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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
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Nationalbibliografie; detailed
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Internet at <http://dnb.d-nb.de>.
© 2018 Wiley-VCH Verlag GmbH & Co.

KGaA, Boschstr. 12, 69469 Weinheim,
Germany
All rights reserved (including those of

translation into other languages). No part
of this book may be reproduced in any
form – by photoprinting, microfilm, or
any other means – nor transmitted or
translated into a machine language
without written permission from the
publishers. Registered names, trademarks,
etc. used in this book, even when not
specifically marked as such, are not to be
considered unprotected by law.
Print ISBN: 978-3-527-34184-9

ePDF ISBN: 978-3-527-80373-6
ePub ISBN: 978-3-527-80371-2
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Cover Design Adam-Design, Weinheim,

Germany
Typesetting SPi Global, Chennai, India
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Printed on acid-free paper
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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
6.2 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
8.2 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
9.2 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
11.2 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
12.2 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
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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].
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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1.2 Historical Overview of Mass Spectrometry 5
Metrology
Scientific, Technical,
or Social problem
Traceability
Information
Analytical
Analytical problem
properties
Analytical
Quality
process
Figure 1.4 Essence and elemental relationships of contemporary analytical chemistry.

(Adapted from Ref. [5], with permission from Elsevier.)
or for botanical/zoological authentication of olive oils and honeys, where

sophisticated sample pretreatment steps and advanced instrumentations with
chemometrics or bioinformatics packages are usually needed to acquire large
volume analytical information for further data mining and model prediction.
In practice, analytical chemistry is inherently a metrological science with
conventional separation, identification, and quantitation procedures. In order
to tackle all sorts of scientific, technical, and social problems, contemporary
analytical chemistry has been evolved nowadays as an autonomous scientific
discipline that develops and applies methods, instruments, and strategies to
obtain information on the composition and nature of matter in space and time
[5] (Figure 1.4).
In the twenty-first century, much effort will be needed to make the analysis
more objective and highly reproducible. Utilization of novel analytical schemes
or frontier technologies, for example, ambient ionization MS, ultra-performance
liquid chromatography (UPLC), surface enhanced Raman spectrometry (SERS),
lab on a chip or micro total analysis systems (μTAS), as well as profound
researches on error propagation, uncertainty evaluation, and measurand trace-
ability using certified reference materials and third-party proficiency tests or
other relevant quality assurance measures are always needed to meet diverse
fundamental, industrial, or regulatory requirements.
1.2 Historical Overview of Mass Spectrometry and Its

Role in Contemporary Analytical Chemistry
Mass spectrometry (MS) is the study and recognition of matter through
the determination of the abundance and the mass-to-charge ratio (m/z) of
ions in gaseous state. The history of MS dates back to the early 1900s, when
English physicist and 1906 Nobel Laureate in Physics Sir Joseph John Thomson
I–
B
A
N
z
C y
H
G x
E J
D
S
I+
F
Figure 1.5 Schematic representation of the parabola mass spectrograph. A, the gas inlet;
B, the anode; C, the discharge tube; D, the port to the vacuum system; E, the cathode; F, the
magnetic shields; G, the water jacket for cooling; H, the insulators; and J, the photographic
plate used to detect the ions. (Adapted from Ref. [6], with permission from Wiley.)
(1856–1940) developed a parabola mass spectrograph as the first prototype of

mass spectrometer to separate different ions by their characteristic parabolic
trajectories in electromagnetic fields and to identify these ions using a pho-
tographic plate (Figure 1.5). In 1913, authored by Thomson, the first book on
MS, Rays of Positive Electricity and Their Application to Chemical Analyses, was
published heralding the advent of MS research for precise characterizations in
all fields of contemporary analytical chemistry [7].
In order to improve MS resolving power to study isotopes, around 1911, Thom-
son’s protégé, Francis William Aston (1877–1945) at the Cavendish laboratory in
the University of Cambridge devised a velocity-focusing sector-based mass spec-
trometer to provide accurate m/z values and published in 1921 the famous paper
“The Constitution of Atmospheric Neon,” [8] which was considered to be the first
paper in applied MS. In 1922, Aston won the Nobel Prize for Chemistry for his
discovery of isotopes in a large number of nonradioactive elements by means of
MS and the enunciation of whole number rule.
During the same period, the Canadian American physicist Arthur Jeffery
Dempster (1886–1950) in the University of Chicago developed a direction-
focusing sector-based mass spectrometer to provide accurate ion abundance
values (Figure 1.6). In the late 1920s, Dempster proposed the combination
of direction focusing and velocity focusing to further improve MS resolution
along with Bartky [9] and around 1934 developed the first dual focusing mass
spectrometer .
The pioneer works of Thomson, Aston, and Dempster were so profound for the-
oretical research, instrumental development, and technological evolution of MS
as a competent tool in contemporary analytical chemistry that they are usually
considered to be the founding fathers of modern MS [10].
With the aid of electronic ionization (EI) facilities and early magnet sector-
based mass spectrometers, MS became an indispensable tool for fundamental
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Figure 1.6 Schematic

representation of Dempster’s
direction-focusing mass
spectrometer that includes E, the
ion-detection device; G, the glass
ion-source housing containing the
filament F that was heated to Pump
produce electrons that bombarded
the platinum sample holder P; and
P
B, the analyzer section surrounded
E
by the magnet. A potential F
difference between the sample
holder and the first slit (S1 ) provided G
the ion acceleration and collecting C
with intermediate slit (S2 ) and S1
S3
collector slit (S3 ). (Adapted from Ref.
[6], with permission from Wiley.)
B
S2 A
particle profiling, isotope characterization, and elemental analysis and was

mainly utilized for the researches of physicists, inorganic chemists, and geo-
chemists prior to the 1940s. Worthy of note also is the utilization of preparative
MS to separate uranium-235 from uranium-238 for the development of the
atomic bomb during World War II.
While early mass spectrometric research was inherently focused on inorganic
analysis, as complaints of detected ions from organic impurities rather than
analytes were documented the potential of MS for organic analysis became
noted by scientists and, accordingly, the 1940s saw the birth of organic MS,
and early commercial mass spectrometers became available in the market
especially for industrial oil or petroleum analysis, where volatile and thermally
stable organic chemicals were frequently needed to be characterized. However,
because gaseous ions had to be formed prior to separation and identification
in early MS instrumentation, only limited organic compounds were suitable for
mass spectral analysis.
Many research efforts and achievements on MS instrumentations had been
acquired to enhance the analytical capability of mass spectrometers till the end
of the 1950s. In 1946, William E. Stephens of the University of Pennsylvania pro-
posed the concept of time-of-flight (TOF) MS, in which ions could be separated
by differences in their straightforward drifting velocities toward the collector.
The merit of the TOF mass analyzer lies in its superior resolving capability, high
accuracy, virtually unlimited mass range, and rapid analyses at the milliseconds
level for a full ionic scan [11]. Nowadays, due to efficient ionization facilities, for
example, electrospray and matrix assisted laser desorption/ionization (MALDI),
TOF mass analyzers have become routine research tools of choice for conducting
research on both small organic molecules and large biomolecules.
In the 1950s, Wolfgang Paul, a German experimental physicist of the University
of Bonn, successfully developed both quadrupole (Figure 1.7) and ion trap, the
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+
– – End view
+ 2r0
Electron beam Ion beam
Filament
+Us U + V cos ωt
Ion source Rod system Collector
Figure 1.7 Schematic view of the quadrupole mass spectrometer or mass filter. (Reproduced
with kind permission of Wolfgang Paul [12], The Nobel Foundation 1989.)
two most-used nonmagnetic mass analyzers. Compared with highly precise and
accurate double focusing mass spectrometers, cost-effective quadrupole and ion
trap mass spectrometers can furnish excellent dynamic range, spectral stability,
and the facileness to perform tandem MS, which are deemed to be ideally suited
for the development of frontier analytical instrument and method; for instance,
Ouyang and Cooks at Purdue University had developed a handheld mass spec-
trometer for future field assays with a miniaturized ion trap mass analyzer oper-
ating at several milliTorr and maintaining sufficient ion capacity [13].
Thanks to the aforementioned mass analyzers and the application of desktop
computers for data acquirement/analysis, the GC, developed around 1952 by
A.T. James and A.J.P. Martin was coupled with the mass spectrometer in the
1960s, and gas chromatography mass spectrometry (GC-MS) became one of the
most widely used analytical instruments for organic analysis or reaction mecha-
nism intepretation in the 1970s, when high performance liquid chromatography
mass spectrometry (HPLC-MS) emerged but was initially not as successful as
GC-MS, because the ionization of analytes coeluting with HPLC mobile phases
was not always possible.
In 1974, Melvin B. Comisarow and Alan G. Marshall of the University
of British Columbia developed Fourier transform ion cyclotron resonance
mass spectrometry (FT-ICR-MS) [14], which determines simultaneously the
mass-to-charge ratio (m/z) of ions based on the cyclotron frequency of the ions
in a fixed magnetic field. It can provide superior resolving power and accuracy as
the ultimate solution for high-resolution MS analysis, as exemplified by Bruker’s
SolariX XR FT-ICR-MS system for metabolomics, proteomics, environmental,
petroleum and energy researches, and an increditable resolving power of 10
million can be achieved using superconductive, refrigerated, and ultrashielded
magnets. Theoretically, in FT-ICR-MS, the excited ions, when trapped in a
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FT–ICR
CH4+
17 DEC., 1973
0.01 amu
Figure 1.8 First FT-ICR mass spectrum. (Adapted from Ref. [11], with permission from Prof.
Alan G. Marshall.)
Penning trap and rotating at their cyclotron frequency as ion packets, can induce
an image current on electrodes as the packets of ions approach the electrodes,
and mass spectrum can be extracted subsequently by Fourier transforming from
the resulting signal called free induction decay (FID) (Figure 1.8).
Other than EI, a series of novel ionization schemes, for example, electrospray
ionization (ESI), atmospheric pressure chemical ionization (APCI), and MALDI
were successively developed from the 1960s to the 1980s, which gave birth to the
technical maturing and commercial prosperity of HPLC coupled with the com-
petency of various mass analyzers for the analysis of small organic compounds
and large biomolecules. In addition, inductively coupled plasma (ICP) ionization
was successfully combined with mass analyzer for inorganic analysis with unpar-
alleled sensitivity and broad applicability.
At the end of the twentieth century, by virtue of the development of various
mass analyzers and ionization strategies, MS had been chronologically utilized
for numerous applications of chemical and biochemical researches: peptide
mapping was investigated in 1990 with electrospray ionization mass spectrome-
try (ESI-MS) [15], noncovalent interactions were studied with ESI in 1991 [16],
oligonucleotide ladder sequencing and protein identification were reported in
1993 [17, 18], MALDI ion imaging was developed in 1994 [19], intact virus
analysis was implemented in 1996 [20], and the year 1999 saw quantitative
proteomics and metabolomics with isotope labels [21].
In the twenty-first century, new mass analyzing technology as exemplified by
OrbitrapTM was further developed together with many fascinating ambient ion-
ization schemes, for example, desorption electrospray ionization (DESI), direct
analysis in real time (DART), and paper spray ionization (PSI). For challenging
explorations, MS was being extensively used in researches of shotgun lipidomics
[22] and human proteome map drafting (Figure 1.9) [23].
Accompanying with the development of MS throughout the years, the role
of MS in contemporary analytical chemistry is obvious and irreplaceable, and
the uniqueness of MS stems from its physical simplicity, outstanding resolving
power, superior mass accuracy, and facile and high-throughput analytical capa-
bility for ionic molecules or fragments. In the twenty-first century, in order to
meet rigorous eco-environmental, social public, macro-economic, or even indi-
vidual ethical demands, and to deal with assorted scientific, technical, or civil
engineering needs, MS, with its perfectionism achieved by MS researchers in the
world, is undoubtedly deemed to be the ultimate solution for contemporary ana-
lytical chemistry (Table 1.1).
Adult tissues Fetal tissues
Liver
Spinal cord Frontal cortex
Retina Testis Heart
Lung Brain
Ovary
Heart Esophagus Gut Placenta
Liver Pancreas Haematopoietic cells
Gall bladder Colon

Adrenal gland
Rectum Common myeloid Common lymphoid
Kidney progenitor progenitor
Urinary bladder Ovary
(a) Prostate Testis

Platelets Monocytes CD4+ CD8+ NK B
T cells T cells cells cells
y2
Intensity
Intensity
Trypsin y4
y
SDS–PAGE digestion y y 7
y1 y3 5 6
Protein extract Time m/z

RPLC Tandem MS Data analysis
Trypsin
(b) digestion bRPLC
Figure 1.9 Overview of the workflow of MS for human proteome map drafting. (a) The adult/fetal tissues and hematopoietic cell types that were analyzed to
generate a draft map of the normal human proteome. (b) The samples were fractionated, digested, and analyzed on the high-resolution and high-accuracy
Orbitrap mass analyzer. (Adapted from Ref. [23] by permission from Macmillan Publishers Ltd: Nature, copyright 2014.)
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Table 1.1 Historical developments in mass spectrometry.
Year Contribution Investigator(s) Remarks
1899–1911 First mass spectrometer J.J. Thomson 1906 Nobel Laureate in

Physics
1918 Electron ionization and Dempster
magnetic focusing
1919 Atomic weights using MS Aston 1922 Nobel Laureate in
Chemistry
1934 Double focusing Mattauch and Herzog
instruments
1946 Time-of-flight mass Stephens
analysis
1949 Ion cyclotron resonance Hipple, Sommer and
Thomas
1953 Reverse geometry double Johnson and Nier
focusing instruments
1953 Quadrupole analyzers Paul and Steinwedel 1989 Nobel Laureate in
Physics (Wolfgang
Paul)
1956 High-resolution MS Beynon
1959–1963 GC/MS McLafferty and Ryahe
1966 Peptide sequencing Biemann, Cone, Webster,
and Arsenault
1966 Chemical ionization Munson % field
1968 Electrospray ionization Dole
1969 Field desorption-MS of Beckey
organic molecules
1974 Plasma desorption-MS MacFarlane and Torgerson
1974 FT-ICR-MS Comisarow and Marshall
1978 Triple quadrupole MS Yost and Enke
1981 Fast atom bombardment Barber
(FAB)
1984 ESI on biomolecules Fenn 2002 Nobel Laureate in
Chemistry
1985–1988 Matrix facilitated laser Tanaka, Karas, and 2002 Nobel Laureate in
desorption/ionization Hillenkamp Chemistry (Tanaka)
1990 Protein conformational Chowdhury, Katta, and
changes with ESI-MS Chait
1991 Noncovalent complexes Ganem, Li, Henion, Chait,
with ESI-MS and Katta
1993 Oligonucleotide ladder Pieles, Zurcher, Schar, and
sequencing Moser
1993 Protein mass mapping Henzel, Billeci, Stults,
Wong, Grimley, and
Watanabe
(Continued)
Table 1.1 (Continued)
Year Contribution Investigator(s) Remarks
1996–2001 Intact viral analysis Benner, Siuzdak, Bothner,

and Fuerstenau
1998 Electron capture Zubarev, Kelleher, and
dissociation (ECD) McLafferty
1999 Nanostructure Wei, Buriak, and Siuzdak
desorption/ionization
1999 Quantitative proteomics Tong, Want, Smith, Shen,
and metabolomics with Tsao, Meng, Brandon,
isotope labels Webb, Siuzdak, Gygi, Rist,
Gerber, Turecek, Gelb, and
Aebersold.
2000 Orbitrap Makarov
2003 Shotgun lipidomics Han and Gross
2004 Desorption electrospray Takats, Wiseman,
ionization (DESI) Gologan, and Cooks
2004 Electron transfer Syka, Coon, Schroeder,
dissociation (ETD) Shabanowitz, and Hunt
2005 Direct analysis in real time Cody, Laramee, and Durst
(DART)
2013 Surgical “intelligent knife” Balog, Sasi-Szabo, Kinross,
(iKnife) Lewis, Muirhead, Veselkov,
Mirnezami, Dezso,
Damjanovich, Darzi,
Nicholson, and Takatz
2014 Draft of the human Kim, Pinto, Wilhelm,
proteome Schlegl et al.
1.3 Desorption/Ionization in Mass Spectrometry

MS is the application of science and art to identify matters in their ionic forms
with magnet sector or nonmagnet sector based mass analyzers, and analyte
ionization is the most crucial procedure for MS. As shown in Figure 1.10,
instrumental configuration of a mass spectrometer for MS characterization
normally comprises a sample inlet, an ionization source, a mass analyzer/filter
and an ion detector. The sample was first introduced into the spectrometer
through a sample inlet, ionized by the ionization source and propelled into the
mass analyzer/filter where sample ions were separated by their characteristic
m/z, and eventually identified by the ion detector.
Small molecules with low boiling points and most inorganic compounds
can be easily ionized with a specific ionization source for successful mass
spectrometric analysis without any desorption or ablation procedures, as
evidenced by ubiquitous applications of EI source prior to the 1960s. However,
for nonvolatile, thermal labile compounds, and polymer or large biomolecules,
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*** START OF THE PROJECT GUTENBERG EBOOK THE SOUL OF

ANN RUTLEDGE: ABRAHAM LINCOLN'S ROMANCE ***
THE SOUL OF ANN RUTLEDGE
ABRAHAM LINCOLN'S ROMANCE
SECOND IMPRESSION
"ABRAHAM, THIS PLACE SEEMS HOLY AND YOU ARE ITS PROPHET"
Page 276
ABRAHAM LINCOLN'S ROMANCE

BY
BERNIE BABCOCK
WITH A FRONTISPIECE IN COLOR BY GAYLE HOSKINS
PHILADELPHIA & LONDON

J.B. LIPPINCOTT COMPANY
1919
COPYRIGHT, 1919, BY J.B. LIPPINCOTT COMPANY
PRINTED BY J.B. LIPPINCOTT COMPANY
AT THE WASHINGTON SQUARE PRESS
PHILADELPHIA, U.S.A.
To J
AUTHOR'S NOTE
In the tremendous output of Lincolniana that has been given to
literature, it seems strange that no adequate story has been given of
one of the greatest loves in history.
Many writers have referred to it and to its moulding power on the
lover's after life. Some have thrown sidelights on the character of
the woman. Some have mentioned her rare gift of song and her
unusual endowment of mind, and one writer has given a careful
description of her personal appearance. But so far as careful and
exhaustive research shows, all this matter has never been woven
into one story.
It is also strange that there has been so much controversy regarding
the religious views of Abraham Lincoln, and by those whose faith is
based on the evidence required by the Great Teacher When He said,
"Ye shall know them by their fruits." Nor should it ever have been
taken as an evidence of lack of faith because he did not accept the
creedal beliefs of his day, for had not the Christ Himself strenuously
denied much that was insisted on in His day, Christianity could never
have been possible.
In this story both the love and the faith of one of earth's noblest
souls is simply and intimately told.
In an age when the cynical opinion is too often heard, that between
men and women there can be no different or more lasting love than
the mating instinct of animals, and at a time when the death of
millions of the world's best men has brought into fresh insistence the
age-long question, "If a man die shall he live again?" a fresh and
different setting forth of Abraham Lincoln's master passion for a
woman, and his calm and unshakable faith in immortality, may be of
more than usual interest and value.
CONTENTS
CHAPTER PAGE
I. One April Day 11
II. In Clary's Grove 23
III. The Railsplitter 33
IV. The Pilgrim 40
V. Swapping Hosses 50
VI. "Fixin' fer the Angels" 60
VII. "Sic 'em, Kitty" 66
VIII. The Test 73
"Thou Shalt not
IX. 83
Covet"
X. The Mysterious Pig 92
Peter Cartwright
XI. 101
Arrives
XII. The Righteous Shout 113
XIII. A Busy Sinner 124
XIV. The Spelling Match 134
XV. "Who's Afraid?" 146
XVI. Politics and Steamboats 157
XVII. Captain Lincoln 163
"Books Beat Guns,
XVIII. 171
Sonny"
XIX. Abe Makes a Speech 175
XX. Story of a Boy 180
XXI. Only Wasting Time 189
XXII. Town Topics 202
XXIII. Alias McNeil 211
XXIV. In the Cellar 221
XXV. Father and Daughter 227
XXVI. Gloom and the Light 232
XXVII. Covering the Coals 245
"He's Ruint Hisself
XXVIII. 256
Forever"
XXIX. God's Little Girl 263
XXX. The End of June 271
XXXI. Stronger Than Death 277
XXXII. The Unfinished Song 286
"Where is Abe
XXXIII. 294
Lincoln?"
For the Things That
XXXIV. 305
Are to be
XXXV. The Poem 310
XXXVI. On the Way 321

CHAPTER I
ONE APRIL DAY
"Ann! Ann! Ann Rutledge! Hallo! Hallo!"
The cheerful voice belonged to a rosy-cheeked girl who shouted in
front of Rutledge Inn, one of the straggling group of log houses that
made the village of New Salem, Illinois, in 1831.
Pausing in front of the Inn, the animated girl repeated her call lustily
as she watched for the closed door to open.
"Hallo yourself, Nance Cameron," a clear, musical voice replied from
somewhere in the rear of the weather-stained building, and the next
moment Ann Rutledge came around the corner.
"Look! Springtime has come! Isn't it splendid to be alive in the
springtime? I found them in the thicket!" and pausing she held out
an armful of plum branches white with their first bloom.
In the moment she stood, an artist might have caught an inspiration.
On one side of the background was a vista of open garden, perhaps,
and meadow, with a glimpse of forest farther back, and over it all
the white-flecked, spring-blue sky.
On the other side was the solid framework that told of days when
there had been no meadow or garden, and of the pioneer labor that
had wrought the change.
In the foreground of this brown and green and blue setting stood a
slender girl in a pink-sprigged calico dress. Her violet eyes were
shaded with dark lashes. Her shapely head was crowned with a
wealth of golden hair in which a glint of red seemed hiding. A white
kerchief was pinned low about her neck, and across her breast were
tied the white strings of a ruffled bonnet which dropped on her
shoulders behind. She pressed her face for a moment in the armful
of blossoms, sniffing deep, and with the joy of youth exclaimed
again, "Isn't it splendid to be alive in the springtime!"
But Nance Cameron had no eye for the artistic at this moment.
"Have you been to the river?"
"River? What's going on at the river?"
"Didn't Davy tell you, nor your father?"
"No, I've just come home across lots from Green's. What's
happening at the river?"
"Everything, and everybody's down seeing it happen. Let's go."
"If you'll wait till I fix my flowers."
"Don't wait—drop them or bring them. Everybody but us is there."
Nance Cameron had turned to the roadway. Ann was about to join
her when she turned back.
"Bad luck! Bad luck!" shouted Nance. "Don't go back!"
"I forgot to shut the back door."
Nance stopped, made a cross in the dirt and spat on it.
"You don't pay attention to your signs worth a cent," she said, as
Ann rejoined her.
"I don't much believe in signs," Ann answered.
"That's where you're silly. A black cat ran across Mrs. Armstrong's
path no later than yesterday after she had her soap in the kettle.
And wasn't that soap a fizzle? And don't Hannah Armstrong know
how to make soap? It was the cat did it, and if I hadn't changed
your luck just now you'd been in for something awful—might never
live to marry John McNeil."
Ann laughed, and they started on their way down the road, that
stretched the length of New Salem's one street toward Sangamon
River.
"What's going on at the river?" Ann asked again.
"Somebody's ark is stuck on the dam. It got stuck just before dark
last night. The crew couldn't get it off and had to wait until morning.
They came up to the store to get some drinks. The town men
gathered in and you never on this earth heard such roars of laughter
as those men let out. Ma couldn't guess what it could be about.
When Pa came in he told her there was the funniest tall human
being he ever set eyes on with the ark crew. Said his legs reached as
high up as a common man's breech belt, his body reached up as
high as another man's arms, and his head was up on top of all that.
And Pa said he told the funniest stories, and the men nearly died. Pa
was laughing yet when he told Ma about it."
"Is the boat stuck yet?"
"She's stuck yet. Dr. Allan and Mentor Graham just went down and I
heard them talking. She's on her way to New Orleans with a load of
barreled pork and stuff. Davy's been up to the store twice. He says
the crew have worked like beavers to get the cargo off the big boat,
but that the water is running in bad and the barrels are slipping to
the end which sticks out over the dam and she's sure to go over.
She's going to make a great splash, and I love splashes. Let's hurry!"
"I hope nobody gets drowned," Ann said.
"Like as not they will, and we'll get to see them fished out. Let's trot
a little."
With the inspiring hope of hearing a splash and perhaps seeing the
first shocking throes of a drowning, the two girls hastened on down
the slope that reached to Rutledge Mill, where the dam was.
It was true, as Nance had said, New Salem was out to witness the
unusual sight of a flat boat on the dam where it had been stuck
nearly twenty-four hours. It was a river craft of the usual flat-boat
size, about forty feet long by fifteen wide, and sides six feet high.
One end was covered with a roof of boards, and there were other
boards fitted with ragged sails to hasten the freight-bearer on its
long journey of 1800 miles to New Orleans.
The crowd on the river bank and the platform of the mill was lavish
with suggestions and advice which were shouted to the crew
working desperately to save the cargo.
Ann Rutledge and Nance Cameron paused a moment to take in the
view of the unfortunate boat, whose rear stuck clear of the water
and into whose fore the barrels were slowly settling. It seemed
nothing could prevent the impending catastrophe.
"Let's get out on the platform. I would like to see that funny, tall
fellow your father told about," Ann said.
Passing through the mill, deserted for the time by the dusty miller,
the girls joined the crowd on the platform and Ann found herself
standing by a peculiar appearing personage, a small man of
uncertain age, who wore foxed breeches and coon-skin cap, and
who had but one good eye which just now was fastened on the fore
of the imperiled boat.
"'Ole Bar's' come back," Ann whispered, punching Nance and turning
her eye toward the old man who stood beside her.
'Ole Bar' was a person of interest, and very peculiar. He was chewing
some sort of a cud rapidly. When an unusually interesting suggestion
was shouted out over the roar of the dam water, he rolled his cud
into a hollow made by the loss of two back teeth and kept quiet until
the moment of suspense was past, when he made up time working
his jaws. Nance only glanced at him now. "I wonder where that tall
baboon is?" she said, craning her neck toward the raft.
"See that thar patch of something that ain't no color the Lord God
ever made nor no shape He ever seen? Well, that's his hat. He's
under it, squattin' in the boat, doin' something to get 'er goin'."
"What's he doing?" Ann ventured.
"Eh—that's it," Ole Bar said with a dry smile. "The rest of the crews
runnin' about like chickens with their heads chopped off, and these
here galoots along shore is yelping like a pack of coyotes after a
buffalo bull. But he's keepin' cool. This kind generally gits something
done. Howsomever, that ark's goin' over. I've been numerous in
turkey-trottin' and bee-runnin' and bar-killin', but I hain't never
before seen an ark in no such fix as this un is."
"Look Nance," Ann whispered. "He's rising up—look!"
A moment his body partially showed. Then he bent low again. The
next moment there was a sudden spurt of water from the bottom of
the boat. The water pumping its way out caught the attention of the
crowd.
"He's emptying her out!" they cried. "How did he do it?"
The tall figure under the colorless, shapeless hat had now lifted
himself, and, as if to straighten his muscles after a long cramped
position, he stretched to a height that seemed to be that of a giant,
threw out his chest, reached his long arms to a prodigious expanse
and took a deep breath.
As he did so Ann felt someone touch her. It was "Ole Bar." "Some
huggin' he could do with them arms in matin' season—hey, Molly,"
he said; and when Ann turned to look at Ole Bar he winked his good
eye at her and waited for an answer.
A shout from the crowd made any answer to this remark
unnecessary. For a moment the towering youth stood before them
like a comical picture, slender, angular, barefooted, his faded yellow
breeches scarce more than clearing his knees and showing a pair of
spindle legs. His uncolored shirt was flung wide open and over one
shoulder was stretched a suspender which held one breeches-leg
higher than the other. As the water pumped itself out and the boat
began to right, they knew that he had bored a hole.
The cheers continued, he lifted his shapeless hat and, with the grace
of a gentleman, waved it a couple of times at the cheering crowd.
Then he pushed back a mop of black hair, clapped his head-covering
down on it and turned to help reload the cargo that had been moved
into small boats.
To bore a hole in the bottom of a water-filled boat was no great
physical task. But the crowd cheered uproariously as the boat
righted herself. Men shouted, women waved their bonnets and
kerchiefs, and Ann Rutledge shook her branches of wild plums.
Again the ungainly young giant waved his hat.
"He's waving at you, Ann," John McNeil, who had joined the girls,
said, coming up behind her. "Wave at him." And she did and laughed
as he swung his limp and tattered hat.
"Where do you suppose that kind grow?" Nance asked. "He looks
like a giant scarecrow, but he's had lessons in manners, the identical
same kind Mentor Graham tells about."
It took but a short time to reload the boat. As she started on her
way the cheers died, and most of the crowd went up the hill to the
village.
"Let's stay to see the last of it," Ann said to Nance.
"You want him to wave at you some more," John McNeil said to Ann.
"Well, go ahead—you'll never see him again."
The boat sailed on. To those on board who looked back a few
moments later, the mill and dam were resolving themselves into an
indistinct patch of gray and brown, against which a bit of pink,
waving something white, stood out. As a farewell answer to the
waving of the white, the mellow music of the boat horn came
floating back.
The sun went down behind the forests bordering the smoothly
flowing Sangamon; the crude craft passed from view.
And yet once again the mellow tones of the primitive horn came
floating back over the forest and across the river.
"What a good sound!" Ann exclaimed. "It's soft as the first shadows,
and it's strong."
"Yes, strong as that man's arms in mating season—hey, Molly?" And
Nance punched Ann in the side.
The girls laughed merrily. "Isn't 'Ole Bar' funny?" Ann said. "He's just
back from an awful exciting trip to Arkansas, wherever that is. He'll
have lots to tell."
"Davy and father will get his stories. But say, Nance, do sounds
make you think of smells?"
"I never thought of such a thing."
"Don't cow-bells make you think of hay and dandelions and grass
and the smell of the cow-lot in the evening?"
"They do go together."
"And don't water running over roots make you think of willow
blooms, and water dripping over stones sound like ferns when the
stems are crushed? And the sound of crows—don't they bring the
smell of the field furrows? And don't bees and honey-locust, and
robins and apple blossoms, go together? I could name a hundred
sounds that have smells for partners.
"Yes, but you're funny, Ann, to think of such things."
"Now I have a new pair. The sound of that horn, away off behind the
trees, will always make me think of the first plum blossoms. The
smell and the sound came together as I shook the branches, and the
smell right here seemed to me exactly the same thing told in
another way as the sound away over the water. O Nance—don't you
love plum blossoms?"
"I don't know as they're any better than dogwood or haw blooms
and I'm not crazy about any of them."
"You're just like John McNeil. John don't like plum blossoms. I nearly
cried when he told me he was going to chop out all the plums and
wild vines on his place. But those on our place will not be cut. Father
has promised me the thicket and the dell on the creek for my flower
garden forever."
"I'd rather have a new belt-buckle. But let's go."
"I'm ready—I'll race you to the top of the bill before the sun drops
behind the trees. One—two—three—off," and with her spring flowers
in her arms and her bonnet flying, Ann with Nance ran shouting up
the hillside in the slanting rays of the April sun.
CHAPTER II
IN CLARY'S GROVE
The evening of the day the imprisoned flat boat made its way
successfully out of New Salem, the Clary Grove gang had a meeting.
Windy Batts was expected to return from Springfield, where he had
gone to prove his fitness for fellowship with the Clary Grove Boys by
thrashing a Springfield strong man who had cast aspersions on his
character as a pugilist.
Clary Grove was a settlement of a few log houses near New Salem,
so called for Bill Clary, the owner of the grove where the select met
to swap stories, discuss news and partake of real liquor.
Every new-comer to the vicinity was sized up. If Clary Grove was
friendly, so much the better for the new-comer. He might not
become a member of the gang. Indeed few were allowed to sit in
close fellowship about the fire with the gang, but he would at least
be let alone.
Windy Batts had expressed a desire to be of the gang. He was,
however, looked upon with a degree of suspicion, as he had done
some exhorting for the Hard Shells, and Clary Grove looked askance
at religion in any form, and while he had boasted of "dingblasting
the daylights out of them shoutin' Methodists," Clary Grove was not
satisfied that he was proper stuff to fellowship with them and their
whiskey.
They awaited his return from Springfield, where he was to prove his
pugilistic ability, with some interest.
The cool, spring air with the tang of frost not yet safely out of it,
made a fire comfortable, and a bright blaze burned between the two
smooth logs on which the gang roosted.
Buck Thompson, the luckiest horse-trader in that section, and Ole
Bar were the first to arrive. Ole Bar sat beside the fire, his jaws
working industriously and his one good eye shining like a spark. No
one of the gang had ever been able to learn what misfortune had
befallen the lost eye of Ole Bar.
That he had been "cleaned of it right and proper" all agreed. Opinion
was divided, however, as to the cause or method, one portion
believing a bear had clawed it out, because of his familiarity with
bears, and others holding to the opinion that some specimen of
womankind was responsible for the loss, because of his oft-
expressed unfriendly feeling toward women.
Jo Kelsy, a fat and favorite brother of the clan, who was always
ready with a new story about a ghost or a witch from his one
treasure, an inherited copy of Shakespeare, was the third to arrive.
His usual costume was varied slightly. He came hobbling in, one foot
encased in a moccasin. Ole Bar glanced at his mismated feet.
"What's bit ye, Jo?" he asked.
"My wife she dropped a five-gallon crock on my foot," he answered.
"Good thing it wasn't your head, for be it known by man and bars,
them as mixes up with wimmen has heads softer than their feet."
Jo laughed good naturedly. Then the three talked of the raft and the
ungainly youth who had resorted to the homely but efficient
expedient of boring a hole.
"I've seen some legs in my day," Jo Kelsy observed, "but none long
as his'n."
"Ain't no longer than yours is, Dumplin'," said Old Bar. "Yours
reaches to the ground and his'n don't go no further. According to my
way of figgerin' his legs wasn't so numerous when it comes to length
as his head. That galoot's got a long head."
A couple more of the gang dropped in, and the talk continued about
the raft and the head raftsman. "Ever see anything like it? Wouldn't
think a backwoodsman could tell such stories as he did last night,
would ye?"
"Nor know enough to get an ark floating when she was stuck so
tight that God hisself couldn't stick her no tighter."
"McNeil was figgerin' on her cargo to see what it was worth."
"Trust McNeil for figgerin' the worth of a cargo—or anything else."
"Ann Rutledge—eh?"
They laughed. Then one said, "I heard him tellin' Hill him and Ann
was goin' to marry and have a big infare. But her Pappy won't let her
till next year. She has to git more schoolin'."
"He better git while gittin's good. John Rutledge is fixed, and he sets
more store by Ann than the whole other eight of 'em."
"McNeil knows all that. But here comes Kit Parsons. Wonder what's
kept him late? Kit, you're late."
"Yeh," and he sat down by the fire.
"What's extry? Been stealin' anything or gettin' religion?"
"Same thing as gettin' religion," he said. "Been fulfillin' the Scripture
injunction."
"Which one?"
"Been replenishin' and multiplyin'."
"Mollie got another litter?" Ole Bar asked with a show of interest.
"Just one this year. But I calculate that a man what grubs for three
which arrives in two years is somewhat religious."
"Bars is that religious," the one-eyed man observed, "only when they
pursue the course of Nature they don't blame it on religion."
After a laugh Ole Bar said solemnly to Kit, "If you young fellers knew
what was good fer you you'd let wimmin alone."
"Where'd you learn so much about wimmin?" Jo asked.
"From bars. Bars rub noses at matin' time and tears the ears offen
each other when the cubs has to be fed. Let wimmin alone and save
the wear on your noses and ears."
"How's a body going to leave any ancestry if he don't never git no
place near a woman?" Buck Thompson asked.
"Ancestry?" repeated Ole Bar. "Well, what under heaven is these
little, wet-nosed ancestry good fer anyhow? Never had no ancestry
myself and I'm gettin' along all right—got along all right while I was
in Arkansas, and anybody that can do that don't need to worry
about leavin' no ancestry."
"Tell us about Arkansas," was the next demand.
Ole Bar shifted his cud into its receptacle and said, "Wall, as you all
know, in bar hunts I've been numerous, but I hain't never seen no
such bars as grow in Arkansas. The bars in Arkansas is the most
promiscuous I've ever seen and don't give a damn for nobody. But,
Squire, lets licker up. I'm gettin' so dry I'm takin' the rattles," and he
reached for the bottle which was passed around.
"Bars in Arkansas grows so fat they can't wobble. You fellers here
that think you're gettin' the real thing when you bag the chipper-
growlers and shite pokers of these parts don't know nothin' about
what's growing in Arkansas. Them bars rear up into the heavens
high as that feller that plugged the ark."
"That smells rather tall," Buck Thompson observed, but Ole Bar paid
no attention.
"The woods in Arkansas is ankle deep with acorns and berries and
other bar food. Everybody there eats bar, bar-ham and bar-sassage.
The beds is covered with bar-skins. They don't use small skins like
wild cat fer nothin' 'cept piller covers."
"Do they have hoss tradin' in them parts?" Buck Thompson inquired.
"Hoss tradin'? Well, I should say 'Yeh.' You galoots think you swap
hosses, but in Arkansas——"
"Hallo, fellers," shouted someone in the outer circle of light.
"It's Windy Batts," several declared at once, and immediately the
man whose qualifications to become a member of the charmed
group had been put to the test, entered the circle of light.
He was scrutinized and with not an altogether approving eye. His
arm was done up in a sling. The forefinger of his right hand was
wrapped in a red, calico handkerchief. Something like a knob stuck
out back of one ear which was covered with a square of muslin,
giving it the appearance of a pat of butter. One eye was black and
both legs seemed to be stiff. Greetings were brief. The main
question was. "Who whipped?"
"Yeh—who hollered?" was asked.
Windy drew near the fire. "It was a great fight," he began. "The
greatest fight that was ever fought in Springfield. We rolled over and
over, him sometimes on top and me sometimes under. It was a
fearful fight. Court turned out to see it and an Indian Chief was
there. He said he never seen nothing like it."
"Who whipped?" was again asked.
"Yeh—who hollered?"
Ignoring these questions, Windy continued.
"The big Indian and the Judge of the Court both said they hadn't
never seen such sledge-hammer blows as I hit. It was them blows
that put my shoulder out of joint. But I fixed his eye. You couldn't
have told it from a knot-hole in a burnt tree. Time he aimed a
second socdologer at me I was ready. The crowd roared like a camp-
meeting. We fell to it. He got a straddle of my head and chawed my
finger. There wasn't no place for me to git holt owing to the fact my
head was pinned in twix his legs. Jean britches didn't taste well and
was ungodly tough. But I was resolute. I found the right place and I
chawed like hell. But would he let go of my finger? No, and I finally
had to knock half his teeth out to git my finger out his mouth."
"You tanned him—hey?"
"You mauled him, Windy?"
"You beat the Springfield stuffing out of him?"
"And nobody parted you?"
Ignoring these questions, Windy took a fresh start. "And there's no
telling how long it might have lasted, us two going 'round and 'round
and up and down and every which way. I was eternally mauling the
ding-blasted daylights out of him when the Judge got hold of me
and asked as a favor if I wouldn't put off the finish till next day. He
said he couldn't get nobody into court if I didn't and so I—I
hollered."
There was a moment of profound silence. Windy shifted his weight
from one stiff leg to the other, stroked his bandaged arm and sighed.
"Spit in his ashes!"
It was the voice of Jack Armstrong that broke the painful stillness.
Immediately every man emptied the contents of his mouth, with no
small force, into the fire, which voiced its protest by a vigorous
spitting and sputtering.
Then Windy was given some advice.
"This ain't no place fer you. You go join them Hard Shells that's fixin'
fer a ten days' fightin' match with the devil. They have the same
runnin' off at the mouth as you have, but they hain't never drawed
no devil's blood yet, and that's your crowd."
Windy's lips moved as if to speak.
"Roll in your molasses sucker and trampoose," was the order.
"Yeh—trampoose," was the repeated order. "Go fight the devil."
"The devil—that's the Clary Grove gang," he muttered as he turned
away.
"Devil-fighter," some one said as his limping figure disappeared in
the darkness.
"If the devil pays any more heed to him than he would to a skit-fly
he's a blame bigger ass than I've ever took him to be," Ole Bar
observed. "Let's licker up."
CHAPTER III
THE RAILSPLITTER
It was two months after the flat boat stuck on the dam at New Salem
and the day following a quiet election in the village, that Nance
Cameron ran over to Rutledge Inn with news of great importance for
Ann.
"Long Shanks has arrived," she announced without ceremony.
"Long Shanks?" Ann questioned. "Who is Long Shanks?"
"The giant scarecrow, the big baboon," Nance answered.
"Baboon," Ann repeated. "Nance what are you talking about?"
"My land, Ann Rutledge, have you forgotten the unhinged giant you
waved plum blossoms at—the captain of the flat boat who looked
like sin, but knew how to use his hat like a gentleman?"
"Oh!" answered Ann. "Has he come?"
"Yes. He got here yesterday. They didn't have anybody to help at
election. Mentor Graham asked him if he could write. He said he
could make his rabbit's foot, and so he helped. Mr. Graham says he
can write well. Besides, he told them stories, and they liked that.
Last night he came to our house."
"Tell me about him. What does he look like close to?"
"He's the homeliest man God ever put breath into. His legs run down
into feet so long he can't find anything big enough to stick them
under, and his arms are nearly as long as his legs. He has a big
head, big nose, big mouth, big ears, lots of black hair, and he's hard
and horny and knotty like a tree—and as green, too."
"Did he talk to you?"
"No, he didn't pay me any heed at all, but he and Ma got to be good
friends before he'd been in the house an hour. She was tired half to
death putting up berries and trying to get supper. She put Johnnie
watching the baby and he let him roll down the steps. The new man
heard him crying and went right out and got him. In five minutes the
baby was laughing. This made Ma feel better and she got talking,
and first thing I knew he was helping her wash dishes and telling her
about what he saw in New Orleans and down the Mississippi. He
talks better than he looks."
"How does he talk? Has he a big, deep voice and mellow, like the
sound of the horn over the tree and river?"
"No, indeed. He sets out thin sounding, but his voice seems to work
down into his chest as he talks and he sounds pretty good. After
supper Pa brought in the cider. Mr. Graham came over and Dr. Allen,
and they got Long Shanks talking and didn't want him to quit.
Mentor Graham took a great liking to him. He lived in Kentucky once
and then Indiana. He asked about the folks in these parts and when
he heard Jo Kelsy owns a Shakespeare he said he was going to try
to borrow it, said he's read the Bible till he knew it by heart and the
Constitution and some other things but never seen a Shakespeare.
When Mr. Graham told him he had fifty books his dull, gray eyes
turned bright as new candles. He's terrible interested in books, but
he don't have any time for girls."
"How do you know?"
"'Cause. Ma asked him if he saw the girl waving at him, when the
boat stuck? He said, 'Yes'm—wasn't it kind of her?'"
"Ma said, 'She's the prettiest girl in town.'"
"He said, 'Yes'm—isn't that nice?'"
"Ma said, 'She's the smartest girl in town.'"
"He said, 'Yes'm—it's worth while to be smart!'"
"Ma told him you was going to marry John McNeil. He said, 'They all
do it.' And he never even asked your name."
"I tell you what; you drop past to-morrow afternoon before supper.
He'll be there then. He won't look at you, he's so funny. But you can
see him."
It was with as much interest as a person goes to a show that Ann
Rutledge went to the Cameron home the next afternoon. She was
doomed to disappointment.
"He's gone," Nance informed her.
"Where?"
"Gone out to split rails for some folks that have come in from
Indiana and are taking a homestead near Turtle Ford. He's going to
split enough rails to fence the clearing. He's to get one yard of
brown jeans dyed with white walnut bark for every four hundred
rails. It's to make some new breeches."
"That's an awful lot of work for a pair of pants."
"Yes, but look at the length of his legs. A fellow with legs like that
will always have to work extra to keep them covered."
"I wanted to see him."
"He's coming back. I heard him telling Pa he was going to open a
store here for a man named Offutt. His wares haven't come yet.
They will be here by the time the new breeches are ready. Then you
can see him. You'll think him half-baboon and half-giraffe and he
won't even notice you only to say 'Yes'm' and pull off his hat."
"Does he have any name? You didn't tell it."
"Name? O yes," and Nance laughed. "He's named after Abraham, of
the Abraham, Isaac and Jacob family. The rest of his name is
Lincoln."
"Abraham Lincoln," Ann repeated. "I don't think that's such a bad
sounding name."
John McNeil called at the Rutledge home the night young Lincoln
went to Turtle Ford to earn his new pants. After the family had gone
to bed and Ann was left to say good-night to the young man she
was engaged to, he said, "Ann, I thought that fellow was captain of
the boat and maybe owned some of the cargo. He's nothing but a
railsplitter."
"He didn't use his hat like a railsplitter."
"He's picked up a few lessons in manners somewhere—maybe saw
somebody doing it in New Orleans."
"No—because it was on his way down that he lifted his hat."
"Well, I don't know where he got it, but he's only a railsplitter just
the same. Hasn't a cent in the world. Didn't know it was a railsplitter
waving to you, did you?"
"It wasn't me he waved at. He never heard of me and don't know
yet that I am living. It was the flowers he liked and I'm glad he likes
flowers if he is a railsplitter."
"I'd like to know, Ann, why you take on so over flowers. What are
they good for?"
"Good for? What a funny question. What is the song of birds good
for and the fragrance of flowers and the beauty of ferns? What is the
music of running brooks good for and the splendor of gold and red
sunsets—what are any of them good for?"
"That's just what I'm asking," John McNeil said seriously. "What are
they good for? Can't eat them, can you? Can't wear them, can you?
Can't sell them, can you? or trade them or swap them for anything?
Women are such funny folks and don't know a thing about values.
But I'm going to leave the plum thicket another year and the corner
in the pasture where the blue flowers grow you like to pick."
"Thank you, John—thank you a whole lot"; and happy because of his
promise, Ann kissed John McNeil good-night.
CHAPTER IV
THE PILGRIM
A few days after Abraham Lincoln had entered service to split rails
for a new pair of breeches, he came to town late one afternoon to
get an ax.
After tarrying a short time to tell a story or two, he started back
about sun-down, his ax, on the handle of which was swung a
bundle, over his shoulder.
As twilight gathered, the ungainly youth took his way along the road
that ran not far from the smoothly flowing Sangamon. His strides
were long and easy, and, away from the small habitations and
contrivances of mankind, he seemed to become one with the big
things of nature, and what was sometimes considered lack of grace
seemed now an easy expression of reserve force.
The roar of the mill-dam sounded musical as if the twilight were
softening its daytime boisterous tumult.
The falling dew seemed loosening up the fragrance of the woods,
the subtle breath of tangled vines and trailing roses, with sometimes
a more decided fragrance, as when the full-sized foot of the
pedestrian brushed into a bed of wild mint.
As he rounded the skirt of the bluff, the rosy tinted sky seemed
suddenly to withdraw itself, and the timbers upon the summit to
move themselves slowly against the crimson and fading gold, like a
row of shadowy sentinels gathered for the night.
A tinkling gurgle from an irregular, dark spot against the foot of the
bluff told of a ravine, and the running stream, whose musical babble,
as it made its way to the river, sounded like the prattle of a child
compared to the river's volume falling by the mill.
As he took his way in the gathering gray of night, the long-limbed
youth cast giant shadows, subtle, indistinct shadows far across the
road and into other shadows, where they merged into the formless
gloom and were lost.
While yet rounding the bluff he heard the barking of a dog and then
the tinkle of a cow-bell. Common sounds these were, but coming on
the stillness from the heights above they lent a sort of musical
enchantment to the quiet and the enfolding mystery of night. Then a
human voice was heard, a woman's voice that seemed to burst
suddenly into the flower of a full blown song.
The youth slowed up a bit and listened. The words thrown out by
the ringing voice sounded clearly:
I'm a pilgrim
And I'm a stranger;
I can tarry, I can tarry but a night.
The young man stopped. The song was to him unusual. The clear
voice took the notes unhesitatingly and rolled them in melodious
movement as she sang the words "p-i-l-grim" and "s-t-r-a-n-ger,"
and then hurrying on gladly, as if it were a matter for great rejoicing
that she could tarry but a night.
The youth dropped his ax and bundle to the ground and turned his
face toward the bluff casting its long shadows. The bell tinkled a
moment in the gathering gloom. Then the voice rang out again on
the evening hush:
Do not detain me,
For I am going
To where the streamlets are ever flowing.
Again there was the peculiar rolling fall and rise on the syllables.
Again the gladness of some exultation, then the refrain "I'm a
pilgrim" with its confidence and its melody.
The voice was nearer now. There was no sound or sight of any
moving object on the bluff, but she was somewhere there and
seemed coming nearer.
The tinkle of the cow-bell made an interlude. Then again the voice
of singing, whether nearer or farther now he did not question. He
was listening to the words:
Of that country
To which I'm going
My Redeemer, my Redeemer is the light.
There is no sorrow
Nor any sighing
Nor any sin there, nor any dying.
The mysterious singer on the heights was farther away now. The
voice was growing fainter as the refrain rang into the stillness, "I'm a
pilgrim—and I'm a stranger—I can tarry—I can tarry——"
The youth leaned forward and listened, breathlessly. But the voice
was dying and the tinkle of the bell came on the stillness, faint as a

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1 Introduction of Mass Spectrometry and Ambient Ionization

2 DART Mass Spectrometry: Principle and Ionization

2.3.3 Formation of the Ammonium Adducts 54

3 Sampling and Analyte Enrichment Strategies for DART-MS 81

4 Optimization of DART and Mass Spectrometric Parameters 97

5 Interfacing DART to Extend Analytical Capabilities 115

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

7 Application of DART-MS for Industrial Chemical Analysis 163

7.3.2 Identiﬁcation of Active Ingredients in Chinese Herbal Medicines 179

8 Application of Direct Analysis in Real Time Coupled to Mass

9 Application of DART-MS in Clinical and Pharmacological

9.3.2 Newborn Screening for Phenylketonuria 227

10 DART-MS Applications in Pharmaceuticals 241

11 Application of DART-MS in Natural Phytochemical

12 Miscellaneous Applications of DART-MS 291

13 Inherent Limitations and Prospects of DART-MS 313

13.1.9 Use of Isotopically Labeled Standards 322

Oct 8th, 2017 Yiyang Dong

About the Editor

Yiyang Dong obtained his bachelor’s degree in Chemistry

Introduction of Mass Spectrometry and Ambient

1.1 Evolution of Analytical Chemistry and Its

Figure 1.1 Portrait of

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

Figure 1.2 Photograph of Robert

Figure 1.3 Wilhelm Ostwald (1853–1932).

A prototype of mass spectrometer for ion separation and identiﬁcation was

Figure 1.4 Essence and elemental relationships of contemporary analytical chemistry.

or for botanical/zoological authentication of olive oils and honeys, where

1.2 Historical Overview of Mass Spectrometry and Its

(1856–1940) developed a parabola mass spectrograph as the ﬁrst prototype of

Figure 1.6 Schematic

particle proﬁling, isotope characterization, and elemental analysis and was

Electron beam Ion beam

Ion source Rod system Collector

Heart Esophagus Gut Placenta

Liver Pancreas Haematopoietic cells

Gall bladder Colon

Urinary bladder Ovary

(a) Prostate Testis