 295
12.7 Application to Distinction of Plants with Similarity 296
12.8 Application to Space 298
12.9 Application to Bituminous Coals 298
12.10 Application to Detection of Nicotine 298
12.11 Other Potential Applications of DART-MS 299
12.11.1 Instantaneous Screening for Counterfeit Drugs with No Sample
Preparation [26-1] 299
12.11.2 Direct Analysis of Drugs in Pills and Capsules with No Sample
Preparation [26-2] 300
12.11.3 Detection of Lycopene in Tomato Skin [26-3] 300
12.11.4 Distribution of Capsaicin in Chili Peppers [26-4] 302
12.11.5 Detection of Unstable Compound Released by Chopped Chives
[26-5] 302
12.11.6 Rapid Detection of Fungicide in Orange Peel [26-6] 304
12.11.7 "Laundry Detective": Identification of a Stain [26-7] 304
12.11.8 Detection of the Peroxide Explosives TATP and HMTD [26-8] 306
12.11.9 Instantaneous Detection of Explosives on Clothing [26-9] 306
12.11.10 Rapid Detection and Exact Mass Measurements of Trace Components
in a Herbicide [26-10] 308
12.11.11 Rapid Analysis of p-Phenylenediamine Antioxidants in Rubber
[26-11] 308
Acknowledgment 309
References 309

13 Inherent Limitations and Prospects of DART-MS 313

Tim T. Häbe, Matthias Nitsch, and Gertrud E. Morlock
13.1 Aspects of Inherent Limitations of DART-MS 313
13.1.1 Gas Settings 314
13.1.1.1 Type of Gas 314
13.1.1.2 Gas Temperature 314
13.1.1.3 Gas Flow Rate 317
13.1.2 Voltage of Electrodes 317
13.1.3 Sample Introduction and Positioning 318
13.1.4 Detection System and Mass Range 318
13.1.5 Matrix Effects and the Need for Chromatography 319
13.1.6 Buffer and Salt Effects 321
13.1.7 Sample Carrier and Solvent 322
13.1.8 Humidity Effects 322
 Contents xiii

13.1.9 Use of Isotopically Labeled Standards 322

13.1.10 Dopant and Derivatization 323
13.2 DART versus Other Ambient Ion Sources 324
13.3 Prospects of DART-MS 326
13.3.1 Automation and Miniaturized DART-MS 326
13.3.2 Sample Preparation, Preconcentration, and Introduction 327
13.3.3 Ion Focusing and Flexible Ion Transportation 327
13.3.4 Quantitative Surface Scanning and Imaging by DART-MS 328
13.3.5 Hyphenation of Effect-Directed Analysis and DART-MS 331
13.3.6 Thermal Separations by Temperature Gradients 331
13.3.7 Aerosol, in situ and in stillo Chemical Reaction and Kinetic
Monitoring 332
13.3.8 High Resolution and Data Analysis 332
13.4 Concluding Remarks 333
References 333

Index 345

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 xv

Preface

All the authors who have contributed to this book have tried to describe that
direct analysis in real time (DART), as a representative ambient ionization
technique initiated by Penning ionization of atmosphere or electron emission
from surfaces, has developed into a potential analytical tool from a mechanistic
perspective for various applications.
In Chapter 1, the evolution of mass spectrometry and its role in contemporary
analytical chemistry have been reviewed, desorption/ionization in mass spec-
trometry is discussed, and ambient ionization and DART are briefly introduced.
In Chapter 2, the principle of DART and ionization mechanisms are well
depicted.
In Chapter 3, to overcome DART limitations in terms of sample uniformity,
ionization energy and efficiency, sample preparation and analyte-enrichment
strategies are provided. In Chapter 4, parameters that influence DART-MS
performance are summarized to optimize and quantitate analytes with improved
sensitivity and accuracy. To further extend analytical capabilities, interfacing
TLC, GC, HPLC, CE, SPR, and IMS with DART-MS has been realized and
summarized in Chapter 5 systematically.
Abundant DART-MS applications for foods/agro-products, industrial chem-
icals, environmental contaminants, pharmaceuticals, clinical/pharmacological
analysis, natural phytochemical research, and relevant DART-MS reports are
comprehensively presented in Chapters 6–12, respectively. In Chapter 13,
inherent limitations of DART-MS are thoroughly investigated. In addition, com-
parisons for DART with other ambient ion sources are made. Furthermore, some
prospective applications, such as DART with high resolution MS, instrumental
automation and miniaturization, surface scanning and imaging, and so on, are
rather promising and encouraging.
I hope both analytical experts and novice investigators will find this book very
useful, and acknowledge all the authors who have contributed to this book with
great appreciation thereof.

Oct 8th, 2017 Yiyang Dong

Beijing University of Chemical Technology
China
 xvii

About the Editor

Yiyang Dong obtained his bachelor’s degree in Chemistry

in 1989 from the East China Normal University where
he acquired knowledge in fundamental analytical chem-
istry and mass spectrometry; then he went on to pursue
his postgraduate study at the Nankai University and got
his master’s degree in liquid chromatography. In 1995,
he went to the Peking University to investigate capil-
lary electrophoresis for chiral separation and obtained
a doctorate of philosophy in separation science in 1998.
Yiyang Dong, PhD He also carried out postdoctoral research at Prof. Kita-
mori’s laboratory in the University of Tokyo, Japan, to
study microfluidics and related miniaturized bioanalytical techniques and tried
to hyphenate these frontier techniques with mass spectrometry (MS) for various
analytical applications later.
In early 2012, Dong joined the Beijing University of Chemical Technology
(BUCT) as a full professor of Chemistry through a talent program and set up
a research laboratory for food safety analysis and risk assessment, where he
developed mass spectrometric and several facile bioanalytical methodologies
for fast identification of small molecular adulterants, additives, and functional
ingredients in various food matrices. It was here that his interest in direct
analysis in real time (DART) and other ambient ionization strategies began
with a cooperatively gelivable investigator Professor Wei Yong from the Chinese
Academy of Inspection and Quarantine (CAIQ).
This research interest continued when Dong’s graduate students Tianyang
Guo and Pingping Fang began to participate in relevant DART research projects.
Recent years have witnessed a broad utilization of DART in various research
fields to introduce DART with representative analytical applications; he is
therefore pleased to be the editor of this book on MS and feels happy to share
with the audience the state of the art.

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 1

Introduction of Mass Spectrometry and Ambient

Ionization Techniques
Yiyang Dong, Jiahui Liu, and Tianyang Guo
College of Life Science & Technology, Beijing University of Chemical Technology, No. 15 Beisanhuan East Road,
Chaoyang District, Beijing, 100029, China

1.1 Evolution of Analytical Chemistry and Its

Challenges in the Twenty-First Century
The Chemical Revolution began in the eighteenth century, with the work of
French chemist Antoine Lavoisier (1743–1794) representing a fundamental
watershed that separated the “modern chemistry” era from the “protochemistry”
era (Figure 1.1). However, analytical chemistry, a subdiscipline of chemistry, is
an ancient science and its metrological tools, basic applications, and analytical
processes can be dated back to early recorded history [1]. In chronological spans
covering ancient times, the middle ages, the era of the nineteenth century, and
the three chemical revolutionary periods, analytical chemistry has successfully
evolved from the verge of the nineteenth century to modern and contemporary
times, characterized by its versatile traits and unprecedented challenges in the
twenty-first century.
Historically, analytical chemistry can be termed as the mother of chemistry,
as the nature and the composition of materials are always needed to be iden-
tified first for specific utilizations subsequently; therefore, the development of
analytical chemistry has always been ahead of general chemistry [2]. During
pre-Hellenistic times when chemistry did not exist as a science, various ana-
lytical processes, for example, qualitative touchstone method and quantitative
fire-assay or cupellation scheme have been in existence as routine quality control
measures for the purpose of noble goods authentication and anti-counterfeiting
practices. Because of the unavailability of archeological clues for origin tracing,
the chemical balance and the weights, as stated in the earliest documents ever
found, was supposed to have been used only by the Gods [3].
During the middle ages (fifth to fifteenth century), alchemists began to
assemble scattered knowledge that later became chemistry. Wet chemistry
using mineral acids with noble metals symbolized the beginning of analytical
chemistry as we know it today, and the evolution continued during the Age
of Medicinal Chemistry (AD 1500–1650) as well as during the phlogiston era.

Direct Analysis in Real Time Mass Spectrometry: Principles and Practices of DART-MS, First Edition.
Edited by Yiyang Dong.
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2018 by Wiley-VCH Verlag GmbH & Co. KGaA.
2 1 Introduction of Mass Spectrometry and Ambient Ionization Techniques

Figure 1.1 Portrait of

Antoine-Laurent Lavoisier and his
wife by Jacques-Louis David, about
1788.

The phlogiston theory was developed by J.J. Becher (1635–1682) late in

the seventeenth century and was extended and popularized by G.E. Stahl
(1659–1734). Some classical analytical methods had been developed since the
seventeenth century: gravimetric analysis was invented by Friedrich Hoffmann
(1660–1742), titrimetric analysis using nature dye indicators was widely prac-
ticed in 1874. Guy-Lussac (1778–1850) developed a titrimetric method for silver
and got remarkable accuracy better than 0.05%, and Antoine Lavoisier who
used balance to confute the phlogiston theory, demonstrated the law of mass
conservation, which earned him the title “father of quantitative analysis.”
In 1826, Jean-Baptiste Dumas (1800–1884) devised a method for the quantita-
tive determination of nitrogen in chemical substances. In 1860, the first instru-
mental analysis, namely, flame emissive spectrometry was developed by Robert
Bunsen and Gustav Kirchhoff (Figure 1.2) who discovered rubidium (Rb) and
caesium (Cs), and up to the latter half of the nineteenth century, about 90 ele-
ments were successfully discovered by the support of analytical chemistry, from
which organic chemistry has benefited a lot. The periodic table of elements was
created by Dmitri Mendeleev (1834–1907) in 1869. In 1876, the paper entitled
“On the Equilibrium of Heterogeneous Substances” published by Willard Gibbs
(1839–1903) introduced and developed systematic chemical concepts as corner-
stones and fundamental principles for analytical chemistry.
The year 1894 was very significant when Wilhelm Ostwald (1853–1932)
published an important and very influential text on the scientific fundamen-
tals of analytical chemistry entitled “Die Wissenschaftichen Grundlagen der
Analytischen Chemie” (Figure 1.3). In addition, a series of chemical revolu-
tions, that is, the first chemical revolution at the molar level from 1770–1790,

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 1.1 Evolution of Analytical Chemistry and Its Challenges in the Twenty-First Century 3

Figure 1.2 Photograph of Robert

Bunsen (right) and Gustav Kirchhoff
(left).

Figure 1.3 Wilhelm Ostwald (1853–1932).

Recipient of the 1909 Nobel Prize for
Chemistry “in recognition of his work on
catalysis and for his investigations into the
fundamental principles governing chemical
equilibria and rates of reaction.”

the second chemical revolution at the molecular level from 1855–1875, and the
third chemical revolution at the electrical level from 1904–1924, were chrono-
logically implemented, which greatly facilitated the emergence and bloom of
modern analytical chemistry, via which instrumental analysis became prevalent
to address assorted analytical needs [4].
4 1 Introduction of Mass Spectrometry and Ambient Ionization Techniques

A prototype of mass spectrometer for ion separation and identification was

invented by English physicist and 1906 Nobel Laureate in Physics Joseph John
Thomson (1856–1940) at the beginning of the twentieth century, and in 1922,
Francis William Aston (1877–1945) at the Cavendish laboratory in the Univer-
sity of Cambridge won the Nobel Prize for Chemistry for his investigation of
isotopes and atomic weights using developed mass spectrometer with improved
mass resolving power and mass accuracy. The spectrometer was developed in
1941, and self-recording Infrared, direct-reading, and self-recording emission
spectrophotometers appeared in 1951. Gas chromatographs (GC) and nuclear
magnetic resonance (NMR) spectrometers were produced in 1953, and the
1959 Nobel Prize for Chemistry was awarded to Heyrovsky for the invention
of polarography. Around 1960, atomic absorption spectroscopy (AAS) was
developed and GC coupled with mass spectrometry (MS) was applied for the
identification of organic compounds. Later in the 1970s, high performance liquid
chromatography (HPLC), with the merits of linking to MS with established
analyte ionization strategies, emerged as a powerful tool to meet analytical
challenges especially for natural product and biomedical researches.
Classical and modern chemistry with intellectual separation, identification,
and quantitation strategies have been well studied and utilized to meet scientific,
technical, and sometimes engineering needs; however, in the twenty-first
century, due to rapid urbanization, mass industrialization, and business glob-
alization, there are many serious problems, for example, resource shortage,
climate change, and environment deterioration, facing the world, and therefore
contemporary analytical chemistry needs to go further to deal with assorted
eco-environmental, social public, macro-economic, or even individual ethical
needs accordingly. Nowadays, micro-morphological imaging, visual identifica-
tion, nontargeted profiling or multianalyte analysis, and ultra-sensitive, superior
selective, high-throughput, in situ nondestructive and rapid cost-effective assay
schemes are frequently needed for numerous analytical purposes, which are, to
name a few, characterization of advanced materials, researches of noncovalent
conjugates, discovery of therapeutic drugs, prognosis of new contagious diseases,
surveillance of process or product quality, safeguarding food security and safety,
management of consumer complaints, preservation of ecosystem, criminal
investigations and forensic science, anti-terrorism practices, archeological
excavations, and explorations of deep earth/sea and space missions. Therefore,
to fulfill these challenging analytical assignments, contemporary analytical
chemistry needs to interact intensively with its sister disciplines, for example,
physics, electromechanics, biology, mathematics, and information science.
Probably the most challenging task in contemporary analytical chemistry lies
in unveiling vital phenomena and life dynamics systematically using analytical
tools developed for proteomics, metabolomics, and lipidomics researches. In
addition, for analytes at the single molecular level or near zero concentrations
where quantized nature of the matter dominates in its natural or complicated
matrices, characterization of analysis capability and assurance of result fidelity
continue to remain formidable tasks. As exemplified by the detection of
persistent organic pollutant dioxins and polychlorinated biphenyls (PCBs) at
part-per-trillion or part-per-quadrillion level, for geographical identification,

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16 1 Introduction of Mass Spectrometry and Ambient Ionization Techniques

Atom gun

Primary Focusing
Vacuum atom beam lens
interface To mass
Probe Secondary
ions spectrometer

Sample
Extraction
grid

Figure 1.13 A schematic view of fast atom bombardment ionization mechanism. (https://
upload.wikimedia.org/wikipedia/commons/thumb/a/ad/FAB_Schematic.jpg/1280px-FAB_
Schematic.jpg. Licensed under CC BY SA 4.0.)

e– Figure 1.14 A schematic view of the direct

Electron exposure ionization method for DEI or DCI.
or chemical (Adapted from Ref. [28], Copyright 1980, The
ionization American Chemical Society.)
source

Sample
molecule in
solid phase

FAB is relatively a soft insensitive ionization technique, and has very limited
amenability to LC/MS. The sensitivity of FAB is usually at a nanomole level and
has a typical mass range of 7000 Da for mass characterization of most target
molecules.
For molecules with relatively no volatility and lability, two desorption ioniza-
tion techniques other than FAB, namely, desorption electron ionization (DEI) and
desorption chemical ionization (DCI) were successfully developed in the 1980s
[28]. As shown in Figure 1.14, in this technique, the solid sample molecules coated
onto the surface of an inert probe tip protrude directly into the ionization region
of the ion source, and the analyte molecules on the probe are desorbed without
decomposition by an apparent volatility enhancement process and ionized either
by electron ionization or by chemical ionization consequently. In 1989, FAB, DEI,
and DCI were comparatively utilized for mass spectrographic analysis of periph-
erally substituted synthetic porphyrins [29].

1.3.4 Electrospray Ionization (ESI)

ESI is a technique used in MS to produce ions using an electrospray in which
a high voltage is applied to a static or continuous liquid flow to create charged
droplets. Thanks to the relevant theoretical base of charged droplet and
electrospray prior to the 1940s, the first use of ESI with MS was reported by Dole

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