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Chiral Analysis
Advances in Spectroscopy,
Chromatography and
Emerging Methods
Second Edition
Edited by
PRASAD L. POLAVARAPU
Vanderbilt University, Nashville, TN, United States
Elsevier
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Chiral Analysis
Advances in Spectroscopy,
Chromatography and
Emerging Methods
Second Edition
Edited by
PRASAD L. POLAVARAPU
CONTENTS
List of Contributors xiii

Prefacexvii
Part One Chirality in Nature 1
1. Chiral Asymmetry in Nature 3

Dilip Kondepudi
1.1 Introduction3
1.2 Chirality: terminology and quantification issues 3
1.3 Chiral asymmetry in nature 10
1.4 Theory of spontaneous chiral symmetry breaking 15
1.5 Sensitivity of chiral symmetry breaking transitions to asymmetric
interactions19
1.6 Examples of spontaneous chiral symmetry breaking 22
1.7 Concluding remarks 25
References25
2. Remote Sensing of Homochirality: A Proxy for the Detection

of Extraterrestrial Life 29
C.H. Lucas Patty, Inge Loes ten Kate, William B. Sparks, Frans Snik
2.1 Introduction29
2.2 Homochirality30
2.3 Chemical and biological mechanisms for creating circular
spectropolarimetric signals 35
2.4 Considerations for the remote sensing of homochirality in our solar
system and beyond 45
2.5 Instrumentation50
2.6 Conclusion and outlook 60
References61
Part Two Spectroscopic Methods and Analyses 71
3. Light Polarization and Signal Processing in Chiroptical

Instrumentation73
Kenneth W. Busch, Marianna A. Busch
3.1 Introduction73
Part A—The polarization of light 73
3.2 Light as a wave 74
v
vi Contents
3.3 Types of polarized light 76

3.4 Production of linearly polarized light 81
3.5 Production of circularly polarized light 98
3.6 Production of elliptically polarized light 101
3.7 Photoelastic modulators 101
Part B—Signal handling 105
3.8 Noise in electrical circuits 105
3.9 Noise reduction strategies 108
3.10 Application of phase-sensitive detection in chiroptical instrumentation 123
Appendix A basic optics 126
Appendix B signal handling 136
References150
4. Chiroptical Spectroscopic Studies on Soft Aggregates

and Their Interactions 153
Vijay Raghavan, Prasad L. Polavarapu
4.1 Introduction153
4.2 OR studies 158
4.3 ECD studies 172
4.4 VCD studies 184
4.5 ROA studies 193
4.6 Summary195
References195
5. Vibrational Optical Activity in Chiral Analysis 201

Laurence A. Nafie, Rina K. Dukor
5.1 Introduction201
5.2 Definitions of VOA 204
5.3 Measurement of VOA 206
5.4 Theoretical basis of VOA 208
5.5 Calculation of VOA 214
5.6 Determination of AC 216
5.7 Determination of ee of multiple chiral species 226
5.8 VOA of solids and formulated products 235
5.9 Summary and conclusions 238
References239
6. Raman Optical Activity 249

Saeideh Ostovar pour, Laurence D. Barron, Shaun T. Mutter, Ewan W. Blanch
6.1 Fundamental principles 250

6.2 Experimental ROA studies 256
Contents vii
6.3 Enhancement of ROA signals 270

6.4 Recent ROA instrumentation developments 273
6.5 Computational modeling of ROA spectra 274
6.6 Concluding remarks: future opportunities 282
References284
7. Chiral Molecular Tools Powerful for the Preparation

of Enantiopure Compounds and Unambiguous Determination
of Their Absolute Configurations by X-Ray crystallography
and/or 1H NMR Diamagnetic Anisotropy 293
Nobuyuki Harada
7.1 Introduction293
7.2 Methodologies for determining AC and their evaluations 294
7.3 Methodologies for chiral synthesis and their evaluations 297
7.4 Camphorsultam dichlorophthalic acid, CSDP acid (−)-1,
and camphorsultam phthalic acid, CPS acid (−)-5, useful
for enantioresolution of alcohols by HPLC and determination
of their ACs by X-ray crystallography 299
7.5 A novel chiral molecular tool, 2-methoxy-2-(1-naphthyl)-propionic
acid {MαNP acid (s)-(+)-2}, useful for enantioresolution of alcohols
and determination of their ACs by the 1H nmr diamagnetic anisotropy
method312
7.6 Complementary use of CSDP acid (−)-1 and MαNP acid (s)-(+)-2
for enantioresolution of alcohols and determination of their ACs
by X-ray crystallographic and 1H nmr diamagnetic anisotropy
methods325
7.7 Conclusions338
References339
8. Chiroptical Probes for Determination of Absolute

Stereochemistry by Circular Dichroism Exciton Chirality
Method345
Kuwahara Shunsuke, Ikeda Mari, Habata Yoichi
8.1 Introduction345
8.2 A chiroptical probe for chiral resolution and determination
of the absolute configuration of aromatic alcohols 346
8.3 A chiroptical probe for determination of the absolute configuration
of primary amines 352
8.4 A chiroptical probe for chirality transcription and amplification
by the forming of [2]pseudorotaxanes 358
8.5 Conclusions363
References363
viii Contents
9. Chiral Analysis by NMR Spectroscopy: Chiral Solvating Agents 367

Federica Balzano, Gloria Uccello-Barretta, Federica Aiello
9.1 Introduction367
9.2 Low-molecular-weight csas 371
9.3 CSAs involving ion pairing processes 383
9.4 Molecular tweezer csas 389
9.5 Synthetic macrocycle csas 391
9.6 Cyclodextrins401
9.7 Natural products 406
9.8 Lyotropic chiral liquid crystals 408
9.9 Chiral sensing 409
9.10 Configurational assignments 409
9.11 Conclusions411
References412
10. Chiroptical Spectroscopy of Biofluids 429

Vladimír Setnička, Lucie Habartová
10.1 Introduction429
10.2 Blood and blood-based derivatives 430
10.3 Hen egg white 446
10.4 Vitreous humor 447
10.5 Urine447
10.6 Chiroclinics—chiroptical methods as diagnostic tools 452
10.7 Concluding remarks 459
References460
Part Three Chromatographic and Electromigration Methods 467
11. Chiral Gas Chromatography 469

Rahul A. Patil, Choyce A. Weatherly, Daniel W. Armstrong
11.2 Commercial stationary phases 471
11.3 Non-commercial stationary phases 490
11.4 Conclusions500
References500
12. Chiral Liquid Chromatography 507

Muhammad F. Wahab, Choyce A. Weatherly, Rahul A. Patil,
Daniel W. Armstrong
12.2 Historical background of chiral liquid chromatography 508
Contents ix
12.3 Interactions in chiral liquid chromatography 509

12.4 Chiral separations in liquid chromatography today 512
12.5 Salient features of chiral liquid chromatography 512
12.6 Major classes of modern chiral stationary phases (CSPs)
for liquid chromatography: the “α” of the resolution equation 515
12.7 Packing process of high-efficiency chiral phases (“N” in the resolution
equation)534
12.8 Method development in chiral LC (adjustment of “k” in the resolution
equation)535
12.9 Special detectors in liquid chiral chromatography 536
12.10 Recent developments in enhancing chiral resolution using
ultrahigh efficiency supports 539
12.11 Instrumental considerations for fast chiral LC 544
12.12 Future directions and developments in chiral liquid chromatography 558
References558
13. Enantioseparations by Capillary Electromigration Techniques 565

Bezhan Chankvetadze
13.2 Separation principle in chiral CE: electrophoretic or chromatographic? 566
13.3 Enantioseparations with charged and uncharged chiral selectors 567
13.4 Enantioselective and nonselective phenomena in chiral CEKC567
13.5 Similarities and differences between enantioseparations
by pressure-driven chromatography and CEKC569
13.6 Modes of enantioseparations in CEKC574
13.7 Chiral selectors 584
13.8 Selector–selectand interaction in chiral CE586
13.9 Mathematical models of CE enantioseparations 589
13.10 Enantioseparations in capillary electrochromatography 593
13.11 Future trends 600
References601
14. Recent Developments in Chiral Separations by Supercritical

Fluid Chromatography 607
Roberta Franzini, Alessia Ciogli, Francesco Gasparrini, Omar H. Ismail,
Claudio Villani
14.2 Chiral stationary phases for SFC610
14.3 Analytical separations 612
14.4 Ultrafast high-efficient SFC separations 618
14.5 Conclusions626
References626
x Contents
15. Chiral Separation Strategies in Mass Spectrometry: Integration

of Chromatography, Electrophoresis, and Gas-Phase Mobility 631
James N. Dodds, Jody C. May, John A. McLean
15.2 Chromatography and mass spectrometry 633
15.3 Liquid chromatography 635
15.4 Electrophoresis–mass spectrometry 637
15.5 Isomer separations by IM-MS 640
15.6 Conclusions643
References644
Part Four Emerging Methods 647
16. Cavity-based Chiral Polarimetry 649

Dimitris Sofikitis, George E. Katsoprinakis, Alexandros K. Spiliotis,
T. Peter Rakitzis
16.2 Optical activity 650
16.3 Single-pass polarimetry 652
16.4 Cavity ring-down polarimetry 654
16.5 Cavity ring-down polarimetry with signal reversals 660
16.6 Continuous-wave cavity-enhanced polarimetry with signal reversals 672
16.7 Future outlook and conclusions 675
References676
17. Quantitative Chiral Analysis by Molecular Rotational

Spectroscopy679
Brooks H. Pate, Luca Evangelisti, Walther Caminati, Yunjie Xu,
Javix Thomas, David Patterson, Cristobal Perez, Melanie Schnell
17.2 Basic principles of molecular rotational spectroscopy 682
17.3 Chiral tag rotational spectroscopy for enantiomer analysis 698
17.4 Three-wave mixing rotational spectroscopy for enantiomer analysis 714
17.5 Conclusions723
References725
18. Chiral Rotational Spectroscopy 731

Robert P. Cameron, Jörg B. Götte, Stephen M. Barnett
18.2 Chiral rotational spectroscopy 732
Contents xi
18.3 Chiral rotational spectra 734

18.4 Chiral rotational spectrometer 743
References747
19. Chiral Analysis and Separation Using Molecular Rotation 753

Mirianas Chachisvilis
19.2 Chiral separations in SFs754
19.3 Chiral separations in REFs762
19.4 Summary776
References776
Index779
LIST OF CONTRIBUTORS
Federica Aiello
University of Pisa, Pisa, Italy
Daniel W. Armstrong
Department of Chemistry and Biochemistry, University of Texas at Arlington, Arlington,TX,
United States
Federica Balzano
Stephen M. Barnett
University of Strathclyde, Glasgow, United Kingdom
Laurence D. Barron
University of Glasgow, Glasgow, United Kingdom
Ewan W. Blanch
RMIT University, Melbourne,Vic., Australia
Kenneth W. Busch
Baylor University, Waco, TX, United States
Marianna A. Busch
Baylor University, Waco, TX, United States
Robert P. Cameron
University of Strathclyde; University of Glasgow, Glasgow, United Kingdom; Max Planck
Institute for the Physics of Complex Systems, Dresden, Germany
Walther Caminati
Department of Chemistry “Giacomo Ciamician”, University of Bologna, Bologna, Italy
Mirianas Chachisvilis
Solvexa LLC, Keswick, CT, San Diego, CA, United States
Bezhan Chankvetadze
Tbilisi State University, Tbilisi, Georgia
Alessia Ciogli
Sapienza University of Rome, Rome, Italy
James N. Dodds
Rina K. Dukor
BioTools, Inc., Jupiter, FL, United States
Luca Evangelisti
Department of Chemistry “Giacomo Ciamician”, University of Bologna, Bologna, Italy
xiii
xiv List of Contributors
Roberta Franzini
Francesco Gasparrini
Jörg B. Götte
University of Strathclyde; University of Glasgow, Glasgow, United Kingdom; Nanjing
University, Nanjing, China
Lucie Habartová
University of Chemistry and Technology Prague, Prague, Czech Republic
Nobuyuki Harada
Tohoku University, Sendai, Japan
Omar H. Ismail
Inge Loes ten Kate
Utrecht University, Utrecht, The Netherlands
George E. Katsoprinakis
IESL-FORTH; University of Crete, Heraklion-Crete, Greece
Dilip Kondepudi
Wake Forest University, Winston-Salem, NC, United States
Ikeda Mari
Department of Chemistry, Education Center, Faculty of Engineering, Chiba Institute of
Technology, Chiba, Japan
Jody C. May
John A. McLean
Shaun T. Mutter
Cardiff University, Cardiff, United Kingdom
Laurence A. Nafie
Syracuse University, Syracuse, New York, NY; BioTools, Inc., Jupiter, FL, United States
Saeideh Ostovar pour
RMIT University, Melbourne,Vic., Australia
Brooks H. Pate
Department of Chemistry, University of Virginia, Charlottesville,VA, United States
Rahul A. Patil
United States
List of Contributors xv
David Patterson
Department of Physics, University of California Santa Barbara, Santa Barbara, CA,
United States
C.H. Lucas Patty
Vrije Universiteit Amsterdam, Amsterdam, The Netherlands
Cristobal Perez
Max Planck Institute for the Structure and Dynamics of Matter, Hamburg, Germany
Prasad L. Polavarapu
Vijay Raghavan
T. Peter Rakitzis
Melanie Schnell
Max Planck Institute for the Structure and Dynamics of Matter, Hamburg, Germany
Vladimír Setnička
University of Chemistry and Technology Prague, Prague, Czech Republic
Kuwahara Shunsuke
Department of Chemistry, Faculty of Science, Toho University; Research Center for
Materials with Integrated Properties, Toho University, Chiba, Japan
Frans Snik
Leiden University, Leiden, The Netherlands
Dimitris Sofikitis
William B. Sparks
Space Telescope Science Institute, Baltimore, MD, United States
Alexandros K. Spiliotis
Javix Thomas
Department of Chemistry, University of Alberta, Edmonton, AB, Canada
Gloria Uccello-Barretta
Claudio Villani
Muhammad F. Wahab
United States
xvi List of Contributors
Choyce A. Weatherly
United States
Yunjie Xu
Department of Chemistry, University of Alberta, Edmonton, AB, Canada
Habata Yoichi
Department of Chemistry, Faculty of Science, Toho University; Research Center for
Materials with Integrated Properties, Toho University, Chiba, Japan
PREFACE
The subject of chirality spans different disciplines and has become a focal
point for the discussion on its role in the origin of life.The ubiquitous pres-
ence of chirality that drives the sustenance of life on this planet raises the
specter of the potential for its presence outside of this planet and for the
existence of extraterrestrial life. These fundamental topics render chirality
an important role for scientific curiosity and investigations. Modern drug
development and pharmaceutical research are heavily influenced by the
role of chirality in their respective goals. Separations of the enantiomers
of chiral compounds, distinguishing among diastereomers, determining the
three dimensional structures of chiral molecules are the topics that domi-
nate natural sciences today and are broadly categorized under the banner
of Chiral Analysis.
The first edition of Chiral Analysis, edited by Kenneth Busch and Mari-
anna Busch, appeared in 2006 describing the current-state-of research at
that time. As fundamental science undergoes never-ending development,
one finds 12 years later, that the then existing methods have undergone
major refinements and several new methods have come into practice. For
active researchers, it is important to stay informed of these developments.
Therefore, the purpose of this second edition is to update the then existing
methods as well as to describe the newly developed methods.
This book is divided into four sections. The first section, Chirality in
Nature, contains two chapters. The first chapter has been updated from the
first edition. The second chapter is newly written and presents state of the
art in remote sensing of homo chirality. The second section, Spectroscopic
Methods and Analyses, presents eight chapters on different chiroptical spec-
troscopic methods. Among these, Chapters 3, 5, 6 and 8 are updated ver-
sions from the first edition, while the others, namely, Chapters 4, 7, 9 and
10 are newly written. The third section, Chromatographic and Electromi-
gration Methods, provides state of the art in chromatographic chiral sepa-
rations in five different chapters. All these five chapters are newly written.
The fourth section, Emerging Methods, contains four new chapters that
describe newly emerged methods in recent years, each describing a new
independent method with novel applications.
xvii
xviii Preface
This book is intended to serve as a guide for those interested in chiral

analysis. Graduate students as well as scientific professionals pursuing chiral-
ity in physical chemistry, analytical chemistry, organic chemistry, biology
and pharmaceutical research will find the relevant topics needed to pursue
their independent research. In addition, researchers interested in chirality, as
well as seasoned practitioners in this area, will find the chapters written by
leading experts in their respective areas, a valuable resource.
I would like to thank all of the authors of the chapters in this volume for
their dedication and willingness in deciphering their scientific innovations
to wider scientific community and for their cooperation throughout this
project.Without assistance from these dedicated scientists this volume could
not have been produced. Finally, I thank Kathryn Morrissey, Acquisitions
Editor at Elsevier, for reaching out to me to undertake this book project.
Prasad L. Polavarapu
PART ONE
Chirality in Nature
CHAPTER 1
Chiral Asymmetry in Nature

Dilip Kondepudi
Wake Forest University, Winston-Salem, NC, United States
1.1 INTRODUCTION
The wide-ranging chiral asymmetry in nature has given rise to a
multidisciplinary interest in chirality. It is remarkable that nature does not
exhibit left–right symmetry at any level: morphological, molecular, and
even at the most fundamental level of elementary particle interactions
[1–3]. At the astronomical level, circularly polarized light has been found in
Orion Nebula [4], indicating the existence of large regions of space with
asymmetry.
Chiral asymmetry in biomolecules—the predominance of l-amino ac-
ids and d-sugars—has profound consequences for pharmaceutical and ag-
ricultural chemistry. It necessitates us to develop a theoretical framework in
which we can quantitatively study chirality and study processes that gener-
ate chiral asymmetry. In this chapter, we will discuss the basic definitions
and nomenclature used to describe chiral systems. This will be followed by
a brief survey of known chiral asymmetries in nature and questions they
raise.We will then present a general theory of spontaneous chiral symmetry
breaking and discuss examples of spontaneous generation of asymmetry.
1.2 CHIRALITY: TERMINOLOGY AND

QUANTIFICATION ISSUES
When an object is not identical to its mirror image, it is said to be
“chiral”. Lord Kelvin, who introduced this terminology, defined it thus:
“I call any geometrical figure, or any group of points, chiral, and say it has
chirality, if its image in a plane mirror, ideally realized, cannot be brought
to coincide with itself ” [5]. A chiral object or a geometrical figure and its
mirror image are thus distinguishable and they could be simply identified
as “left-handed” or “right-handed”, a terminology that can readily be un-
derstood because we are asymmetric in the use of our hands. But there is
a subtle issue here: how do you specify what we mean by a “left-handed
Chiral Analysis. http://dx.doi.org/10.1016/B978-0-444-64027-7.00001-X

Copyright © 2018 Elsevier B.V. All rights reserved. 3
4 Dilip Kondepudi
Figure 1.1 Examples of basic chiral units. All complex objects can be reduced to a set of
basic chiral units. As shown in the lower part, every basic chiral unit can be associated
with a directed circle and a vector which together define a right- or left-handed helix.
object” to the one who does not know what it is, say to a being on a dis-
tant planet? Could we send this information as a radio signal coded as a
sequence of digits (“0” and “1”)? The answer to this question turns out to
be negative; it is not possible to specify what one means by “left” or “right”
in a linear sequence of digits. A three-dimensional object or a chirally asym-
metric phenomenon in nature is needed to specify this information [6–8].
While Kelvin’s definition clearly identifies chiral object, we often have
a need to distinguish between a simple chiral object, such as a tetrahedral
molecule with four different atoms, and a complex chiral object, such as a
protein. To describe chirality of assemblies of simple achiral building blocks,
we may define a basic chiral unit as an object that cannot be divided into two
or more chiral objects; any disassembly of such a unit will result in achiral
subunits. Some examples of basic chiral units are shown in Fig. 1.1. Ac-
cording to this definition, a helix made of a continuous line segment is not
a basic chiral unit; however, a helical assembly of sphere consisting of four
spheres is a basic chiral unit. All basic chiral units can be associated with a
direction of rotation and an arrow that together define a helix as shown
in Fig. 1.1. (In certain situations, one might identify the direction of rota-
tion with an axial vector, while the arrow is a vector. The combination of
Chiral Asymmetry in Nature 5
a vector and an axial vector defines chirality.) Through such association, we

can specify the absolute configuration of all basic chiral units. The chiral-
ity of a large assembly of simple achiral units has to be described in terms
of chirality of such basic chiral units. We will discuss more about this point
later in this chapter.
1.2.1 Cahn–Ingold–Prelog classification of chiral molecules

In the case of chiral molecules, a system of rules that identifies the absolute
structure of the two enantiomers as R (Rectus, Latin word for “right”) and
S (Sinister, Latin word for “left”) was proposed by Cahn et al. [9]. These
rules have been adopted by IUPAC.The two molecular structures are called
enantiomers of a chiral molecule. This designation is particularly suited for
chiral organic molecules in which a carbon is bonded to four different
atoms or groups, R1, R2, R3, and R4 as shown in Fig. 1.2. Each of the
four groups bonded to the carbon are ranked by the atomic number of the
atom directly bonded to the carbon, higher atomic number corresponding
to a higher rank. If two or more atoms have the same atomic number, then
other atoms in each group’s chain are compared until a difference is found.
If all the atomic numbers are the same, then atomic masses are used instead
Figure 1.2 An example of R-enantiomer in accordance with Cahn–Ingold–Prelog rules.

The four groups, R1–R4, attached to the central carbon are ranked, R1 > R2 > R3 > R4.
Pointing the lowest ranked group away from the viewer, the clockwise rotation
R1 → R2 → R3, defines the molecule as R-enantiomer. If the rotation is in the counter-
clockwise direction, then it is a S-enantiomer.
6 Dilip Kondepudi
for ranking the groups. Thus, a CH3 has a lower rank than CH2OH or
CH2CH3; similarly, the isotope D has a higher ranking than H. In Fig. 1.2,
the ranking is assumed to be R1 > R2 > R3 > R4. For such a molecule,
the “arrow” is defined as that pointing from the central carbon to the group
with the lowest rank, R4. The rotation direction is obtained from the three
highest ranking groups by moving from the highest to the lowest ranking
group, that is, R1 → R2 → R3. If this rotation and the arrow define a right-
handed helix, the molecule is classified as R; if the helix is left-handed, the
molecule is classified as S. It is possible that the two of the four groups, say
R1 and R2, are stereoisomers. In that case, the Cahn–Ingold–Prelog rules
specify a precise way of ranking the two groups. These rules may be found
in Ref. [9].
Before the Cahn–Ingold–Prelog rules were formulated, the terminology
for identifying the two enantiomers of a chiral molecule was based on opti-
cal rotation. Linearly polarized light of a particular wavelength undergoes
a rotation as it propagates through a solution or a crystal of a chiral com-
pound. A solution or solid that rotates linearly polarized light is said to be
optically active. In fact, the discovery of optical activity by the physicist Biot
in 1815 and Louis Pasteur’s insight that it was related to molecular asym-
metry gave us a general means to identify enantiomers. Consequently, the
handedness of a molecule was identified by its optical activity. If the light
was rotated clockwise as it approaches the viewer (Fig. 1.3), the solution
was designated “dextro-rotatory” or “+” and the enantiomer causing such a
rotation was called d-enantiomer; if the light rotated counter-clockwise, the
rotation was called “levo-rotatory” or “−” and the corresponding enantiomer
is called l-enantiomer. This designation does not give us the absolute mo-
lecular structure, that is, one cannot say which one of the two mirror-image
structures of the molecule gives rise to the observed optical rotation. In
fact, the optical rotation for a given compound depends on the wavelength
of the light and it can be dextro at one wavelength and levo at another.
Figure 1.3 Optical activity is the rotation of linearly polarized light as it passes through
the sample. As shown in the figure, if the direction of polarization rotates clockwise as
it approaches the viewer, the substance is dextro-rotatory and is designated “d” or “+”. If
the rotation is in counter-clockwise direction, the substance is levo-rotatory or “l”. or “−”.
Optical activity arises when the refractive indices of left- and right-circularly polarized
light are unequal.
Figure 1.4 The terminology “l- and d-amino acids” refers to the geometric structure as
shown. Solutions of l-amino acids can be levo- or dextro-rotatory.
In addition, for a given wavelength, the direction of rotation can change

with the solvent. Clearly the designation “R and S” specifies the molecular
structure more precisely and it is preferred over the “l and d” designation.
Since optical activity is readily measured and often used to analyze chiral
products of a reaction, if the optical activity of enantiomer is known, it is
specified by combining the R–S and l–d notation; thus R(–) indicates that
the R-enantiomer is levo-rotatory.
In addition to the R–S designation, another designation that is also used
in the context of amino acids and sugars identifies the enantiomers as l and
d, which in the case of sugars is tied to the designation given to glyceralde-
hyde. This designation refers to the absolute structure as shown in Fig. 1.4.
This designation is independent of the side chain and hence all l-amino
acids have a similar basic structure. However, depending on the side chain,
an l-amino acid may be designated R or S, a point that needs to be noted
when using the R/S designation for the biologically dominant l-amino
acids.
1.2.2 Optical rotation

The angle through which linearly polarized light is rotated, that is, the opti-
cal rotation, is usually denoted by α. Optical rotation is due to the difference
in the refractive indices of right- and left-circularly polarized light. Linearly
polarized light may be considered as a combination of the right- and left-
circularly polarized light, that is, linearly polarized light may be resolved
into right- and left-circularly polarized components. If the two compo-
nents travel at different speeds, the resultant linear polarization undergoes a
rotation. If nR and nL are the refractive indices of right- and left-circularly
8 Dilip Kondepudi
polarized light, respectively, for light of wavelength λ, traversing a path in a

chiral medium of length l, the optical rotation α is given by
πl
α= (n − nR ) (1.1)
λ L
In most practical situations, to a good approximation, optical activity of
a solution is directly proportional to its concentration and the path length
(length of the polarimeter tube). In addition, α also depends on the wave-
length, the solvent, and the temperature. Consequently, specific rotation,
[α], of light of wavelength λ, at a temperature T is defined as
λ
[α ]Tλ = (1.2)
lc
in which c is the concentration in g/mL and l is the path length in decimeters.
1.2.3 Enantiomeric excess

Optical activity of a solution is proportional to the difference in the amounts
of the two enantiomers. This difference, which is a measure of the chiral
asymmetry of the systems, is often quantified in terms of enantiomeric excess
(EE), which is defined as
|[ R ] − [S ]|
Enantiometric Excess= (1.3)
([ R ] + [S ])
in which [R] and [S] are the concentrations of the two enantiomers. It is a
measure of asymmetry relative to the total amount of the substance, not an ab-
solute measure of the difference in the amount of R and S. As we shall see be-
low, in formulating a general theory of spontaneous chiral symmetry breaking,
the difference ([R] − [S]) is mathematically more convenient to use than EE.
1.2.4 Crystal enantiomeric excess

In nucleation of chiral crystals, asymmetries can arise due to chirally auto-
catalytic processes. In this case, the asymmetry is due to the difference in
the number of levo- and dextro-rotatory crystals. For this reason, one might
define a crystal enantiomeric excess (CEE) as
Nl − Nd
CEE = (1.4)
Nl + Nd
in which Nl and Nd are the number of levo- and dextro-rotatory crystals.

This quantity measures the asymmetry in nucleation, not in the total num-
ber of molecules.
1.2.5 Chirality measures

When we look at chiral objects, we often have a sense that one is “more
chiral” than another. This notion could be intrinsic to the chiral objects
themselves or in their interaction with other chiral objects. For example,
when we compare two molecules that are in the shape of a twisted H, one
could say the one with the larger twist angle is “more chiral”, which is a
measure intrinsic to the object.The specific rotation for a given wavelength
and other well-specified conditions, a measure not intrinsic to the object,
could be used to compare the chirality of molecules, the molecules with
larger rotation being “more chiral”.
It is desirable to have the measure be such that: (i) the value of the chiral-
ity measure changes continuously with the shape of the object and is equal
in magnitude but opposite in sign for enantiomers, (ii) the chirality measure
is zero if and only if the object is achiral. It turns out that it is impossible to
define a universal measure with these two properties! This is because enan-
tiomers of certain chiral objects can be transformed from one to the other
through a series of states which are all chiral—just as a left-hand glove can
be transformed to a right-hand glove by turning it inside out one finger at
a time. Examples of such transformations were noted by Mislow [10,11].
Molecules in which such a transformation can be realized are called “mo-
lecular gloves”. During such a transformation, the corresponding chirality
measure has to change continuously from positive to negative (or vice ver-
sa) and hence must cross zero.The transformation, however, consists entirely
of chiral states. Hence, there must be a chiral state whose chirality measure is
zero, contrary to the requirement (ii). If an R-enantiomer of a molecule can
be transformed into an S-enantiomer through intermediate states which are
all chiral, it means there is no well-defined achiral state at which the change
from R to S occurs; hence the point at which the change in designation is
made is arbitrary: the notion of “left” and “right” cannot be made absolute.
Avoiding the ambiguity that arises with the sign of a chirality measure,
the intrinsic chirality of an object can be viewed, for example, in terms of
how different the two enantiomers are from each other. In this regard, sev-
eral measures have been proposed [12–17]. Buda et al. [13] define a degree
of chirality as: “the value of a real-valued, continuous function that is zero if
and only if the object is achiral. The degree of chirality is the measure of
10 Dilip Kondepudi
an absolute quantity and its value is therefore the same for both enantio-
morphs of the measure object”. An example of the degree of chirality is the
maximum amount of overlap between a chiral object and its enantiomer.
Clearly, in this measure, the degree of all achiral objects is zero and all chiral
objects is nonzero.
Only chiral objects can distinguish between the enantiomers of a chiral
molecule. Could we not define a measure of chirality on the basis of in-
teraction of reference chiral object with all chiral molecules? For example,
could we take optical rotation (at specified wavelength, temperature, and
other conditions) as a measure of chirality? This approach too has difficul-
ties because there are some chiral molecules [11] whose optical activity
is for all practical purposes immeasurable and there is no simple, reliable,
theoretical way to predict what it would be. Furthermore, a molecule that
is classified as “left-handed” on the basis of optical rotation with one achiral
solvent, may have to be classified as “right-handed” with another achiral
solvent which indicates that this notion of “left” and “right”, derived from
the interaction of the molecule with right- and left-circularly polarized
photons of a particular wavelength, is also dependent on the environment
and somewhat arbitrary.
Though there is no universal measure of chirality, it must be noted that
there are situations in which quantifying chirality could be extremely useful
in organizing and understanding chiral interactions [18–20].
1.3 CHIRAL ASYMMETRY IN NATURE

That nature does not treat “left” and “right” equally is not only re-
markable, but also puzzling because the fundamental laws have a high de-
gree of symmetry in many respects. All basic laws of physics are invariant
under translations in space and time and rotations in space. Electromag-
netic phenomenon is also invariant under mirror reflection, more precisely,
parity (which is equivalent to mirror reflection and a rotation). But other
fundamental interactions, at the nuclear level, are not invariant under par-
ity. In this section, we will briefly survey the chiral asymmetries found at
various levels of scale, from the nuclear level to the level of morphology of
mammals.
1.3.1 Asymmetry in nuclear processes

Chiral asymmetry in nuclear processes responsible for β-radioactivity was
discovered in 1957 by Wu [21]. Some unstable nuclei “decay” to a lower
state of energy by emitting electrons or positrons, also called β-particles.

The isotope of cobalt, cobalt-60, for example, emits electrons. The nucleus
of cobalt-60 has spin, but a stationary particle with a spin is not chiral; it
does not possess handedness unless there is a direction associated with spin
that could be used to define chirality. (In identifying the “north pole” using
the right hand, we are imposing the chirality of the hand on the spinning
sphere; a stationary spinning object is not chiral.) If there is an additional
direction associated with a static spinning object, however, one could define
left and right. In the case of radioactivity in cobalt-60, when the nuclei are
placed in a magnetic field, their spin axes line up along the magnetic field.
In cobalt-60, nuclei aligned in a magnetic field, more electrons were emit-
ted from one of the two hemispheres, thus indicating the handedness of this
phenomenon. If the two hemispheres of a spinning sphere are not identical,
then that object is chiral because the lack of identity of the two hemispheres
could be used to define a direction, which along with the rotation defines
a helix.
Further studies of β-radioactivity revealed that the emitted electrons
themselves exhibit asymmetry. Since electrons have spin, one can associate
left- or right-helicity to each electron by projecting its momentum vector
along the spin axis. It was found that the electrons emitted by radioactive
nuclei are predominantly left-helical. Chiral asymmetry in β-radioactivity
appears in other ways as well.The emission of β-particles is accompanied by
the emission of elusive particles called the neutrinos, which also have spin.
All neutrinos generated in β-radioactivity are left-helical and antineutrinos
are right-helical. Neither right-helical neutrinos nor left-helical antineu-
trinos have been detected; they are presumed not to exist. If there were
equal number left-helical neutrinos and right-helical anti-neutrinos then
we might say that left–right symmetry is restored, but this would require a
balance between matter and antimatter. As far as we can tell, there is matter
in the universe but not antimatter.The consequence is that present universe
is filled exclusively with left-helical neutrinos.
1.3.2 Asymmetry in atoms

We now move from the level of the nucleus to the level of the atom.
Before the forces that held the particles in the atomic nucleus were dis-
covered, physicists knew two fundamental forces in nature: gravity and
electromagnetism. With the discovery of the nucleus, in which positively
charged protons and uncharged neutrons were held together, new forces
came to light. Soon after, studies in nuclear physics showed that there were
12 Dilip Kondepudi
Figure 1.5 Asymmetry in electro-weak interactions. The interaction between the elec-
tron and the nucleons depends on the electron helicity; the interaction energies of
the left- and right-helical electrons are unequal. Due to electro-weak interaction, the
ground-state energies of enantiomers are unequal.
basically two types of nuclear forces, which were termed, “strong” and
“weak” forces. The weak forces were responsible for β-radioactivity, while
the strong force was responsible for nuclear fission and fusion. Ever since
James Clerk Maxwell realized that the laws of electricity and magnetism
can be unified as “electromagnetic” laws, there has been a strong interest
among physicists to unify different forces. Einstein, for example, tried very
hard, but unsuccessfully, to unify gravity and electromagnetism. But the
search for unification of fundamental forces continues and one of its great
achievements is the unification of electromagnetic and weak forces, which
necessitated the coining of the term “electro-weak” force. The formula-
tors of the theory of electro-weak force, Steven Wienberg, Abdus Salam,
and Sheldon Glashow were awarded the Nobel Prize for Physics in 1979.
The exact nature of this unification is not important for us, but the chi-
ral asymmetry this unification revealed is. One of the predictions of the
electro-weak theory is that the electron interacts with the nucleons (par-
ticles in the nucleus, protons, and the neutrons) with a force that depends
on its helicity. Left- and right-helical electrons are acted upon by different
forces (Fig. 1.5). This fact brings the chiral asymmetry to the level of at-
oms, making them optically active. Atoms were thought to be spherically
symmetric entities with no chiral attributes until the electro-weak force
between the electron and the nucleons was discovered. A tube filled with
vapors of the element bismuth, for example, is found to be levo-rotatory
[22]. Due to electro-weak interactions we only find levo-bismuth in na-
ture, its mirror-image twin does not exist. The optical activity of atoms,
though very small, has been measured and found to be as predicted by
the electro-weak theory, of the order of 10−7 radians, depending on the
density of the vapor [22].
1.3.3 Asymmetry in molecules

The electro-weak interaction between the electron and the nucleons also
brings chiral asymmetry to the level of molecules. In most chemistry texts
it is stated that the ground-state energies of enantiomers are identical. This
would be the case if the interaction between the electron and the nucleons
were entirely governed by the laws of electromagnetism which are parity
invariant. But since the electron–nucleon interaction has also a component
of the parity violating weak-force, the ground-state energies of enantio-
mers must be different. This difference has been calculated by Mason and
Tranter [23,24] using electro-weak theory and it is found to be of the order
of 10−14 J/mol, too small to be detected by current experimental methods.
Calculations done on amino acids, indicate that the ground-state energies
of l-amino acids are lower than those of d-amino acids. Since then, many
more accurate calculations have been performed by Schewerdtfeger’s group
[25–30] and some recent theoretical calculations found that the effect in
excited states could be larger by a factor of 103 [31,32].This raises hope that
we might be able to measure electro-weak energy differences in enantio-
mers in the laboratory.
1.3.4 Biomolecular asymmetry

Louis Pasteur’s discovery in 1857 that microbes metabolized only the dex-
tro-rotatory sodium-ammonium-tartrate is a momentous one. It not only
presented us with one of the most fundamental and universal aspects of the
biological chemistry, it left us with a fundamental question regarding life: Is
chiral symmetry essential for the evolution of life? With our present knowl-
edge of biochemistry we know that, all of life is dominated by l-amino acids
and d-riboses. In the words of Francis Crick, “The first great unifying prin-
ciple biochemistry is that the key molecules have the same hand in all organ-
isms” [33]. The food we eat, the medicines we take, and pesticides we use all
have to conform to the chemistry dictated by this asymmetry.The evolution-
ary origins of this asymmetry remain an enigma. Though we have learned
much about processes that can spontaneously generate chiral asymmetry in
the last 15 years, we are still far from having plausible examples of processes
that could have caused the dominance of l-amino acids and d-riboses.
1.3.5 Morphological asymmetry

The asymmetry in the morphology of living organisms is all too well-
known: Most of the spiral seashells are right-helical; the organ placement in
14 Dilip Kondepudi
mammals is asymmetric—except for the rare one-in-ten-thousand inver-

sion in humans (a condition called situs inversus). Chiral asymmetry of the
brain is reflected in behavior: about 90% of humans in all societies and cul-
tures are right-handed. A good compendium of asymmetries in the animal
world was assembled by Neville in his Animal Asymmetries [34].
Morphological asymmetry is inherited. How does this happen? This
question has a different significance compared to other inherited traits that
are coded in a DNA sequence of A, T, G, and C. Handedness cannot be
coded in a linear sequence of letters, that is, the information about the
placement of the liver on the right, for example, could not be coded in a
sequence such as ATTGCGGTAC … while placement on the left be coded
in a different sequence GTTACCTGA…. To understand why this is so, we
only have to look at the process that places the liver on the right in a mir-
ror to realize that the sequence ATTGCGGTAC …could also carry the
code to place the liver on the left.The information about right or left has to
come from some existing asymmetry. Although asymmetry is easy to find at
the molecular level of l-amino acids and d-riboses, we do not know how
the molecular asymmetry gets translated to morphological asymmetry. The
connection between the structure of amino acids and organs is similar to the
connection between bricks and the shape of a building. Clearly the shape of
a building is quite independent from the shape of a brick; yet morphological
asymmetry seems to have its origins at the molecular level. Elucidating this
link is one of the great challenges of developmental biology [35].
1.3.6 Astrophysical asymmetries

On the astronomical scale, asymmetry was found in large regions of in-
terstellar space in the form of circularly polarized light. Bailey et al. [4,36]
reported the detection of infrared circularly polarized light in star-forming
regions of Orion Nebula. Though this is not a global asymmetry, it never-
theless shows that chiral asymmetry can arise in vast regions in the universe
and it may have important implications for the origin of molecular asym-
metry in these regions.
An obvious place to look for chiral asymmetry on the astrophysical scale
is in spiral galaxies. With respect to an observer on the earth, all galaxies
are receding and hence have a well-defined direction of motion. For spiral
galaxies, if we combine the direction of the spiral with the recession veloc-
ity vector, we can define a helicity or handedness of spiral galaxies. The
Carnegie Atlas of Galaxies [37] is a good resource to look at the statistics
of spiral galaxies. A simple count of the left- and right-helical spiral galaxies
shows an equal number, indicating no apparent asymmetry. However, if the

statistics are extended to the different classes of spiral galaxies, an interesting
trend seems to emerge [38]. Spiral galaxies are classified into ordinary spirals
(S) and barred spirals (SB), a classification initiated by Edwin Hubble. The
two classes of galaxies show opposite asymmetries that cancel each other.
If we assign +1 to “Z-shaped” spirals and –1 to the “S-shaped” in a
sample of 540 galaxies that consists of both S and SB spirals, the sum was
found to be –4 (–0.172 standard deviations from zero), indicating that there
is no observable asymmetry in the total sample. But in a subsample of 378
galaxies of class S, the sum was found to be –26 (–1.34 standard deviations
from zero), while in the subsample of 162 galaxies of class SB the sum was
+22 (+1.73 standard deviations from zero). The probability of observing
these sums as a consequence of random fluctuations in a system that has
no real asymmetry is 0.09 for class S and 0.04 for class SB. With such low
probabilities for the observed statistics, we may consider the above data as
an indication that there is an asymmetry in the distribution of the subclasses
of ordinary spiral galaxies and barred spiral galaxies but of opposite sign.
More details and references to previous work on this topic can be found in
Ref. [38].This observation should be considered only an indication and not
a definite conclusion that there is chiral asymmetry in subclasses of spiral
galaxies; to be certain, analysis based on a larger dataset is essential.
1.4 THEORY OF SPONTANEOUS CHIRAL

SYMMETRY BREAKING
The chiral asymmetry at the biomolecular level lies in stark contrast
to the paucity of chemical reactions that spontaneously generate asymmetry.
When chiral molecules are synthesized from achiral reactants, we find equal
amount of the two enantiomers. Since chemical reactions are governed by
the electromagnetic laws that are mirror-symmetric, the rates of production
of the two enantiomers are equal. The deviation from chiral symmetry due
to the electro-weak component of the interaction is too small to influence
chemical reactions on the laboratory volume and time scales. (As we shall
see below, when very large scales of time and volume are involved, even very
small asymmetries can have a large effect.) The mirror-symmetry of the
electromagnetic laws implies that a process and its mirror image are equally
realizable in nature; thus, if we ignore the electro-weak interactions, there
can be no noticeable difference in chemical reaction rates of enantiomers.
But, identical reaction rates need not always lead to equal amounts of the
16 Dilip Kondepudi
two enantiomers. In reactions that are autocatalytic, symmetric kinetic rate

laws could produce asymmetric product.The products of a chemical process
need not reflect the symmetries of the process that generated it. When this
happens, the system is said to exhibit “spontaneous symmetry breaking”.
In mathematical terms, the solutions of a system of differential equations
need not have the same symmetries as the system of equations; the solutions
could “break the symmetries” of the system. This phenomenon could be il-
lustrated using a simple model that is an extension of a model suggested by
Sir Charles Frederick Frank in 1953 [39].
The modification to Frank’s model was made to elucidate the ther-
modynamic nature of the model and to assess the impact of small external
asymmetries on such models. This modified model is shown in Fig. 1.6. In
Figure 1.6 An autocatalytic reaction scheme in which XL and XD have identical kinetic
rate laws. However, in an open system, this reaction gives rise to a state of broken sym-
metry in which the concentrations of XL and XD are unequal. Lower part of the figure
shows a “bifurcation diagram” used in describing the transitions to asymmetric states.
The parameter α = (XL − XD)/2 is a measure of the asymmetry. λ = [S][T], the product of
the concentrations of S and T, is the bifurcation parameter. When the value of λ exceeds
λC the system becomes unstable and makes a transition to an asymmetric state in which
α is not zero.
this model, achiral molecules, S and T react to form a chiral molecule XL

or XD. The molecule X is chirally autocatalytic: XL catalyzes the production
of XL and XD catalyzes the production of XD. In addition, XL and XD react
to form an inactive product P. The system consists of a “reaction chamber”
into which there is an inflow of reactants S and T and an outflow of P.
For a given set of flows, the system reaches a stationary state in which the
concentrations of all the species remain constant. The flows maintain the
concentrations of S and T at a constant value. If the flows are reduced to
zero, the system will eventually reach thermodynamic equilibrium in which
the concentrations of XL and XD are equal. If the flows are slowly increased
from zero, the concentrations of S, T as well as XL and XD increase but still
the concentrations of XL and XD remain equal until the concentrations of S
and T reach a critical value. Below the critical value, any difference in the
concentrations of XL and XD that might arise through a random fluctuation
will decay to zero; here the symmetric state of equal XL and XD is stable. Above
the critical value, the system becomes “unstable” in the sense any small dif-
ference between the concentrations of XL and XD will grow; the system can
no longer maintain the symmetry between XL and XD. If the concentrations
of S and T surpass the critical value, the system will be forced to make a
transition to an asymmetric state in which concentrations of XL and XD are
not equal.Which one will be greater is entirely random, but one of the two
enantiomers will dominate. This symmetry-breaking transition is summa-
rized in the lower part of Fig. 1.6.
In the terminology of nonequilibrium chemistry, the system undergoes
a nonequilibrium transition to a symmetry breaking state. The thermo-
dynamic state thus reached through a nonequilibrium transition is more
ordered or has more structure. This structure is maintained by the “dissipa-
tive” or entropy-generating chemical processes; they were therefore called
“dissipative structures” by Ilya Prigogine, who was awarded the 1977 Nobel
Prize in Chemistry for his contributions to nonequilibrium thermodynam-
ics. There are numerous other examples of dissipative structures that are a
result of symmetry breaking transitions [40]. The above example also makes
it clear that only a system far from thermodynamic equilibrium can gener-
ate and sustain asymmetry of the form we see in proteins and DNA.Though
the racemization rates of amino acids are very small, a steady generation of
l-amino acids is necessary to maintain the chiral purity of active proteins.
The above model can be used to illustrate general features that all chiral
symmetry breaking transitions will exhibit. As shown in Fig. 1.6, there is a
quantity α = ([XL] − [XD])/2 which is a measure of the asymmetry; α = 0
18 Dilip Kondepudi
represents a symmetric state in which two enantiomers are present in equal

amounts; α ≠ 0 represents an asymmetric state in which one of the two
enantiomers is in excess. α is more mathematically convenient than EE
in analyzing symmetry-breaking transitions. The parameter λ = [S][T] is a
measure of the system’s distance from thermodynamic equilibrium because,
through appropriate inflow of S and T, their concentrations are maintained
at a nonequilibrium value. It is also called the bifurcation parameter. If λ is
such that it corresponds to equilibrium values of [S] and [T], the system will
be in a symmetric state corresponding to α = 0. When λ reaches a critical
value, indicated by λC, the systems begin to become unstable to small devia-
tions of α from zero; if λ > λC, then random fluctuations in α will grow and
drive it to either a positive or a negative value (a steady state) depending on
the fluctuation. At λ = λC, two new asymmetric solutions “bifurcate” from
the symmetric solution. In the vicinity of the critical point λC, it is possible
to obtain an equation for the time evolution of α that will have the same
general form for all systems that break chiral symmetry [41,42]. This equa-
tion is of the form
dα (1.5)
= − Aa 3 + B( λ − λC )α + ε f (t )
dt
In this equation, the coefficients A and B depend on the kinetic rate
constants; the term ε f (t ) represents random fluctuations in which ε is
the root-mean-square value of the fluctuations and f(t) a normalized ran-
dom variable with zero mean. (As a first approximation, one may assume
f(t) to be a Gaussian white noise.) The fluctuations make the evolution of α
stochastic or random. Normally, random fluctuations in concentrations are
quite unimportant for predicting the time-variation of concentrations dur-
ing the reaction and the final product distribution. The kinetic rate equa-
tions enable us to predict these within the accuracy of the experiments.
Not so in systems that spontaneously break chiral symmetry; the evolution
of α is random, not deterministic. For example, if λ moves from a value
below the critical point to a value above the critical point, α could evolve
from zero to a positive or a negative value. Hence, we can only assign a
probability, P+ or P–, that α will evolve to either value because final state
of α depends on a random fluctuation. In the absence of a chiral influence
that favors one of the enantiomers, we must have P+ = P– = 0.5. Eq. (1.5),
which contains a term representing random fluctuation, is an example of
a Langevin equation. For such equations, with appropriate specification of
the property of the random variable f(t), it is possible to obtain an equation
for the evolution of the probability distribution P(α,t), called the Fokker–
Planck equation. We shall not discuss these mathematical details in this in-
troductory chapter but focus on the general theoretical aspects. Note that
the mirror symmetry of the chemical reactions is manifest in the general
equation (1.5) in that both α and –α are its solutions. When we consider
steady states (dα/dt = 0) if α = –α = 0, then the solution is symmetric; on
the other hand, if α ≠ 0, the system has two possible solutions, α and –α,
each representing a state of broken symmetry. For any chemical system that
is capable of spontaneous chiral symmetry breaking, the general equation
of the form (1.5) can be derived using group theory, without reference to
particular details of the kinetic mechanism; in addition, general expressions
relating the coefficients A and B to the kinetic rate constants can be derived
[42]. This theory is similar to the Ginzberg–Landau theory of second-order
phase transitions.
1.5 SENSITIVITY OF CHIRAL SYMMETRY BREAKING

TRANSITIONS TO ASYMMETRIC INTERACTIONS
The above general formalism can be used to analyze the effects of
small asymmetric interaction on symmetry breaking transitions. For ex-
ample, we can analyze how circularly polarized light might influence the
symmetry breaking transition if it enhances the reaction rate of one of the
two enantiomers. Due to the asymmetric interaction, the probabilities of
transition, P+ and P–, to asymmetric states will be different from 0.5. Let us
say, that due to the asymmetric interaction, the forward rate constant of the
reaction S + T → XL is larger than that of S + T → XD by a factor g, that is,
the rate constant kL = kD (1 + g), in which kL and kD are the rate constants of
the two reactions, respectively. Given such a chiral influence, the task is to
determine the probabilities P+ and P– = (1 − P+). Using the same general
approach that leads to Eq. (1.5), the following modification of this equa-
tion can be obtained in the presence of the asymmetric interaction [41,42]:
dα
= Aα 3 + B( λ − λC )α + Cg + ε f (t ) (1.6)
dt
in which C is a constant that depends on the kinetic rate constants. As

before, for any given set of reactions, one can obtain C using general expres-
sions [42]. The effect of the bias term Cg is countered by the random fluc-
tuations whose strength, as measured by the root-mean-square value, is ε .
20 Dilip Kondepudi
Figure 1.7 In the presence of a chiral influence that favors one enantiomer (here cor-
responding to α > 0), the bifurcation diagram in Fig. 1.6 is modified to the one shown
above. As λ increase from a value below λC to a value above λC, the system makes a tran-
sition to the favored upper branch with a higher probability. In this figure, a fluctuating
trajectory of α shows its evolution to the favored branch in which α > 0. This process
is very sensitive to small chiral influences. The probability of transition to the favored
branch is given by the formula (1.7).
At first sight, it might seem that if Cg ε then the effect of the chiral
interaction on P+ would be negligible. But a careful analysis shows that
the system could in fact be very sensitive to the chiral interaction even if
Cg ε [41]. Such sensitivity arises when the parameter λ sweeps through
the critical value, λC, from a subcritical to a supercritical value. Let us assume
that this sweep of λ happens at an average rate of γ, that is, λ = λ0 + γt in
which λ0 < λC and t is the time (Fig. 1.7). It turns out that the sensitivity of
the system to the chiral interaction, which is reflected in the deviation of P+
from 0.5, depends on the sweep rate γ. Lower values of γ make the system
more sensitive. The analytical expression for P+ in the presence of the chiral
interaction is [41]
14
1 N Cg  π 
∫
− x 2 /2
P+ = e d x in which N = (1.7)
2π −∞ ε / 2  Bγ 
This result, which has been verified in electronic systems [43], shows
that even when Cg ε the value of P+ could be as high as 0.98 depend-
ing on the value of γ. The theory can also be generalized to symmetry
breaking transitions for symmetries other than the mirror symmetry [44].
The significance of this result is in what it implies for the relation be-
tween symmetry breaking at different levels. If symmetry breaking transi-
tions occur at various levels, the occurrence at one level might depend
very sensitively on a small asymmetry at a lower level. This type of theory
has the potential of revealing how asymmetries at various levels could be
interconnected. Also, this theory is general enough that it applies at all levels,
wherever spontaneous chiral symmetry breaking occurs.
One of us has suggested the use of such theory in analyzing the higher-
level chiral asymmetries in macro molecules such as proteins [8]. A complex
chiral structure, such as a protein molecule could be analyzed in the follow-
ing way. We begin with identifying the basic chiral objects in the system. In
this case, the amino acids. To see the chirality at the next level, we replace
each basic chiral unit by an achiral unit such as a sphere. In this string of
spheres we now identify the basic chiral units. In the helical parts of the
protein, for example, we will see chirality at the next level, that is, in the
secondary structure. As is well-known, all the helices in proteins are right-
handed because the amino acids are all l-Enantiomers. Now the folding of
a string of spheres can itself be seen as a symmetry-breaking transition; the
folding can give rise to right- or left-handed helix with equal probability
if there is no chiral bias. In this transition, if we take into account that the
spheres represent l-amino acids, then there is a chiral bias arising from a
lower level and influencing the helices to go right-handed. From the above
theory, we may expect the transition to be a helix very sensitive to even
small chiral biases (in the case of l-amino acids, the bias is probably not
small). To identify the chirality at the next level, that is, at the level higher
than helices, we replace each of the helices by a cylinder and each of the
beta-sheets with a ribbon. In this string of cylinders and ribbons, we can
now identify basic chiral units depending on how this string folds. Thus,
the chirality of the protein can be seen at various levels and it might as well
show a systematic asymmetry at higher levels. If this is so, using the above
theory, or another appropriate theory, we can see how an asymmetry at one
level influences the next higher level.This gives us a way to understand how
asymmetry propagates from one structural level to another. It may well be
that in some macromolecules the asymmetry slowly vanishes at higher and
higher levels.
An interesting consequence of the theory of spontaneous chiral sym-
metry breaking is that it provides a relationship between the strength of
a chiral influence and the timescale at which it can influence a symme-
try breaking transition. By applying this theory we find, on a timescale of
15,000 years, electro-weak parity violation could influence the outcome of
a symmetry breaking process in a chemical system whose reactor volume
is 1 km × 1 km × 10 m. Thus, in the context of chemical evolution in the
oceans, such processes are relevant. Though there have been many sugges-
tions, at this time we do not have much understanding of when and what
22 Dilip Kondepudi
stage of life’s evolution chiral asymmetry arose. Hence, we can only say that
the possible link between the dominance of l-amino acids and electro-
weak asymmetry cannot be ruled out on the basis that the latter’s chemical
influence is too small. Our observation, however, is not a proof that such a
link exists.
1.6 EXAMPLES OF SPONTANEOUS CHIRAL

SYMMETRY BREAKING
The theory presented in the last two sections has been formulated
in the 1980s. Stimulated by these theories, laboratory examples on spon-
taneous chiral symmetry emerged in the 1990s. The simplest example of
spontaneous chiral symmetry breaking can be demonstrated in stirred crys-
tallization of NaClO3 [45].Though the molecules are not chiral, the crystals
of this compound are chiral. The two enantiomeric forms of crystals of
NaClO3 can be easily detected through their optical rotation. An aque-
ous solution of NaClO3 is not optically active, it has no chirality. But if we
prepare a saturated solution of NaClO3 and allow the solvent to evaporate
so that crystals form, each crystal is either levo- or dextro-rotatory (l- and
d-crystals).When crystallization is performed, as it is usually done, in a crys-
tallization dish, without in anyway disturbing the solution, statistically equal
number of l- and d-crystals are found.This was as expected—no asymmetry.
Spontaneous chiral symmetry breaking occurs if the crystallization is done
while the solution is continuously stirred. In almost every stirred crystal-
lization, more than 98% of the crystals were either l or d! Fig. 1.8 shows a
typical experimental result when a large number of stirred and unstirred
Figure 1.8 Histogram of CEE in unstirred (a) and stirred (b) crystallization of NaClO3.
CEE = (Nl − Nd)/(Nl + Nd) in which Nl and Nd are levo- and dextro-rotatory crystals, respec-
tively Ref. [45]. In unstirred crystallization, the distribution is centered at zero but for
stirred crystallization it is bimodal with peaks close to ±1.
Figure 1.9 Asymmetry generation in the synthesis of a Co-complex, Ref. [48]. The
distribution is not bimodal, but the large random EE shows the existence of chiral
autocatalysis.
crystallizations are performed. This was the first clear experimental demon-
stration of the phenomenon of spontaneous chiral symmetry breaking in
batch or a macroscopic scale and it is distinct from obtaining asymmetry in
crystallization due to chiral impurities. (The nucleation of a chiral crystal
could itself be thought of chiral symmetry breaking on a microscopic scale).
The details of the mechanism, the needed chiral autocatalysis and mutual
competition, were elaborated in our later studies [46,47]. Though a fun-
damental theory of the chirally autocatalytic nucleation in stirred systems
does not exist at this time, there are good empirical theories for this step of
the kinetics. Using one of these empirical rate laws, it is possible to simu-
late most of the experimental results through stochastic computer codes,
including the stochastic behavior such as the random variation of the CEE
as a function of the stirring rate [47].
The spontaneous symmetry breaking that was found in NaClO3 is not
an isolated phenomenon. Later work showed that this phenomenon is gen-
eral and can occur in several compounds; it also occurs in the crystallization
from a melt. Other similar chemical systems were also identified where the
first example of chiral autocatalysis at the molecular level has been dem-
onstrated in the synthesis of a chiral cobalt complex (Fig. 1.9) [48,49]. A
detailed discussion of these examples and related references can be found
in a review [50].
One of the key reaction steps in the generation of chiral asymmetry
is chiral autocatalysis. Chirally autocatalytic reactions are hard to find in
24 Dilip Kondepudi
organic reactions. Soai et al. have reported a family of such reactions which
are proven to be extremely sensitive to chiral influences [51–53]. Even very
small amount of initial asymmetry is greatly amplified in these reactions
[54–57]. In some cases, the sensitivity to even very small amounts of impu-
rities is so great it was found to be too difficult to eliminate it altogether in
the laboratory [58].
Spontaneous chiral symmetry breaking can also be observed in Lang-
muir monolayers [59] and in molecular aggregation [60]. In the aggrega-
tion of molecules, Ribo et al. [60] reported chiral selection induced by
vortex motion. They also reported that sensitivity to vorticity depended
on the rate at which the system sweeps through the aggregation point, a
feature predicted by the theory presented in Section 1.5. Purrello’s group
has reported influence of chiral additives on the assemblies of porphyrins
[61–63].The assemblies of porphyrins can be chiral though the porphyrins
themselves are not chiral molecules. Since this is a case of chiral symmetry
breaking, we could expect a very high degree of sensitivity to chiral influ-
ences during the process of assembly. Purrello’s group has demonstrated
that once a particular chirality is induced in the assembly by a chiral ad-
ditive, the assembly maintains its chiral structure if the chiral additive is
removed.
Fifteen years after the original discovery of chiral symmetry breaking
NaClO3 crystals by Kondepudi et al. [45], an interesting variation of chiral
symmetry breaking in NaClO3 was discovered by Viedma [64]. This sym-
metry breaking occurs in the solid-state. In this experiment, equal masses
of l- and d-crystals were ground into a powder and placed in a saturated
solution (so they do not dissolve). Then these crystals were continuously
ground by placing glass beads and magnetic stir-bar in the solution. After a
day of continuous stirring of this solid phase it was found that the crystals
converted to predominantly one chiral form or the other; the symmetry of
equal amounts of l- and d-crystals was broken by the grinding process. The
mechanism involves the dissolution of very small crystals (because solubility
increase for smaller crystals) and the growth of larger crystals [65,66].Theo-
retical modeling reveals intricacies of this process [67,68] that is so simple
to perform in the lab.
At this point it is fair to say that there is no dearth of examples of systems
that show chiral autocatalysis [69] and symmetry breaking, and we may
expect interesting applications of the sensitivity of such systems to chiral
influences in the future.
1.7 CONCLUDING REMARKS

We inhabit a world that exhibits chiral asymmetry. In the words of
Louis Pasteur, “L’univers est dissymmétrique”. But we do not know much
about the exact origins of these asymmetries though our knowledge of
chemical systems that spontaneously generate asymmetry has grown in the
last 15 years. The origin of biomolecular asymmetry, for example, still re-
mains lost in a cloud of speculations.
The asymmetries in nature at all spatial scales make us wonder if they
are somehow related. Since the symmetry breaking transitions are highly
sensitive to chiral influences, it is possible that the asymmetries at vari-
ous levels are related, the asymmetry at one level being the small influ-
ence that acts on the symmetry breaking process at the next higher level.
Thus, the asymmetry at the molecular level of amino acids and DNA
somehow might propagate to higher level and influence the asymmetric
organ placement during morphogenesis. Although it is easy to see the
propagation of asymmetry from one level to another at the primary and
secondary structures of proteins, the asymmetry and its propagation are
not so evident at higher levels. It is a real challenge to elucidate the path
through which molecular asymmetry finds its way to morphology of an
organism [35].
Propagation of asymmetry in macromolecular aggregates is of much
interest. As noted by Thomas et al. [70–72], the asymmetry of the mono-
mer units does not always propagate to the higher level of aggregation. To
understand the propagation of asymmetry at various levels, we need new
theoretical approaches and experimental methods. Given the high level of
interest in this topic, we may expect rapid progress in this field.
ACKNOWLEDGMENTS
We gratefully acknowledge the contributions of undergraduate and graduate students and
postdoctoral fellows to the work presented in this chapter. This work was supported by NSF
(grant CHM-9527095) and by the Japan Society for the Promotion of Science.
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smallpox, and the babe of three months took it from her. After that
Mrs. Judson herself was taken seriously ill, and for two months lay
helpless on a mat on the floor of the wretched little hut, where she
had taken up her abode, to be near her husband in the prison. When
the child recovered, the mother was unable to nurse her, so that,
being deprived of her usual nourishment, the infant suffered greatly.
Neither a nurse nor a drop of cow’s milk could be procured in the
village. However, by making presents to the jailers—nothing could be
done without presents—she obtained leave for Dr. Judson to come
out of prison daily, in order to carry the emaciated little creature
round the village, to the houses of those women who were suckling
children, and to beg them for pity’s sake to give each a little, to keep
the life in the child!
In this way the twenty-two weary months of his captivity passed,
amidst hardships, sickness and anxiety unspeakable. At length
release came. On the advance of the English army up the Irrawaddy,
Dr. Judson was sent for to the Burmese camp, being then a most
valuable man, to serve as interpreter and translator, and to negotiate
terms of peace; and thus their long captivity came to a close.
Ardently as Judson longed to see his mission established in Upper
Burma in his day, sixty years were destined to elapse before the
society to which he belonged secured a permanent footing there. It
was after the annexation in 1886 that work was permanently taken
up by them in Mandalay. A handsome church has recently been
erected there at a cost of about £3,000, by contributions from
America and Burma, as a memorial of Dr. Judson, and the mission
has met with a fair share of success. In addition to Mandalay, three
other stations have been taken up by the American Baptist Mission
in Upper Burma—viz., Sagaing, Myingyan and Meiktila, and one
medical missionary has gone to the Shan States. Bhamo was
occupied previously, during King Theebaw’s reign, for work amongst
the Kachin tribes.
The Society for the Propagation of the Gospel (S. P. G.) began its
work in Mandalay under the comparatively favouring auspices of
King Mindohn, the father and immediate predecessor of Theebaw.
This monarch built for the mission, at his own cost, very commodious
and handsome premises of teak wood, consisting of a church, a
mission house, and a school, which still remain. In the church is a
handsome font, the appropriate gift of Queen Victoria to this church,
built by the munificence of a heathen king! Theebaw, when a boy,
was a pupil in that school, and there was no thought then of his
succeeding to the throne. He made very little progress with English
study, though he had a good reputation for Buddhist lore.
Owing to the massacres and other grievous disorders of
Theebaw’s reign, the mission had to be closed for several years, the
missionaries, along with all the other English residents, having to
leave Mandalay. On the annexation being declared, the S. P. G.
mission was reopened, and subsequently another station was
opened at Shwebo, and these two stations, with a sub-station at
Madeya, have experienced a fair share of prosperity since.
During the six years these two missions have been re-established
in Upper Burma, the effects of the climate upon the health and lives
of the missionaries have been very marked. Both missions have
already their record of the faithful dead—mission workers, both male
and female, who have fallen in the prime of life, and one before she
had well begun her mission work. In both missions, too, during that
time several valued workers have had to leave the country, worn
down by sickness, and unable to endure the climate.
The Wesleyan Mission commenced work in Mandalay at the
beginning of 1887. Up to date we number three European
missionaries, two Singhalese workers (from Ceylon), and three other
native preachers, and we have occupied three stations, Mandalay,
Pakokku and Kyaukse. The story of our work will appear in the
subsequent pages.
“WE NUMBER THREE EUROPEAN MISSIONARIES, TWO SINGHALESE
WORKERS, AND THREE OTHER NATIVE PREACHERS.”
Coming now to the subject belonging to the second half of this

chapter,
THE FALSE MISSIONARY IDEAL,
I wish to deal with a matter, partly suggested by the recital of
the sufferings of Judson just related, upon which something
needs to be said. It has often appeared to me that there still
lingers, in the minds of many people, a very erroneous ideal
of missions and missionaries, which it is quite time to do away
with. A recent writer has aptly expressed the notion to which I
refer in these words:—
“The more barren the missionary’s lot of all comfort, the
greater the degree of self-denial and privation that can be
encountered, the better. What he has really undertaken is to
carry the Gospel to the destitute, and so to live as to secure
the longest, fullest and most complete career of usefulness
along that line. But this is not the view of the malcontents;
they regard him as a spectacle, an ascetic, an object lesson
in self-denial. It is not so much what he does as what he
suffers. The chief end is the impression which he makes on
men’s minds by his self-mortification.”
This may seem at first sight rather a strong putting of the
case, but I think it will be apparent, as we proceed, that it is
nearer the popular notion than the reader may at first be
prepared to admit. The first witness I will cite is John G.
Paton, missionary to the New Hebrides. If the reader has not
yet read his book, let me urge him to do so without delay. In
the earlier days of his missionary life on the island of Tanna,
he passed through a period of almost unexampled trial from
the brutal savagery of the natives, owing to the fact that there
was no such thing as law, justice, or protection of any kind to
be obtained. His trials were such as few men could have
endured, and lived. The people were utterly uncivilised,
bloodthirsty, quarrelsome, superstitious and vindictive. Human
life was scarcely of any value among them, and they were
cannibals. His life was attempted times without number. Other
missionaries and native Christian teachers were murdered,
and done to death by them one way or another, and how he
escaped death amongst them seems nothing short of
miraculous.
At length a crisis more acute than usual came, and the
wicked and superstitious malice of the Tannese broke out
against him to such a degree that he was driven out of the
island, all his property was looted, and he barely escaped with
his life. In his distress he went over to Australia to recruit his
health, which must have needed it after such a strain. Of what
occurred there I quote his own statement:—
“Some unsophisticated souls who read these pages will be
astonished to learn, but others who know more of the
heartless selfishness of human creatures will be quite
prepared to hear, that my leaving Tanna was not a little
criticised, and a great deal of nonsense was written, even in
Church magazines, about the breaking up of the Mission. All
such criticism came, of course, from men who were
themselves destitute of sympathy, and who probably never
endured one pang for Jesus in all their comfortable lives.
Conscious that I had, to the last inch of life, tried to do my
duty, I left all results in the hands of my only Lord, and all
criticisms to His unerring judgment. Hard things also were
occasionally spoken to my face. One dear friend, for instance,
said, ‘You should not have left. You should have stood at the
post of duty till you fell. It would have been to your honour,
and better for the cause of the Mission, had you been killed at
the post of duty like the Gordons and others.’
“I replied, ‘I regard it as a greater honour to live and to work
for Jesus than to be a self-made martyr. God knows that I did
not refuse to die; for I stood at the post of duty, amid difficulty
and danger, till all hope had fled, till everything I had was lost,
and till God, in answer to prayer, sent a means of escape. I
left with a clear conscience, knowing that in doing so I was
following God’s leading, and serving the Mission too. To have
remained longer would have been to incur the guilt of self-
murder in the sight of God.’”
These sentiments, especially the words I have italicised, do
honour alike to Paton’s devotion and to his common sense,
and they are a just rebuke of a very false ideal.
Happening to take up one day an influential religious
newspaper, I met with a notice of John G. Paton’s book,
which spoke in very high terms of it, and of him, concluding
with the following sentence, in which the editor most
innocently and unconsciously brings up in another form this
same false ideal, even after reading the book; which shows
how prevalent the error is, and difficult to eradicate. “Now that
civilisation is spreading, and owing to the general extension of
facilities for travel to every part of the earth, it is to be feared
that such records of missionary experience will soon be
amongst the things of the past.” “It is to be feared” say the
stay-at-home people, and editors in easy chairs. Any
missionary, especially Paton himself, would have said, “It is to
be hoped.” If the reader will but ponder that word “feared,”
and take in all that it means, he will see that it is the very
notion Paton complains of, and that I am here seeking to
correct.
We still need to take to heart Dr. Johnson’s exhortation to
“clear our minds of cant.” After praying times without number
that cannibalism, and all the cruel horrors and barbarities of
heathenism might come to an end, we are found fearing that
our prayer is so near being answered, that soon there will be
no more such tales to tell!
The immense wave of sympathy that was evoked through
the lamented illness and death of Father Damien, and which
spread throughout the civilised world, was another proof of
the prevalence of the “object lesson” ideal of the missionary.
Missionaries had been at work succouring and tending lepers
for many years before that, and a noble society, the Mission
to Lepers, established in 1874, has now some thirty homes
for lepers under its care, in India, Burma and China, under the
management of twelve different Protestant missionary
societies. But all this work goes on in comparative obscurity,
the whole of it together not attracting one hundredth part of
the sympathy and notice that this one case of suffering
attracted. Father Damien died of leprosy. “This, this is what
we want; this touches our hearts and our pockets,” cries out
universal Christendom. It seems it is not mission work but
missionary sufferings the people want to hear about. A false
ideal.
A further proof how widespread is this notion will appear
from a recent article in the March number of the Missionary
Review of the World for the year 1892. The writer states it as
frankly as words and repetition can express it, quite
unconscious that there is anything wrong about it. The article
is on “Missionary Fellowship.” It is not written by a missionary;
no missionary could possibly write such rank nonsense. This
is what he says: “Suffering, after all, is the test of missionary
character.... It is not so much what the missionary does as
what he is, and what he is can be shown only by suffering for
the Gospel’s sake.” He goes on to say that it is Judson’s and
his wife’s sufferings in Burma, more than their missionary
labours, that “canonise them as martyrs of modern missions”;
and there is a good deal more “high falutin’” of the same kind.
To my mind this is a false and absurd ideal—mischievously
false. Men have gone on thinking it, and occasionally saying
it, until they fail to see the falsity and absurdity; but if we think
for a moment we must admit that the Bible tells us that every
missionary’s work, every Christian’s work, must be the test of
the man, and not his sufferings, and gives no countenance
whatever to this error. Our sufferings are matters for which we
are not personally answerable in any way, except as we may
cause them ourselves; otherwise they are beyond our control,
and can be therefore no test of the man. Judson would have
been one of the very greatest of missionaries, all the same, if
he had never seen the inside of a Burmese prison. His
lifetime of earnest evangelistic labours, his Burmese Bible, his
two dictionaries, his Burmese grammar, his other precious
literary remains, and the many souls saved through his
instrumentality, and long since gone to glory—these are the
enduring monuments that entitle him to our reverence, and
constitute that bright example which some of us are humbly
trying to follow. His sufferings were indeed severe, but to
dwell upon them, and laud them as being of far more
importance than his work, not only does an injustice to the
memory of the man himself, but it feeds a false ideal, and
keeps from view the real purpose for which we go to the
heathen.
The sooner we give up this nonsense entirely, and take our
stand upon truth and common sense, the sooner shall we find
the sound, and only sure basis for that increase of missionary
enthusiasm, which is so much needed at the present time. So
long as our enthusiasm is based upon any such shadowy and
precarious foundation as the sufferings of missionaries,
whether supposed or real, so long will the results disappoint
us.
But there is a further objection against this false ideal, on the
ground that abroad, in the mission field, it gives rise to a powerful
and subtle temptation in some minds, and leads to waste of precious
power. In most mission fields the hardness of the hearts of many of
the heathen, and the deep sense of isolation from the people which
the missionary feels, and which is inevitable from the difference of
race, language and habits, are so distressing, that there are few
conscientious souls that have not felt, at some time or other, a strong
tendency towards an ascetic mode of life: “O! let me do this, let me
do that, let me do anything, if I can only come nearer the people.”
There is quite enough tendency to this abroad, without its being
further stimulated by a demand at home.
“But what do you mean by asceticism? Where do you draw the
line?”
By asceticism I mean the deliberate—sometimes even
ostentatious—cutting down of provision as to food, clothing, dwelling,
and general comfort, to a point obviously below the standard of
health and efficiency; this standard being naturally fixed at an
approximation to that of the mode of life to which the missionary has
previously been accustomed. My own experience of missionary life,
extending over nineteen years, is that I have always had to work
much harder than if I had been in England, and, whilst the mode of
living must needs be very plain and temperate to be healthy, the food
must be nourishing, and the surroundings in a fair degree of comfort,
or it will soon lead to a collapse.
I do not condemn economy; God forbid! No one believes in that
more than I do. I entertain strong views as to the importance of a
humble, simple, unostentatious manner of life, and have always
practised it. Nor do I wish to state that the missionary has no need of
self-denial. A man cannot be even a disciple without self-denial.
Without it, as a missionary he would be useless; and I may testify, in
all simplicity, that I have known what it was to practise it, and have
reaped the sweet and precious fruits of it. But if that hymn of Keble’s
is true anywhere it is true in the missionary’s life—
“The trivial round, the common task,

Will furnish all we ought to ask;
Room to deny ourselves; a road
To bring us, daily, nearer God.”
“All we ought to ask”; missionary life with its labours, cares and
anxieties, often in an exhausting climate; its frequent and sore
disappointments, its loneliness, the separation from friends and
children, and the special call sometimes to new and untried spheres
of duty; its sense of heavy responsibility in having to stand practically
alone, at the head of a band of native helpers, and to be expected to
supply enthusiasm for everybody about him—these, the necessary
and unavoidable trials, are the legitimate means of denying himself;
and they afford infinite scope for useful, holy service, and they are
quite enough, without going further afield, like Don Quixote, in
search of more.
I trust my readers will bear with me whilst I give the details of
some cases I have known, where honoured brethren and sisters
have felt moved to attempt the ascetic method, in order that we may
observe how it works.
I knew a pious devoted missionary of another Society. He was a
man of decidedly ascetic life. One of the ordinary diseases of the
country, not generally fatal, assailed him. His constitution, in the
opinion of those best able to judge, was so weakened by his ascetic
life that he could not rally, but died in the prime of life. Humanly
speaking, he died before his time, and one fails to see that his death
constitutes any adequate object lesson, to compensate for the loss
of his active usefulness. A missionary’s continued and useful life
ought to be a much greater benefit to a country than the deposit of
his remains in the soil, and the example of a living worker is surely
more influential than the memory of one departed.
I knew a missionary and his wife, earnest, devoted, exceedingly
kind to the people, and successful. From the first of their settling in
the country, their asceticism was so marked that their friends, who
saw it, pleaded with them to eat more food and better food, but in
vain. Being new to the country, they did not know the risks they ran.
After barely two years of earnest work, ill health compelled their
retirement from the field, with scarcely any prospect of ever
returning. And yet there was no kind of necessity for them to live
thus. They appeared to think there was some virtue in self-denial of
this type, merely for its own sake.
Another case of the same kind was that of an unmarried
missionary lady, with a strong natural tendency to asceticism. She
was an able and diligent missionary, and well acquainted with the
language. After some years of missionary life, the tendency grew
upon her to such an extent, that she withdrew more and more from
association with her own people, lived with none but natives, on
native food, and broke off one comfort after another, until even bread
was too much of a luxury! After a year or eighteen months of this
ascetic life, her health broke down so completely that she had to
return home to America or die.
One of our brethren in India has told us his story of a similar
attempt. It was a sense of duty that urged him to come down to
native diet, native dress, and general mode of life; and very loyally to
this sense of duty did he persevere for many months. But, to his
infinite sorrow, he found that instead of bringing him any nearer to
the people, it seemed only to increase the distance; for it aroused
their suspicions as to his motives for doing so. He found at length
that he could have reached them better if he had moved amongst
them in the ordinary way. But meanwhile the penalty of all this had
come; his health so completely broke down, clearly in consequence
of this method of living, that he had to leave India, and now for
several years he has been laid aside completely in England, unable
to do any regular work. He is the victim of an honest, and very
persistent, but mistaken attempt to live an ascetic missionary life.
As regards the wearing of the native dress, it has often been
assumed that to do so must needs place a missionary more in touch
with the natives. But in India it is not found that such is really the
case. With the exception of the Salvation Army, this is the only case
in India where I ever heard of its being attempted, and it had quite
the contrary effect. I have heard that a venerable missionary once
tried it in Burma, but the peals of laughter that greeted his
appearance in the streets instantly convinced him that he could gain
nothing by that method. There are probably cases where it is
advisable, and even almost necessary, to assume the dress of the
country. Each case should be judged upon its own merits, and it
greatly depends what kind of a dress it is. In India and Burma they
like to see the man be himself, and they respect you for keeping to
the customs you have been brought up with.
The following is a faithful account of an heroic, but ill-judged
and disastrous, missionary enterprise in Burma, in substance
as I had it from the lips of one of the survivors, who paid me a
visit in Mandalay, a few of the particulars being supplied by
another missionary well acquainted with the facts. I wish that
all my readers could have heard the touchingly simple recital,
and witnessed the gentle and refined Christian bearing of this
excellent brother. It is the narrative of a small mission, sent
out by evangelical Christians in Denmark to the Red Karens,
an independent tribe of demon worshippers, dwelling in
Karennee, on the eastern frontier of Burma. My informant is a
Dane. It will be observed that the bane of the whole enterprise
was the ascetic idea, imbibed at home, and in this case
carried out to the bitter end. The case serves to show also
what a formidable difficulty to foreign evangelism we have in
the mere matter of the climate.
Near the close of 1884, two young men, Danish
missionaries, Hans Polvsen and Hans Jansen, arrived in
Burma, with the purpose of establishing this mission. On their
arrival they looked the very picture of health. They had both
been inured to hard work from their youth, and they were
devout men, and entirely given up to work for the Master.
Though receiving aid at first from home, they hoped soon to
make the mission self-supporting. They therefore undertook
to do all the manual labour themselves. Where others rode
they would walk. Where others employed natives they would
do their own work. They would cook their own food, and live
in the simplest manner, even like the natives of the land. Had
the sphere of their mission been the wilds of America, or any
country at all similar in climate to their native Denmark, it
would have been the right policy, and they might have
succeeded. But they soon had painful proof that there are
laws in Nature, from which even missionaries are not exempt;
and one of these laws is that we cannot do with impunity in
the tropics what we may do in the temperate zone.
Some time after their arrival, an opportunity occurred for
going into Karennee, and they prepared to start for their
destination. By way of preparation they gave away all their
extra goods, medicines, clothing, etc., fancying that Matthew
x. encouraged such a course. We cannot but place in contrast
this conduct with that of a man like Livingstone. His was a
self-denying work, if ever there was one; he believed in doing
the work God called him to do, no matter what difficulties
stood in the way. But he was no believer in asceticism—i.e.,
needless suffering for suffering’s own sake. He relates in his
“Last Journals” how, when he found his medicine chest was
hopelessly lost, through the carelessness of a native carrier,
he felt as if his death warrant were sealed. But these people
thought it right to give away their medicines and goods on
leaving the confines of civilisation. Before leaving Toungoo
they were faithfully warned by experienced missionaries of
the American Baptist Mission, that such a course as they
were entering upon, at the beginning of the rains, was
exceedingly hazardous; but their notions of trust in
Providence prevented them from paying any heed to this
counsel.
They reached Karennee, after a rough journey over the
mountains and through the jungles, and proceeded at once to
put up for themselves a house, and establish the mission
according to their ideas. It is difficult for any one not knowing
the country to conceive how hard their lot would be. Their
sufferings were extreme. Hard work and exposure, together
with poor food, and only the shelter of a bamboo house, that
afforded no proper protection from the pitiless rains, and
damp, cold blasts, soon broke down their health. Fever, the
great bane of tropical malarious regions, soon found them
out. Hans Polvsen died before the rains were over, and
Jansen was brought into Toungoo by the American Baptist
missionaries, more dead than alive, and kindly nursed and
brought round. A new party from Denmark now reached
Toungoo, consisting of Knudsen, his wife, and Miss Jansen,
the sister of Hans, and the four set out for Karennee. Here the
former experiences were renewed; for the party had not yet
learnt wisdom, even by such terrible sufferings. Soon they
were all very ill. Miss Jansen died: after that a babe, born to
the Knudsens after reaching Karennee, was also taken. The
stricken father had to get up from his sick-bed to make the
coffins. They could get no meat, no bread, no milk, none of
the ordinary comforts of civilised life, nothing but an inferior
kind of rice, which they could not eat when sick, and which no
European could thrive and work upon, even in health. Jansen
was warned by an English doctor passing through the place
with troops, that he must get away from Burma, or he would
soon die. He went to Toungoo again, recovered a little, and,
against the earnest advice of the doctor there, who warned
him that he went at the peril of his life, he determined to start
on a third journey for their chosen mission field. But he never
again entered Karennee. On reaching the foot of the great
mountain range, he seated himself beneath the shade of a
beautiful arching clump of bamboos, and there breathed out
his devoted life. It is characteristic of the popular, but false
ideal of the missionary life entertained by many people at
home, that, as my informant put it,—for by that time his eyes
were opened to see the matter in its true light,—“They were
inclined to make more of the ‘heroism’ of that unwise act of
returning, and dying on the way, than they would if he had
fulfilled a long career of useful service.”
The Knudsens became so completely broken down in
health that they too were compelled to leave Karennee. Thus
this little mission, begun with the highest of motives and
carried on with quenchless, self-sacrificing, prayerful zeal,
was entirely and hopelessly wrecked, through its adherence
to ascetic principles, and had to be finally abandoned, after
five years of heroic, but utterly wasted, labour and suffering,
and without any appreciable impression being produced upon
the natives of that region.
I shall naturally be asked, “What then about those larger
missionary organisations, in different parts of the world, that put
asceticism (not economy) avowedly in the forefront, as one of their
leading principles?” Well, I will only say of them, in brief, that where it
is asceticism as defined above, and not mere economy, facts and
experiences have proved that, in the tropics, it has resulted in a far
heavier death-rate, in far more total or partial failures of health, and,
as human nature has its limits of endurance, in a considerable
addition to the numbers in the column headed “retired from the
work.” A proper deduction made from the working strength of such
missions, on account of these non-effectives, would show, perhaps,
that the cheapness supposed to be attained, is more apparent than
real.
On one occasion it was pointed out to the great Napoleon that he
was losing a great many men in a battle; he is credited with the
cynical reply, “You cannot have omelettes without breaking eggs.” In
like manner one at least of these organisations has said boldly, “You
cannot have a war without losing soldiers.”
True; but if the greater part of this loss is clearly needless and
preventible, and if it is the result of want of proper provision being
made, and through the neglect of proper precautions of the most
ordinary kind—then even the sacredness of the purpose does not
justify the recklessness of the methods.
“Alas, that bread should be so dear!

And flesh and blood so cheap!”
There remains only one more point which I need to mention, and
that is the utter futility of the ascetic method, if it is used with any
intention of impressing the Oriental mind. The utmost degree of
asceticism which any European could ever think it right to adopt, in
the discharge of his duties as a missionary, would, to an Oriental, fall
far short of his ideal of self-denial, and would not be worth the name.
A writer, with wide experience of India, has put this so well, that I
may as well quote his words.
“The Hindus understand real asceticism perfectly well, and revere
it as a subjugation of the flesh; and if the missionary and his wife
carried out the ascetic life as Hindus understand it, lived in a hut, half
or wholly naked, sought no food but what was given them, and
suffered daily some visible physical pain, they might stir up the
reverence which Hindus pay to those who are palpably superior to
human needs. But in their eyes there is no asceticism in the life of
the mean white, the Eurasian writer, or the Portuguese clerk, but
only a squalor unbecoming a teacher, and one who professes, and
must profess, scholarly cultivation.”
I have ventured, not without due reflection, to point out in this
chapter what seems to be a very false ideal of missions and
missionaries. The setting up of the missionary as a spectacle, an
object lesson in self-denial, may be a time-honoured institution, but it
ought certainly to give way now to some more rational method of
recommending this important enterprise. I do not mean to say that
this mistake has been universal, or even general. Many people of
knowledge and common sense have risen above it. But the
evidences of this idea to be found still in prominent places at home,
and the instances of it abroad, which are here cited, prove that there
has been in popular thought too much leaning in that direction, and
show that there is need to point out the fallacy, and the evil of it.
When the simple recital of missionary facts includes the actual
experience of unusual trials and perils—as, alas! must still be the
case sometimes—it will always command sympathy and attention;
but to represent these things as at all comparable in importance to
mission work, or to suppose that they essentially belong to it, is
neither true nor judicious. And I have shown that, when this tendency
is yielded to in the mission field, it leads to an asceticism which
produces no increase of usefulness, but a speedy termination of the
missionary’s labours.
Note.—Since writing the above chapter, an article has appeared

in the Indian Medical Record on “Missionaries and Mortality,” which
is so much to the point, and from such an unexceptionable,
independent, and competent source, that my readers ought to have
the benefit of an extract from it:—
“We would only be just to claim for the missionary every safeguard
that we apply to the lives of Europeans in other callings in India.
Good, wholesome food, suitable clothing, a proper dwelling-house,
and ordinary English home comforts are certainly the least that might
be assured to missionaries working in India. Deprived of these vital
necessaries, it is no wonder that men unused to the enervating
influence of the tropics, burdened with cares and anxieties in the
arduous work of an Indian mission field, should rapidly succumb to
conditions so trying and hostile to their constitutions.
“We have endeavoured to obtain all the information we could upon
this important subject, and we are astounded, both from our own
personal experience, and from reports which reach us from
numerous quarters, at the fearful havoc that goes on yearly in the
ranks of the various missionary bodies who labour in these foreign
mission fields. We have seen scores and scores of men come to the
country seemingly full of vigour and spirits, who within two or three
years either die at their posts, or retire disabled temporarily, and
often permanently, with enfeebled health or utterly ruined
constitutions.
“From one of the statements sent us we learn that the mortality
has been as high as twenty-two per cent. in a society that only finds
a small portion of the monthly maintenance allowance for its
missionaries. In another society that works on similar lines the death-
rate is eighteen per cent. per annum. In another, in which the
members work without any allowance, and are compelled to find
their food, shelter, and clothing among the very poorest of the Indian
people whom they seek to convert, the mortality has been as high as
thirty-two per cent. per annum; while its invalid list yields abundant
evidence that its methods, while they may be praiseworthy in their
ascetic simplicity, are too sacrificial to European life to justify their
toleration and continuance.
“Missionary zeal and missionary enterprise have done more for
India than any State effort could ever hope to accomplish, and the
best work has been done by those societies which, having a due
regard for the health and safety of their workers, have provided for
the proper conservation and protection of their lives; and lives thus
prolonged and preserved have brought with them accumulated
experience, which has yielded the advantage not only of laying the
foundations of lasting and useful work, but of seeing it cared for,
nourished and brought to fruitful perfection by the hands that
inaugurated it. Work to be productive of good in the mission fields of
India must be lifelong. The short service system is both imbecile and
expensive. The languages and habits of the varied peoples of this
vast empire cannot be familiarised sufficiently for effective work in a
few years. But to enjoy good health and to protect the lives of
missionary workers, it is the bounden duty of the great religious
societies of England and America to make a full and ample provision
for the support and comfort of their representatives in India.”
CHAPTER XVI.
OUR EARLY EXPERIENCES IN THE BURMA
MISSION.
I would like to give the reader some intelligent idea of what it

means to establish a new mission in a new country, with an
elaborate religion like Buddhism in possession of the field, and
difficult to dislodge.
We make our way up the Irrawaddy by one of the splendid
steamers of the Irrawaddy Flotilla Company, and in due time we land
at Mandalay, and climb the steep bank of the river, and there we are
with our few boxes, strangers in a strange land, knowing nobody
belonging to the place, not a word of the Burmese language, with no
mission house to turn into, no native Christians, and, worst of all, no
native helpers. After thirteen years of very happy work in Ceylon,
where we have a flourishing mission and a large staff of native
helpers, it required a stout heart to face the difficulties of pioneer
work, and no little faith, hope and perseverance. Especially did we
miss the aid of our native brethren.
The chief value of the European missionary, and of the European
generally, in the East, is in his capacity as a leader of men. Upon him
devolves the initiation, and the vigorous working out, of plans of
aggression, and he has to find the enthusiasm for everybody about
him. But if the European is brain, and heart, and hand to the mission,
his native brethren are equally indispensable as the eyes, ears, and
feet. My native brother has a knowledge of his country, and of his
people, and of all that is going on, extensive, accurate, and intimate
beyond anything I can ever attain unto, and he is in touch with his
own people as no foreigner can ever be—no, not if he spends half a
century among them. This invaluable help I greatly missed.
For some days I lodged with the Rev. J. H. Bateson in a Buddhist
monastery, which had been assigned to him by the military
authorities. He had arrived from England three weeks previously, in
the capacity of Wesleyan Chaplain to the Upper Burma Field Force.
It was one of a considerable number of buildings that had been
“annexed” for the temporary accommodation of the troops, and
which were afterwards handed over again to the Buddhist monks. It
was a fine, substantial teak building, raised six or seven feet from the
ground, with a broad verandah back and front, and consisted of
three rooms. The roof was of the usual fantastic Burmese style, in
triple form, and at one end it terminated in a rather tall spire; and the
whole of the building, as usual with monasteries, was richly
decorated with elaborate carvings in wood. Amidst some
disadvantages as a residence it had one very obvious advantage,
that we paid no rent for it.
The first duty lying before me was obviously to commence the
study of the language, and along with that, to look about and find the
best sites for establishing our mission centres, and for the first few
months I gave my attention closely to those matters. Whilst I was
making these preparations for laying the foundations of our future
mission work amongst the natives of the country, there was
abundance of work also ready to hand amongst the soldiers and
other English-speaking people, congregated in a large military and
civil station like Mandalay. Mr. Bateson had to undertake long
journeys to other military stations at intervals, in the course of his
duties as chaplain to the troops, and it fell to my lot to attend to the
English congregation in his absence. I have heard and read of some
missionaries who have held that it was no part of their duty, as
missionaries to the heathen, to preach in English at all. But I never
could see that a white skin, and the fact that a man speaks English,
should be deemed to disqualify him from receiving Gospel
ministrations; and I can see no reason why the time and attention
given to our own countrymen need be allowed to interfere materially
with the missionary’s work for the natives. It is in circumstances such
as those of Upper Burma at that time, and amidst the rough
experiences of pioneer life in a new country, that our countrymen
most need the ministrations of the Gospel. In a heathen land and

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Chiral Analysis: Advances in

Spectroscopy, Chromatography and

Emerging Technologies in Engineering Mahesh P. K.

Chiral Separations and Stereochemical Elucidation:

Advances in Business Statistics, Methods and Data

Advances in Metal Oxides and Their Composites for

Advances in Nanosensors for Biological and

Spectroscopy and Dynamics of Single Molecules: Methods

Emerging Technologies in Environmental Bioremediation

Operator Analysis: Hilbert Space Methods in Complex

Copyright © 2018 Elsevier B.V. All rights reserved.

Library of Congress Cataloging-in-Publication Data

British Library Cataloguing-in-Publication Data

For information on all Elsevier publications visit our website at

Publisher: Susan Dennis

Typeset by Thomson Digital

List of Contributors xiii

Part One Chirality in Nature 1

1. Chiral Asymmetry in Nature 3

2. Remote Sensing of Homochirality: A Proxy for the Detection

Part Two Spectroscopic Methods and Analyses 71

3. Light Polarization and Signal Processing in Chiroptical

3.3 Types of polarized light 76

4. Chiroptical Spectroscopic Studies on Soft Aggregates

5. Vibrational Optical Activity in Chiral Analysis 201

6. Raman Optical Activity 249

6.1 Fundamental principles 250

6.3 Enhancement of ROA signals 270

7. Chiral Molecular Tools Powerful for the Preparation

8. Chiroptical Probes for Determination of Absolute

9. Chiral Analysis by NMR Spectroscopy: Chiral Solvating Agents 367

10. Chiroptical Spectroscopy of Biofluids 429

Part Three Chromatographic and Electromigration Methods 467

11. Chiral Gas Chromatography 469

12. Chiral Liquid Chromatography 507

12.3 Interactions in chiral liquid chromatography 509

13. Enantioseparations by Capillary Electromigration Techniques 565

14. Recent Developments in Chiral Separations by Supercritical

15. Chiral Separation Strategies in Mass Spectrometry: Integration

Part Four Emerging Methods 647

16. Cavity-based Chiral Polarimetry 649

17. Quantitative Chiral Analysis by Molecular Rotational

18. Chiral Rotational Spectroscopy 731

18.3 Chiral rotational spectra 734

19. Chiral Analysis and Separation Using Molecular Rotation 753

This book is intended to serve as a guide for those interested in chiral

Chiral Asymmetry in Nature

1.2 CHIRALITY: TERMINOLOGY AND

Chiral Analysis. http://dx.doi.org/10.1016/B978-0-444-64027-7.00001-X

a vector and an axial vector defines chirality.) Through such association, we

1.2.1 Cahn–Ingold–Prelog classification of chiral molecules

Figure 1.2 An example of R-enantiomer in accordance with Cahn–Ingold–Prelog rules.

In addition, for a given wavelength, the direction of rotation can change

1.2.2 Optical rotation

polarized light, respectively, for light of wavelength λ, traversing a path in a

1.2.3 Enantiomeric excess

1.2.4 Crystal enantiomeric excess

in which Nl and Nd are the number of levo- and dextro-rotatory crystals.

1.2.5 Chirality measures

1.3 CHIRAL ASYMMETRY IN NATURE

1.3.1 Asymmetry in nuclear processes

state of energy by emitting electrons or positrons, also called β-particles.

1.3.2 Asymmetry in atoms

List of Contributors xiii

Part One Chirality in Nature 1

1. Chiral Asymmetry in Nature 3

Part Two Spectroscopic Methods and Analyses 71

3.3 Types of polarized light 76

5. Vibrational Optical Activity in Chiral Analysis 201

6. Raman Optical Activity 249

6.1 Fundamental principles 250

6.3 Enhancement of ROA signals 270

9. Chiral Analysis by NMR Spectroscopy: Chiral Solvating Agents 367

10. Chiroptical Spectroscopy of Biofluids 429

Part Three Chromatographic and Electromigration Methods 467

11. Chiral Gas Chromatography 469

12. Chiral Liquid Chromatography 507

12.3 Interactions in chiral liquid chromatography 509

13. Enantioseparations by Capillary Electromigration Techniques 565

Part Four Emerging Methods 647

16. Cavity-based Chiral Polarimetry 649

18. Chiral Rotational Spectroscopy 731

18.3 Chiral rotational spectra 734

19. Chiral Analysis and Separation Using Molecular Rotation 753