Professional Documents
Culture Documents
chromatography
a century of discovery
19002000
the bridge to the sciences=technology
edited by
Charles W. Gehrke
Professor Emeritus of Biochemistry, University of Missouri,
Columbia, Missouri, USA
Robert L. Wixom
Professor Emeritus of Biochemistry, University of Missouri,
Columbia, Missouri, USA
Ernst Bayer
Professor of Organic Chemistry, University of Tubingen,
Tubingen, Germany
2001
ELSEVIER
Amsterdam London New York Oxford Paris Shannon Tokyo
chromatography
a century of discovery
19002000
the bridge to the sciences=technology
The Evolution of Chromatography. The Bridge to the Sciences=Technology. Some of the early scientists who invented, rediscovered, and=or
advanced chromatography include: M.S. Tswett, L.S. Palmer, R. Kuhn, A.W.K. Tiselius, A.J.P. Martin, R.L.M. Synge, F. Sanger, S. Moore and W.B.
Stein, and the Awardees in Chapters 2, 4, 5 and S-9, S-10, and S-11.
Who is the next farsighted scientist?
ISBN:
0 444 50114 2
1 The paper used in this publication meets the requirements of ANSI/NISO Z39.48-1992 (Permanence of Paper).
Printed in The Netherlands.
Preface
Chromatography A Century of Discovery 19002000 The Bridge to the
Sciences=Technology, is a documentary of seminal events, developments, discovery,
and history of chromatography in the 20th century that presents the beginnings and
story of chromatography which revolutionized the sciences for students, researchers,
and science for the 21st century. Its central theme is the impact of chromatography as a branch of science on different facets of science analytical chemistry,
instrumentation, biomedical-, environmental-, pharmaceutical-, and space sciences, etc.
Who are the Chromatography Award winners? They were nominated by their
colleagues, evaluated by their peers and recognized for outstanding contributions. Each
Awardee was recognized as a recipient of one or more international or national Awards
for their investigations in the separation sciences. The 13 most important Awards and
their respective sponsoring professional societies are listed in the outline of Chapter
2. We invited over 100 Awardees in Chromatography to write about their unique
activities and careers in their own words and to share how their advances have impacted
the science disciplines.
The book represents the combined thinking and contributions of many chromatographers and colleagues. E. Bayer (Professor of Chemistry, Director of the Research
Center for Nucleic Acid and Peptide Chemistry, of the University of Tubingen) is Editor
in Europe. Chapter 2 is a compilation of international and national award winners in
chronological order (most since 1975) from 13 professional societies and associations
for 19002000. Among the very early group (1900s1920s) were M.S. Tswett, L.S.
Palmer and C. Dhere, who contributed fundamentally to liquid adsorption chromatography. From E. Lederer on (1931), classical column chromatography was widely used
across Europe. R. Kuhn and L. Zechmeister of Europe and H.H. Strain of the USA were
widely recognized as pioneers in this field.
The 1940s saw the seminal work of A.J.P. Martin and R.L.M. Synge on liquidliquid
partition chromatography, which then was utilized by them in the development of paper
chromatography. At that time, A. Tiselius systematized the various chromatographic
processes. Ion-exchange chromatography also started in the 1940s, with the Manhattan
Project group utilizing the new synthetic polymeric resins for the separation of rare
earths. Soon after, S. Moore and W.R. Stein (in the 1950s) extended IEC to the
separation of amino acids and E. Glueckauf, in England, provided the interpretations
of the basis of IEC separation. W.E. Cohn at Oak Ridge used IEC for the analysis of
nucleic acids, and S. Moore and W.R. Stein, together with D.H. Spackman developed
the first instrument the amino acid analyzer. E. Cremer in Austria, J. Janak in
Czechoslovakia, C.S.G. Phillips in England and A.A. Zhukhovitskii in the Soviet
Union carried out pioneering work on gas adsorption chromatography, but the real
VI
Preface
Preface
VII
This book is recommended for Students in the Sciences and Research, Chromatographers at all levels: professional scientists; research chromatographers in
academia, government, and industry; science libraries in academia, industry and professional societies, historians and philosophers of science; and educators and students
at both high school and university levels. This book describes Chromatography as
the Bridge a key foundation built in the 20th century for major advances and
discoveries yet to come across the sciences of the 21st century.
C HARLES W. G EHRKE
ROBERT L. W IXOM
and E RNST BAYER
(Editors)
VIII
Dedication
To our scientific colleagues:
Who are the pioneers and builders of chromatography.
Who have contributed to this historical compendium.
Who have provided scientific thought, experiments, evaluation and communications
to the world at large, and who interact with leaders in communities, states and international realms. Our sincere thanks are extended to the many accomplished scientists
from around the world who have graciously and diligently presented their research
findings in their contributed papers. Their efforts have allowed this treatise to present
an international, and a comprehensive perspective of the field of chromatography. In
this fast-developing science and technology, their research findings have and will, play
important roles in the advancement of science in many disciplines.
To our respective research institutions:
Whether academe, government, corporate, institutes, and foundations that have
supported this and other scientific research enterprises.
To our respective family members:
Who have given freely of their tangible support and valuable suggestions.
Our thanks are also extended to the editors of Elsevier Science.
IX
Acknowledgements
The Editors of this book had the benefit of many discussions and advice from other
chromatographers. However, one scientist stands out, Leslie S. Ettre, who not only
contributed four chapters, but has served valiantly on many policy issues, a variety of
specifics and relationships, and as a friendly critic. With his multiple experiences as
editor and his wealth of earlier chapters, reviews, historical explorations and several
books, the knowledgeable reader will not be surprised that we, the Editors, have
deeply appreciated the above role. Chapters 5 and 6, in recognition of achievements in
chromatography are a logical extension of the 1979 book by Ettre and Zlatkis titled 75
Years of Chromatography A Historical Dialogue.
We, the Editors, have had many helpful conversations with and advice from D.W.
Armstrong, V.G. Berezkin, P.R. Brown, T.L. Chester, C.A. Cramers, P. Flodin, G.
Guiochon, S. Hjerten, Cs. Horvath, W.G. Jennings, R.E. Kaiser, K. Jinno, B.L. Karger,
J.J. Kirkland, F.M. Lancas, K. Macek, P. Sandra, L.R. Snyder, R. Tijssen, K.K. Unger,
C. Welch and Y. Zhang.
We have appreciated the persistence and thoroughness of Nicole Hininger, a University of Missouri student, who served as a Library Research Assistant. Many valuable
suggestions and some difficult online searches were provided by the excellent Reference
Librarians at the University of Missouri: Brenda Graves-Blevins, Janice Dysart, Rebecca S. Graves, E. Diane Johnson, Paula Roper and Caryn Scoville. The Editors have
received helpful input from the librarians of the Chemical Heritage Foundation initiated
by the (American Chemical Society and other sponsors, Philadelphia, Pennsylvania) and
Chemical Abstracts (American Chemical Society, Columbus, OH). Preparation of copy
for this book is in large part due to the excellent secretarial skills plus accuracy and
patience of Crista B. Chappell, Nancy Harrison, Cinda Hudlow, Cynthia Mercado, Kara
Seidel, Valerie Wedel, and Kelly Willcut at the University of Missouri, Columbia, MO
and University of Tubingen, Germany.
The Editors have warmly appreciated the graphic artwork by Sammae Heard, MU
Graphic Artist, and the pen and ink drawings by Corrine Barbour, MU Graduate Art
Student.
Research, preparation, writing and editing this book was supported financially by the
University of MissouriColumbia, Missouri, USA:
Chancellor, Richard L. Wallace, Vice Provost Jack O. Burns, and their Office of
Research.
School of Medicine, and Dean Robert Churchill.
College of Agriculture, Food and Natural Resources, and Dean Thomas Payne.
Department of Biochemistry, and Chair William Folk.
Acknowledgements
XI
Editors
Charles William Gehrke was born on July 18, 1917 in New York City. He studied at
The Ohio State University, receiving a B.A. in 1939, a B.Sc. in Education (1941) and an
M.S. in Bacteriology in (1941). From 1941 to 1945, he was Professor and Chairman of
the Department of Chemistry at Missouri Valley College, Marshall, Missouri teaching
chemistry and physics to World War II Navy midshipmen (from destroyers, battleships,
and aircraft carriers in the South Pacific) for officer training. These young men returned
to the war as deck and flight officers. In 1946, he returned as instructor in agricultural
biochemistry to The Ohio State University in 1967 receiving his Ph.D. in 1947. In
1949, he joined the College of Agriculture at the University of MissouriColumbia
(UMC), retiring in Fall 1987 from positions as Professor of Biochemistry, Manager
of the Experiment Station Chemical Laboratories, and Director of the University
Interdisciplinary Chromatography Mass-Spectrometry facility. His duties also included
those of State Chemist for the Missouri Fertilizer and Limestone Control laws. He was
Scientific Coordinator at the Cancer Research Center in Columbia until 1997.
Gehrke is the author of over 260 scientific publications in analytical and biochemistry.
His research interests include the development of quantitative, high-resolution gas- and
liquid chromatographic methods for amino acids, purines, pyrimidines, major and modified nucleosides in RNA, DNA, and methylated CAP structures in mRNA; fatty acids;
biological markers in the detection of cancer; characterization and interaction of proteins, chromatography of biologically important molecules, structural characterization
of carcinogenRNA=DNA adducts; and automation of analytical methods for nitrogen,
phosphorus, and potassium in fertilizers. He developed automated spectrophotometric
methods for lysine, methionine, and cystine.
He has lectured on gasliquid chromatography of amino acids in Japan, China, and at
many universities and institutes in the United States and Europe. Gehrke analyzed lunar
samples returned by Apollo flights 11, 12 and 1417 for amino acids and extractable
organic compounds as a co-investigator with Cyril Ponnamperuma, University of
Maryland, and with a consortium of scientists at the National Aeronautics and Space
Administration (NASA), Ames Research Center, California, and the University of
Maryland, College Park, MD.
Awards and honors
In 1971, he received the annual Association of Official Analytical Chemists (AOAC)
Harvey W. Wiley Award in Analytical Chemistry. He was recipient of the Senior Faculty
Member Award, UMC College of Agriculture, in 1973. Invited by the Soviet Academy
of Sciences, he gave a summary presentation on organic substances in lunar fines at
XII
Editors
Charles W. Gehrke and Robert L. Wixom. Photograph taken on the University of Missouri Campus,
Columbia, MO, USA, July 2000.
Ernst Bayer. Photograph taken at the Symposium on Environmental Technologies in the Research Center of
PETROBRAS, Brazilian Oil Company, September 2000.
Editors
XIII
the August 1974 Oparin International Symposium on the Origin of Life. In 1975, he
was selected as a member of the American Chemical Society Charter Review Board
for Chemical Abstracts. Sponsored by five Central American Governments, he taught
chromatographic analysis of amino acids at the Central American Research Institute for
Industry in Guatemala, 1975.
Gehrke was elected to Whos Who in Missouri Education, recipient of the UMC
Faculty-Alumni Gold Medal Award in 1975 and the Kenneth A. Spencer Award from
the Kansas City Section of the American Chemical Society for meritorious achievement
in agricultural and food chemistry, 19791980. He received the Tswett Chromatography
Memorial Medal from the Scientific Council on Chromatography, Academy of Sciences
of the USSR, Moscow, 1978 and the Sigma Xi Senior Research Award by the UMC
Chapter, 1980. In 1986, Gehrke was given the American Chemical Society Midwest
Chemist Award. He was an invited speaker on Modified Nucleosides and Cancer in
Freiburg, German Federal Republic, 1982, and gave presentations as an invited scientist
throughout Japan, Peoples Republic of China, Taiwan, Philippines, and Hong Kong
(1982 and 1987). He was elected to the Board of Directors and Editorial Board of the
AOAC, 19791980; President-Elect of the Association of Official Analytical Chemists
International Organization, 19821983; and was honored by election as the Centennial
President in 19831984. He developed Libraries of Instruments, an interdisciplinary
research programs on strengthening research in American Universities.
Gehrke is founder, board member, and former Chairman of the Board of Directors
(19681992) of the Analytical Biochemistry Laboratories, Inc., a private corporation
of 250 scientists, engineers, biologists, and chemists specializing in chromatographic
instrumentation, and addressing world-wide problems on pharmaceutical and environmental issues to the corporate sector. He is a member of the board of SPIRAL
Corporation, Dijon, France.
Over 60 masters and doctoral students have received their advanced degrees in
analytical biochemistry under his direction. In addition to his extensive contributions
to amino acid analysis by gas chromatography, Gehrke and colleagues have pioneered
in the development of sensitive, high-resolution, quantitative high-performance liquid
chromatographic methods for over 100 major and modified nucleosides in RNA, DNA,
tRNAs and mRNA, and then applied these methods in collaborative research with
scientists in molecular biology across the world. At the 1982 International Symposium
on Cancer Markers, Freiburg, German Federal Republic, E. Borek stated that Professor
Gehrkes chromatographic methods are being used successfully by more than half of the
scientists in attendance at these meetings.
His involvement in chromatography began in the early 1960s with investigations on
improved GC methods for fatty acid analysis. Gehrke is widely known for developing
a comprehensive quantitative gas chromatographic method for the analysis of amino
acids in biological samples and ultra-micro methods for life molecules in moon
samples. This method was used and advanced in the analysis of lunar samples when
he was co-investigator with NASA. In the 1970s, his major interests shifted towards
the development of quantitative HPLC methods for the analysis of various important
substances in biological samples, especially the modified nucleosides in tRNA as
biomarkers in cancer research.
XIV
Editors
1987
1990
1993
1997
19541995
In 1989 and 1993, C.W. Gehrke and C. Ponnamperuma of the University of Maryland
were named co-principal investigators on a proposal to address the scientific technical
Editors
XV
XVI
Editors
Editors
XVII
Bayer is internationally recognized with many honors for his research in different
areas:
1978
A.J.P. Martin Award and the Tswett Medal of the USSR Academy of Sciences,
for outstanding contributions to the development of chromatography.
1981
British Petroleum Energy Research Prize and the Max-Bergmann Medal for
Peptide Chemistry for the development of Chirasil-Val and its application to
study racemization of peptides and amino acids.
1985
Philip Morris Research Prize, Men and Environment for the development
of a thermocatalytic, biomimetic process to convert biomass and sludge to a
petroleum like oil.
1986
Tswett Chromatography Award for research in chromatography.
1989
First Class Merit Cross of the Federal Republic of Germany; in 1990, the
International Rheinland-Prize for Environmental Protection for development of
analytical methods relevant for the environment, and the Richard Kuhn Medal
of the German Chemical Society for his research in structure elucidation of
metal proteins and antibiotics.
1993
Fritz Pregl Medal of the Analytical Chemistry Society of Austria.
1994
Fresenius Prize of the German Chemical Society for his contributions to
analytical chemistry and the Grand Merit Cross of the Federal Republic of
Germany.
1997
Maria Sklodowska Curie Medal of the Polish Chemical Society for his contributions to natural compound chemistry, and in 2000, the MTE. Golay Award
for his contributions to capillary HPLC, capillary electrochromatography and
hyphenated techniques.
2000
Halasz Medal of the Hungarian Society.
2001
American Chemical Society National Award in Chromatography.
Bayer has served in many positions in the German Chemical Society, as a member of
the editorial staff in many scientific journals, in government and science commissions,
as a member of the IUPAC analytical chemistry nomenclature commission and member
of committees of scientific congresses.
XVIII
Chapter Outline
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Chapter Outline
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XIX
43
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Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
International symposia on (gas) chromatography by the (British) Chromatographic Society
(19562000) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Symposia on gas chromatography organized by the Instrument Society of America (1957
1963) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
International symposia by the French Society G.A.M.S. (19611969) . . . . . . . . . . .
International symposia on advances in chromatography (19631988) . . . . . . . . . . .
International symposia on high-performance liquid chromatography (HPLC) (19732000) . .
International symposia on capillary (gas) chromatography (19752000) . . . . . . . . . .
Danube symposia on chromatography (19761993) . . . . . . . . . . . . . . . . . . .
COLACRO Latin American congresses on chromatography and related techniques (1986
2000) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Pittsburgh Conference on Analytical Chemistry and Applied Spectroscopy (PITTCON)
(19502000) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Seminal concepts and new discoveries . . . . . . . . . . . . . . . . . . . . . . . .
Relation of seminal concepts and awardees . . . . . . . . . . . . . . . . . . . . . .
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XX
Chapter Outline
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Introduction
Books and Booklets
Journal Papers and Book Chapters
General
Chapter Outline
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Introduction
Nobel Awardees Who Advanced Chromatography
Nobel Awardees Who Used Chromatography
Natureof Paradigm Shifts
Paradigm Shifts in Chromatography:
a.
Carotenoids
b.
Other Natural Products
c.
Chromatography of Amino Acids, Peptides and Proteins
d.
Affinity Chromatography
e.
Chiral Chromatography
f.
Supercritical-Fluid Chromatography
g.
Instruments for Chromatography
Further Developments in Chromatography
a.
Size-Exclusion Chromatography
b.
High-Performance Liquid Chromatography
c.
Detectors in Chromatography
d.
Hyphenated /Coupled /Tandem Techniques in Chromatography
e.
Women Scientists in Chromatography
Summary (see Chapter 1 for Pioneers in Chromatography)
Introduction
Gas Chromatography Instrumentation, Detectors and Columns
Liquid Chromatography Pumps, Detectors and Columns
B.
Introduction
Supports, Stationary and Bonded Phases
a.
Column Development An Abbreviated History Walter G. Jennings
b.
Future Advances in Column Technology Ronald E. Majors
Contributions by Other Chromatographers
XXI
XXII
Chapter Outline
S-12. Chromatography The Bridge to the Environmental, Space and Biological Sciences Charles W. Gehrke (a continuation of Chapter 4)
S-13. Chromatography around the World References for Chapter 6 are
given in Chapter S-13; the printed volume has Japan (Kiyokatsu
Jinno), Russia (Victor G. Berezkin), China (Yukui Zhang and Guowang
Xu), Latin America (Fernando M. Lancas) and The Netherlands (Hans
Poppe, Peter J. Schoenmakers and Robert Tijssen)
S-14. Future Chromatographers of the 21st Century Contributions by 24
Younger Scientists
S-15. Chromatography for the Next Millennium: Continuing Discovery and
Emerging Technology Perspectives by 41 Chromatography Awardees
5.
Chapter Outline
6.
7.
XXIII
Author and Scientist Index for the Supplement see the Internet Chem Web
Preprint Server (http:==www.chemweb.com=preprint=)
Subject Index for the Supplement (Chapters S-7 to S-15)
XXIV
List of Contributors
The Editors are pleased that 125 living Awardees and contributors have responded to
our request for their concise research presentations. Their presentations and institutional
addresses may be found in Chapters 5 and 6. The contributors in Chapter 5 are presented
in alphabetical order. Similarly, biographical information and a thesis abstract for 24,
mostly 1999 Ph.D. investigators, may be found in Chapter S-14. Both are listed in
Author Index (d=deceased). For complete addresses see the contribution in Chapters 5
and 6 of each scientist=contributor.
Daniel W. Armstrong
Iowa State University
Ernst Bayer
Universitat Tubingen
Viktor G. Berezkin, Corresponding author,
Institute of Petrochemical Synthesis
Prominent chromatographers from
Russia:
Vadim A. Davankov
Laboratory at the Institute of
Element-Organic Compounds
Boris V. Ioffe d
State University, Leningrad (St.
Petersburg), Russia
Andrei V. Kiselev d
State University of Moscow
Karl I. Sakodynskii d
Karpov Institute of Physical Chemistry,
Moscow
M.S. Vigdergauz d
Institute of Organic and Physical
Chemistry
Aleksander A. Zhukhovitskii d
All-Union Research Institute for Geological
Prospecting of Petroleum (VNI GNI)
M.I. Yanovskii d
Morton Beroza
USA
Gunter Blobel
Rockefeller University
Jerald S. Bradshaw
Brigham Young University
Phyllis R. Brown
University of Rhode Island
Tom L. Chester
Miami Valley Laboratories, Proctor and
Gamble Corporation
Carel A. Cramers
Lab. of Instrumental Analysis
John V. Dawkins
Loughborough University
Heinz Engelhardt
Universitat Des Saarlandes
Leslie S. Ettre
Yale University
Michael B. Evans
United Kingdom
Per G.M. Flodin
Artimplant AB
List of Contributors
XXV
James S. Fritz
Iowa State University
Hiroyuki Hatano d
Kanagawa Dental College
Charles W. Gehrke
University of Missouri
Nobuo Ikekawa d
Niigata College of Pharmacy
J. Calvin Giddings d
University of Utah
Daido Ishii
Kumamoto Institute of Techology
Robert Grob
Anal. Chem. Consultant
Hiroshi Miyazaki
Niigata College of Pharmacy
Georges Guiochon
University of Tennessee
Tsuneo Okuyama
Tokyo Dental College
Andras Guttman
Novartis Agricultural Discovery Institute
Shigeru Terabe
Himeji Institute of Technology
Steven B. Hawthorne
University of North Dakota
James W. Jorgenson
Univ. of North Carolina
Frederich G. Helfferich
The Pennsylvania State University
Jorgen Hermansson
Chrom. Tech. AB., Stockholm
Barry L. Karger
Northeastern University
Herbert H. Hill
Washington State University
Jerry W. King
National Center for Agricultural Utilization
Research
Stellan Hjerten
Biomedical Center
Csaba Horvath
Yale University
Daido Ishii
Kumamoto Institute of Technology
J. Jack Kirkland
Agilent Technologies
Ernst G. Klesper
University of Technology
John H. Knox
University of Edinburgh
Reed M. Izatt
Brigham Young University
Jaroslav Janik
Academy of Sciences of the Czech Republic
Egil Jellum
Institute of Clinical Biochemistry
Clyde N. Carducci
University of Buenos Aires
Walter G. Jennings
J&W Scientific Company
Remolo Ciola
Refinery Research Center
Armando M. Moreno
Universidad Nacional Autonoma de Mexico
Shoji Hara
Tokyo College of Pharmacy
Joaquim Lubkowitz
Separation Systems, Inc.
XXVI
List of Contributors
Milton L. Lee
Brigham Young University
Jacques Rijks
The Netherlands
Hendrik Lingeman
Vrije Universiteit
Charles H. Lochmuller
Duke University
Frederick Sanger
Cambridge University
James E. Lovelock
Combe Mill, UK
Karel Macek
Czech Academy of Sciences
Gerhard Schomburg
Max-Planck Institut
Ronald E. Majors
Agilent Technologies
Robert E. Sievers
University of Colorado at Boulder
Karin Markides
Uppsala University
Colin F. Simpson
United Kingdom
Jan B. Sjovall
Karolinska Institutet
Michel Martin
Ecole Superieure de Physique et de Chimie
Industrielles
Hamish Small
Dow Chemical Co. (Retired)
Daniel E. Martire
Georgetown University
Robert B. Merrifield
The Rockefeller University
Hiroshi Miyazaki
Kawasaki, Japan
E. David Morgan
Keele University
Milos V. Novotny
Indiana University
Janusz Pawliszyn
University of Waterloo
Roger M. Smith
Loughborough University
Lloyd R. Snyder
LC Resources Inc.
Jun Suzuki
Soda Aromatic Co., Ltd.
Shigeru Terabe
Himeji Institute of Technology
Toyohide Takeuchi
Gifu University
Robert Tijssen, Corresponding author,
Universiteit van Amsterdam
Other co-authors from the Netherlands:
William H. Pirkle
University of Illinois
Hans Poppe
University of Amsterdam
Colin F. Poole
Wayne State University
Peter J. Schoenmakers
University of Amsterdam
Jerker O. Porath
Uppsala University
Klaus K. Unger
Johannes Gutenberg-Universitat
Michel Prost
Spiral Corp., Dijon, France
Irving W. Wainer
Georgetown University Medical Center
List of Contributors
XXVII
Harold F. Walton
Retired, USA
Robert L. Wixom
University of Missouri-Columbia
Phillip C. Wankat
Purdue University
Edward S. Yeung
Iowa State University of Science and
Technology
Christopher J. Welch
Merck & Co., Inc.
Ian D. Wilson
Drugs Kinetics Group - Zeneca
XXVIII
Contents
Preface . . . . .
Dedication . . . .
Acknowledgements
Editors . . . . .
Chapter Outline .
List of Contributors
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V
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IX
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XI
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687
691
695
705
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1
39
55
69
99
601
Contents
S-13. Chromatography Around the World References for Chapter 6: in Part A Japan (Kiyokatsu
Jinno), Russia (Victor G. Berezkin), China (Yukui Zhang and Guowang Xu), Latin America
(Fernando M. Lancas) and The Netherlands (Hans Poppe, Peter J. Schoenmakers and Robert
Tijssen)
S-14. Future Chromatographers of the 21st Century Contributions by 24 Younger Scientists
S-15. Chromatography for the Next Millennium: Continuing Discovery and Emerging Technology
Perspectives by 41 Chromatography Awardees
Appendices 17 Robert L. Wixom and Charles W. Gehrke
Author and Scientist Index for the Supplement
Subject Index for the Supplement
XXIX
CHAPTER 1
CONTENTS
A.
B.
C.
D.
E.
F.
G.
H.
I.
J.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Possible approaches . . . . . . . . . . . . . . . . . . . . . . .
Nature of this chapter . . . . . . . . . . . . . . . . . . . . . . .
The initiation in Switzerland and Russia . . . . . . . . . . . . . . . . . . .
Adsorption chromatography (19001950s) . . . . . . . . . . . . . . . . .
Partition chromatography (1940s1950s) . . . . . . . . . . . . . . . . . .
C.1.
Liquidliquid partition chromatography (LLC) . . . . . . . . . . . .
C.2.
Gasliquid partition chromatography (GLC) . . . . . . . . . . . . .
Paper- and thin-layer chromatography (two forms of planar chromatography) . .
D.1.
Paper chromatography (PC) . . . . . . . . . . . . . . . . . . . .
D.2.
Thin-layer chromatography (TLC) . . . . . . . . . . . . . . . . .
Ion-exchange chromatography (IEC) (1930s1960s) . . . . . . . . . . . . .
Chromatography of petroleum . . . . . . . . . . . . . . . . . . . . . . .
The literature of chromatography . . . . . . . . . . . . . . . . . . . . . .
Integration of seminal concepts with chromatography leaders . . . . . . . . .
From the inventors to the builders of chromatography . . . . . . . . . . . . .
I.1.
Other early chromatography leaders . . . . . . . . . . . . . . . .
What is required to be one of the award winners? . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References for introduction . . . . . . . . . . . . . . . . . . . .
References for Mikhail S. Tswett . . . . . . . . . . . . . . . . . .
References for predecessors of Mikhail S. Tswett . . . . . . . . . .
References on Leroy S. Palmer . . . . . . . . . . . . . . . . . . .
References on other early followers of M.S. Tswett . . . . . . . . . .
References on partition chromatography (LLC) . . . . . . . . . . .
References for gasliquid chromatography (GLC) . . . . . . . . . .
References on paper- and thin-layer chromatography (TLC) . . . . . .
References on ion-exchange chromatography (mainly early investigators)
References for petroleum chromatography . . . . . . . . . . . . . .
References on the literature of chromatography . . . . . . . . . . .
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11
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12
15
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21
23
26
27
27
29
30
32
32
32
33
33
33
34
34
35
35
36
37
Chapter 1
References on From the inventors to the builders of chromatography . . . . . .
References for summary . . . . . . . . . . . . . . . . . . . . . . . . . .
37
38
INTRODUCTION
This chapter presents chromatography as a branch of science that bridges a century
of science and discovery. Chromatography represents the premier analytical method of
the 20th century for the advancement of a variety of disciplines of science. The evolution
of chromatography is depicted in the frontispiece as a bridge and shows some of the
inventors the builders who advanced chromatography and who constructed the
foundation of chromatography for later sciences and technology.
To continue with J. Calvin Giddings thoughts [1], the cloud of dust and gases
gathered and coalesced to form our planet Earth. Metal ions separated forming crystals
and ores iron in brassy-yellow pyrite (FeS2 ) or hematite ore (Fe2 O3 ), silicon in
clear, hexagonal cross-section of crystallized quartz (SiO2 ), multi-colored wavelite with
a radial fibrous structure (Al3 (OH)3 (PO4 )2 5 H2 O, red cinnabar (HgS) and lead in the
shiny, gray, cubes of galena (PbS). The suns energy, captured in photosynthesis led to
the separation of a carbon-prevalent biosphere and an oxygen-rich atmosphere (21%);
nitrogen was concentrated in the atmosphere (70%), but is also abundant in the proteins
and nucleic acids of plant-, microbial-, and animal cells. Much more recently, Homo
sapiens has learned to distinguish protein- vs. carbohydrate-rich foods, isolated natural
products for medical use (e.g., quinine for malaria, etc.), and extracted natural dyes from
concentrated plant sources (blue indigo from Indigofera genus; yellow quercitin from
the black oak, Quercus velutina; red carmine from the female cochineal insect, etc.).
After the Big Bang and evolution, mankind has traveled in time through the late
stages:
Agricultural
Revolution
!
Industrial
Revolution
(1700s1800s)
!
Scientific=Technology
Revolution
(1800s1900s)
!
Information
Explosion (late
1900s2000s)
Present-day culture and science rests upon the scientific traditions and cultures of
Egypt, Mesopotamia, Greece, Rome, Islam, China and Western Europe; however, we
have spiraled far beyond these roots [2]. Within this context and in the past century,
chromatography and separation science have incubated and grown with a flourish.
But how do we scientists place a handle a meaningful organizational structure on
chromatography a body of knowledge that is now too large for many scientists to
fully grasp?
Possible approaches
As stated in the preface, the goal of this book is to recognize the pioneers and
the builders of chromatography, their discoveries and their personal recollections.
Interwoven in their contributions and in other chapters will be seminal concepts, and the
developmental events during the past century. By undertaking the above goal, we are
also embarking on writing a history of this branch of science. Several approaches may
be found for organizing a presentation in the field of history of science:
Portrayal of the sequence of scientific discoveries and their interrelationships.
(Example: M. Florkin and E.H. Stotz (Eds.), Comprehensive Biochemistry, Elsevier
Publishing Co., Vols. 134, 19721986.)
Scientific biographies of the leading members of the branch of science under
review. (Examples: L.S. Ettre and A. Zlatkis (Eds.), 75 Years of Chromatography
A Historical Dialogue, Elsevier, 1979; or M. Florkin and E.H. Stotz (Eds.),
Comprehensive Biochemistry Sections on Personal Recollections, Elsevier, Vols.
3540, 19831997.)
Flow of major concepts and hypotheses in a branch of science, the evidence for
the same, and sometimes or even frequently, their modification or even disavowal.
(Example: T.S. Kuhn, The Structure of Scientific Revolutions, University of Chicago
Press, Chicago, IL, 1962, 1970 and 1996.)
Schools of scientific discipline, usually led by a distinguished scientist guiding
his=her colleagues, postdoctoral associates and graduate students.
The above examples suggest the merits of each approach. Indeed some treatises
include more than one approach. The Frontispiece Bridge emphasizes the crucial
role of the earlier scientists=chromatographers to recognize the distinctive merits of
chromatography, to build the scientific structure of chromatography and to enhance the
connection the bridge to other scientific disciplines. Last, but not least, these
scientists inspired others to continue to construct bridges. Since chromatography is a
relatively young branch of science, this book emphasizes the scientific biographies of
international and national awardees and contributors in chromatography and separation
science. Some authors of other chromatography books have a brief historical description
for their specific chromatography area that is being described. V.G. Berzekin has written
to us that this book is also the Bridge from the XIX to the XXI Century. Thus, let us
begin.
Chapter 1
(A) are presented at the end of each subsection in italics along with the chapter number
and subsection, i.e., C-4B refers to Chapter 4-B, S-7D refers to a chapter in the
Supplement (http:==www.chembweb.com=preprint) and A-5G to Appendix 5-G. Each
main chromatographer is followed by a See Chapter 5B plus a letter code that defines
their area of chromatography as described in 5B.
a high government official in the Crimea. Tswett had high hopes for an early academic
appointment, but soon found that without a Russian advanced university degree this
was not possible. Therefore, he moved to St. Petersburg and while having a temporary
position in a laboratory, he carried out scientific research so that he could submit a
thesis and receive an academic degree. This was accomplished in the fall of 1901 at
the University of Kazan where he duly received a Russian Magisters degree. Soon
afterward he moved to Warsaw, in Russian-occupied Poland, and in the next 14 years,
he was active there, first at the University, then in 1907 at the Veterinary Institute, and
finally, from 1908 on at the Polytechnic Institute, although always in relatively minor
positions.
It should be noted that the controversy concerning the non-acceptance of his Swiss
academic degree and then, for the next 15 years, the impossibility for him to obtain a
senior university appointment made Tswett very bitter. He considered this discrimination
because of his foreign background; as a conclusion, he became a loner and reacted very
harshly even to the mildest criticism. His strong polemic nature became a serious
handicap in his professional life and was justly criticized when, in 1918, he was
nominated for the Chemistry Nobel Prize [2].
Tswetts thesis work for the Magisters degree dealt with the physico-chemical
structure of plant chlorophyll [3] and represented the start of his research which
eventually led to the development of chromatography. It is very intuitive to follow
the successive steps of Tswetts investigations because these demonstrate his logical
thinking.
Tswetts aim was to isolate chlorophyll as close as possible to its natural state.
During this work he found that while polar solvents (e.g., ethanol) can be used to extract
chlorophyll from leaves, non-polar solvents (e.g., petroleum ether) are unable to do this.
However, after chlorophyll was isolated from plants, it could be easily dissolved in these
solvents. Tswett correctly concluded that this behavior is not due to simple solubility
problems or to a chemical change of chlorophyll in ethanol to a soluble form, but
is rather due to the interference of the molecular forces of the tissue, that is to say,
to adsorption, and to the relative strength of the solvents compared to the adsorption
forces of the plant tissues.
The next step in his work was the study of the interaction of plant pigments with over
100 different powdered organic and inorganic materials which may act as adsorbents,
aiming to establish the general adsorption behavior of these substances. Eventually,
these investigations led to a method permitting the separation of chlorophylls and some
carotenoids by stepwise selective adsorption and extraction. The results of these studies
were summarized by Tswett in a major lecture presented on March 21, 1903, in Warsaw,
which was published two years later in a local scientific periodical [4].
From this method it was not far to realize that separation by adsorptiondesorption
can also be carried out in a continuous way [5,6]. From 1903 to 1905, Tswett
developed this method and first referred to its existence (calling it only a new,
reliable method, without giving any details) in two polemic publications criticizing
the results of Hans Molisch (18561937), then Professor at the University of Prague,
on the pigments of brown algae. After being hard-pressed to present actual data and
disclose the way his investigations were carried out, Tswett finally submitted in June
Chapter 1
and July 1906 his fundamental two papers to the Berichte der deutschen botanischen
Gesellschaft, the journal of the German Botanical Society, published in the Fall.
The first [7] dealt with his investigations of plant chlorophylls while the second [8]
discussed in detail the new separation method developed by him, which he for the first
time called chromatography. These two papers contain all the important aspects of
chromatography, including proper selection of the adsorbent, proper utilization of the
solvents and the possibility of using columns with different diameters (from 23 mm up
to 1020 mm) and lengths.
These papers created considerable controversy and in the following years Tswett
carried out a lot of polemics with scientists in different countries who have worked in
the same field [9]. (For a detailed discussion of this controversy, see the papers by T.
Robinson [10] and L.S. Ettre [11,12].) Meanwhile Tswett summarized the knowledge
he gathered on plant pigments, particularly chlorophylls, in a book published in 1910 in
Russian [13]. A separate section of his book dealt with adsorption and chromatography
and in it, Tswett further expanded the description of the technique and its use, also
emphasizing the possibility of preparative separations on columns having a diameter of
30 mm and packing length of 80 mm.
Between 1906 and 1911, Tswett further expanded his research on plant pigments,
including the carotenoids. It is practically unknown that this name for the polyene
pigments used universally since the 1930s was first proposed by him, in a paper
published in 1911 [14]. However, from 1912 on, he published almost nothing; his health
started to deteriorate and then came World War I with the interruption of normal life.
Warsaw was occupied by German troops in the summer of 1915 and the Polytechnic
Institute was evacuated to Nizhnii Novgorod, but there was no possibility to carry out
any research there. Finally, in 1917, Tswett was appointed a full Professor of Botany
and the Director of the Botanical Gardens at the University of Yureev (today: Tartu, in
Estonia). He moved there in September 1917, but within a few months, German troops
also occupied the Baltic area. A few months later, the Russian professors moved to
Voronezh, in Russia, to start a new State University. Tswett was already very ill at that
time, and he died in Voronezh on June 26, 1919, only 47 years old. Thus, the life of one
of the most original thinkers of this period ended prematurely.
During his lifetime, Tswetts work on chromatography was not appreciated and was
belittled by his peers. However, within a decade after his death, its importance was
finally recognized and applied in almost every branch of science. Today, 80 years after
his death, we consider chromatography as one of the most important inventions of the
20th century.
By Leslie S. Ettre
See Chapter 5B, a, b
Many other references on M.S. Tswett are available [15]. Though Tswett is generally
regarded as the father of chromatography, several other scientists have been identified
as making brief entries in the 1800s into the general area of chromatography. The
names and contributions of the predecessors of M.S. Tswett follow with appropriate
reference(s):
Friedlieb F. Runge (17941867) was a German chemist who studied the spread of
coal tar dyes on paper and made self-grown pictures for the Friends of Beauty;
this area might be considered a precursor of the later (1940s) paper chromatography
[1].
Friedrich Goppelsroeder (18371919) was a student of Friedrich Schoenbeim
(17991867) and improved the latters approach for separation of dyes on hanging strips of unsized paper by capillary migration. Though he published a 1906
monograph, and again in 1909, his work was ignored and then lost until the 1940s
[2].
Chapter 1
chlorophylls and xanthophylls. His 1908 thesis was published in a specialized journal
and was soon forgotten. Soon, thereafter, he went to Africa and left the area of
chromatography [1].
Theodor Lippmaa (18921944), an Estonian scientist, received his Ph.D. in botany
in 1926 from Tartu University and published six research papers in 1926 on
thuyorhodine, later renamed rhodoxanthin, a plant pigment. For two of these
papers, he followed Tswetts chromatographic procedures despite the criticism of
Tswetts work in the 1920s. His subsequent research was unrelated botanical studies
in Africa and Europe that were a precursor to present-day environmental protection
[2].
Charles Dhere (18761955) was the first scientist in Europe to recognize the
overall importance of chromatography [3]. Dhere studied medicine in Paris (M.D.
in 1898), but never practiced as a physician. After several years at the Sorbonne,
he joined the University of Fribourg, Switzerland in 1900 as an Associate Professor
of physiology, biological chemistry and microbiology (such joint appointments were
common in this period), and then in 1908 as a full Professor until his 1938
retirement. His service at Fribourg included two periods as Dean of the Faculty of
Science (19161917 and 19331934). His primary interest was the investigation of
biological substances, mainly by ultraviolet and fluorescence spectroscopy. One of
Dheres students, Wladyslaw Franciszek de Rogowski (18861945) from Poland,
received his doctorate in 1912, examined the chromatography on CaCO3 columns
of chlorophylls and their UV absorption and confirmed the earlier findings of M.S.
Tswett. Another Dhere student, Guglielmo Vegezzi (18901955) from Switzerland,
started his thesis work in 1913, and after military service, completed his doctoral
work in 1916. He extended Rogowskis methods with minor modifications to study
invertebrate pigments, such as those from bile and liver of escargot and the eggs of
the spider crab. His research with Dhere is summarized in six papers (19161917).
Then he joined the Swiss Federal Administration of Alcohol. Dhere prepared the first
thorough summary of M.S. Tswetts life and scientific work a 50 page paper in
the journal, Candollea. Apparently, Dhere, Rogowski and Vegezzi did not undertake
further investigations in chromatography after the period described.
Thus to evaluate, L.S. Palmer conducted chromatography research from 1910 to
1918, wrote nine papers on carotenoids, and most importantly, wrote a rather thorough
1922 chromatography book [6]. Palmer cited Goppelsroeders research, but not that of
Kranzlin, Dhere, Rogowski and Vegezzi in his 16 pages of references in 2 columns in
his book. (Scientific communication was more limited at this period in the absence of
airplanes for travel to research conferences, radio, TV, the Web and the Internet.) To
summarize, L.S. Palmer in the United States and Charles Dhere in Europe were the
middle men, the conservers of Tswetts insights and the bridge to the research of Edgar
Lederer and Richard Kuhn some 20 years later.
For adsorption chromatography, the next major event came in the laboratory of
Richard Kuhn who had a long, distinguished record of research. One of his research
assistants, Edgar Lederer, had read the above book by Leroy S. Palmer (about 1930)
and soon thereafter found the book and papers by Michael Tswett. The other part of
this story, described under R. Kuhn, is that Kuhn, Winterstein and Lederer published
10
Chapter 1
11
natural products by chromatography. Though he retired in 1959, his lucid books were
very effective in the subsequent development and spread of chromatography [7,8].
See Chapter 5B, b
Most scientists remember A.W.K. Tiselius and associate him with free-flow electrophoresis, but his fertile mind led also to significant developments in chromatography
in the 1940s and 1950s as described by one of his students, Per Flodin in S-9A.
Aloysius I.M. Keulemans (19081977) was another prominent chromatographer.
Most of his career was at the University of Technology, Eindhoven, The Netherlands,
where he conducted research on gas chromatography and developed a significant
program to guide the next generation of chromatographers; this included over 200
research papers plus 150 M.S. and 20 Ph.D. degrees for students from his institute.
The 1957 and 1959 editions of his textbook on gas chromatography described reports
from chromatographers (J.J. Van Deemter, F.J. Zuiderweg, A. Klinkenberg and H. Boer
at Shell Development, Amsterdam, The Netherlands) and E. Glueckauf and N.H. Ray
(England) and other early investigators [9,10]. The Keulemans books were translated to
a number of different languages and served as a major source of information to practical
chromatographers (cited in A-4E).
See Chapter 5B, b
Adsorption chromatography may be extended to become a preparative liquid chromatography [11,12]. This introduction for adsorption chromatography, whether liquid or
gas chromatography, may be supplemented by other sources [13,14]. At this point, an
overall look on the developing patterns for the varieties of chromatography is presented
(Fig. 1.1).
Note: Additional comments and references may be found later in Chapter S-9B (R.
Kuhn, P. Karrer) and A-4A, A-4E and A-5Ga.
12
Chapter 1
Fig. 1.1. Outline of the historical flow of scientific thought in chromatography (1900-1960s). This figure
will serve as an outline for subsequent sections. Partition chromatography and its sequential development
occurred over the 1940s to 1960s period. Note: Additional comments and references may be found in later
Chapters S-9A, S-9B (R. Kuhn, R. Karrer), A-4A, A-4E and A-5G.
13
and others). Since the development of the GC method, the needed instruments and
detectors required major considerable capital investment, blocks of time, and organized
effort, it is not surprising that scientists with the petroleum companies having major
analytical problems moved rapidly ahead. The observation that many components of
petroleum are volatile at room temperatures (C2 C5 ), mild temperatures (C6 C10 ), or
the elevated temperatures usually used in GC (up to 300C) had a key role in the above
advance. Subsequently, elevated temperatures have been regularly used and may be at a
fixed temperature, or a programmed temperature increase during the GC.
GLC has advanced rapidly on many, more or less, simultaneous developments
with respect to the support and stationary phase, column selection an elongated
tube, flow controllers, carrier gas sample inlet devices, column ovens, power supplies,
detection systems, and troubleshooting. The original qualitative method developed
in two directions: a rigorous quantitative method and a semi-preparative approach.
Initially, columns were packed with the desired stationary phase, but then gave way,
under M.J.E. Golays invention and investigations in the late 1950s and 1960s, to open
tubular columns [36]; the latter may be capillary columns (usually less than 0.35 mm)
or larger diameter (up to 2.5 mm). Initial columns were made from stainless steel tubing,
which was replaced by glass capillaries when techniques were developed to prepare a
stable internal coating. Later glass capillaries were replaced by fused-silica columns.
These columns are usually used as a coil and strengthened by a polyimide outside
coating. A thin, uniform film (0.25 m) of the desired stationary phase is frequently
coated on the inside wall of the capillary column.
Carrier gases for GLC must be pure and inert; they have usually included hydrogen,
helium, or most frequently nitrogen. Since the sample must be delivered to the head of
the GC column with a minimum initial bandwidth, sample inlets, also called injectors
or injection ports, may be a vaporization injector (high temperatures to vaporize the
sample rapidly), or on-column injectors (deliver sample directly into the column).
Special microsyringes are used to introduce the sample into the injector. The carrier
gases (H2 , He, N2 ) undergo a straight line increase in viscosity with the temperature rise
(0350C), but a pressure rise (up to 5 atm) had a negligible influence on viscosity [7].
Multiple detectors are now available and are discussed in Chapter S-10. Another
wave of research in the 1960s was to modify the non-volatile compounds by preparing
volatile derivatives, such as: methyl esters for organic acids, reaction with trialkylsilyl
(R3 Si) groups to form TMS ethers, use of N-methyl-trifluoroacetamide for steroids; anhydrides (acetic-, trifluoroacetic- or pentafluoropropionic anhydride, etc.) employed for
alcohols and phenols; use of acetone to form ketals, etc. The reagent, bis trimethylsilyl
trifluoroacetamide (BSFTA, a C.W. Gehrke patent), has been widely used for amino
acids, nucleosides, proton donors, etc. The list of derivatives is much longer; their
selection requires insight and knowledge of the substrate, the derivatizing reagent, the
column and the instruments for detection.
The more detailed earlier history of GC has been described [5,6,8]. Though gas
chromatography is usually for an analytical objective, several modifications have
led to making it a preparative GC [9]. The lively interaction between ideas, gas
chromatographers, and international symposia (19631988) has been carefully reviewed
[10,11]. Many of the GC pioneers (about 21 scientists=awardees) of the 1950s have
14
Chapter 1
departed from us; their names and some references to describe their research and lives
may be found in Appendix 2 and=or the Author=Scientist Index.
Note: To be brief, the potential realm for GC in the 1960s has undergone a marked
outreach by many new investigators. Many made contributions to the L.S. Ettre and
A. Zlatkis book [5]; their research, contributions and short biographies are described
briefly in Tables 2 to 4 of Section G of this chapter and later in Chapters 4, 5, S-9
and S-11. Readers will find valuable additional information and the subsequent flow
of historical thought in E. Bayers contribution [8]. Eighty-four gas chromatographers,
who made notable contributions for this subarea, are listed in the Author=Scientist Index
with the code letter d. (Our code letters for seminal concepts and new discoveries
by chromatographers are described fully at the end of this chapter, Table 1.2.) Further
information on gasliquid chromatography may be found in the Appendices [12] and
recent reviews [1317].
Others have stated that chemistry has permeated throughout modern human life.
The use of chromatography is so much around us and yet is hidden from most
peoples attention; year after year, chemical analyses are performed to protect our
food, water, air, medicines, etc. The lead organization in this area since the 1900s
publishes the book, Official Methods of Analysis of AOAC International (formerly
the Association of Official Analytical Chemists), edited by William Horwitz [18]. Their
15th edition, 1990, lists 229 refereed chromatographic methods, of which 130 are
GC, 82 are LC, and 17 are general. These methods are associated with classes of
compounds: organic acids, alcohols, aldehydes and ketones; monosaccharides; lipids,
fatty acids and their derivatives; sterols, steroids and pseudohormones; antibiotics and
other drugs, vitamins and vitamin antagonists, flavoring agents, mold metabolites,
pesticides, PCBs, nitrosoamines, methyl mercury, dyes, TNT and other nitro derivatives,
plus other miscellaneous compounds. Of course, chromatographic procedures have been
developed and studied collaboratively to measure many other substances. The 17th
edition of AOAC Methods (2000) has 2700 chemical and microbiological methods,
85 new methods, and 110 newly modified methods, and is now available [18]. The
American Society of Testing Materials (ASTM) has 15 sections and 73 reference
volumes for the 1999 Annual Book of ASTM Standards (coal, pipes, wood, air
pollution, etc.), in which Vol. 14.02 has 18 chromatographic methods, covering GC,
LC, SFC, ion chromatography, detectors and sampling [19]. Another important source
of GC abstracts was the Gas Chromatography Literature, Abstracts and Index
[20], published by the Preston Technical Abstracts Co. These examples illustrate the
penetration of chromatography into the food-, beverage-, pharmaceutical- and other
consumer industries.
Modern chromatography may not be recognized by the lay citizen, but its pervasive nature surrounds him=her and society.
Note: To supplement these notes on early years, see C-1F, C-2, C-4, C-5, C-6A, C-6E,
C-6E, S-11 and A-4E.
15
16
Chapter 1
but with the then lack of available spreading equipment, achieving a uniform layer
of sorbent was difficult. Egon Stahl made improvements in sorbents and spreading
apparatus (1956 and 1958 papers). By hindsight, the turning point, or the breakthrough,
seems to be the subsequent books on TLC by E. Stahl (1962, 1967) and J.G. Kirchner
(1967, 1978) [79].
TLC is also partition (or sometimes adsorption) chromatography using plates to
hold the sorbent; plates are usually 20 20 cm glass sheets (or 5 20, 10 20 and
20 40 cm), but may be also plastic sheets or aluminum foil. Sorbents for partition
chromatography include silica gel, cellulose, polyamide powders, Florisil, kieselguhr,
etc. The silica gel may be substituted to be a less polar form, i.e., silica > amino silica
> cyano silica > octadecyl (C18 ) silica. The particle size of TLC sorbents is between
10 m and 50 m. Alumina (Al2 O3 ) as a sorbent provides the conditions of adsorption
chromatography. Sometimes a binding agent (usually plaster of Paris, calcium sulfate
monohydrate) is needed to hold the silica gel to the plate. Pulverized ion-exchange
resins or Sephadex may be used to mimic IEC or SEC. The performance of a TLC
sorbent depends on the specific surface area, pore volume, mean pore diameter and pore
size distribution, plus particle distribution, and size. The test sample is applied near
the bottom edge of the plate, which is then dried and placed into a closed rectangular
tank. Many solvent systems have been tested, but the choice depends on the nature
of the mixture to be separated and the character of the sorbent. Other variations of
TLC include forced-flow planar chromatography (FFPC), overpressured-layer planar
chromatography (OLPC) and centrifugal force planar chromatography (CPC) [10].
Thus, thin-layer chromatography has become a widely used separation method due
to its rapidity of separation, simplicity in its use, low volume of solvent needed and
rather low cost, plus a variety of now commercially available prepared plates and apparatus. Like paper chromatography, TLC may be one-dimensional or two-dimensional.
One-dimensional TLC allows application of multiple spots of unknown solutes to be
tested for purity. Earlier TLC was mainly a qualitative identification and separation tool
in the 1950s1960s (usually a 10200 g sample size and a 250 m thickness layer).
With improved commercially available sorbents came uniform particle size and a variety
of sorbents compatible with detection instruments; then TLC became more quantitative
(usually 5500 ng of sample and 150 m thickness). When smaller particle size (6 m)
and a narrow particle range are utilized, the conditions for high performance TLC
(HPTLC) are met.
When the layer thickness is increased to 2502000 m, TLC becomes a preparative
tool (5500 mg of sample in 501000 l of solution). TLC has many other variations,
such as reversed phase TLC and modified silicas (added magnesium acetate for
phospholipids, added potassium oxalate for polyphosphoinositides, added ammonium
sulfate for heat charring and detection of solutes, or added silver nitrate to detect
compounds with C C, double bonds, etc.
Note: The number of articles in the research journals proceeded rapidly in the 1960s
and 1970s, leading to additional books [7], and eight more books in the 1990s decade
[8]. Recent excellent reviews are more detailed than appropriate for this introduction
[912]. Thus TLC as a qualitative research tool, has had considerable amplification in
uses, and has made inroads to serve also as a quantitative procedure. The preceding
17
changes in the direction of chromatographic science (Fig. 1.1) in the past century are
major milestones that have led to many other new discoveries (see Table 1.3 of this
chapter and S-9).
18
Chapter 1
for the preparative scale [24]. A major issue of the J. Am. Chem. Soc. published 15
papers on wartime IEC research in 1947 [6a]:
Oak Ridge National Laboratory (ORNL) (papers by E.R. Tompkins, J.-X. Khym, and
W.E. Cohn) Ion exchange as separations method.
ORNL (papers by G.E. Boyd) The exchange adsorption of ions by organic zeolites.
Iowa State College (papers by F.H. Spedding and co-workers Separation of rare
earths by IEC.
Miscellaneous papers by J.A. Ayers, J.A. Marinsky, W.C. Bauman, R. Kunin and R.J.
Myers.
Other early reports on IEC during World War II (F.H. Spedding and E.R. Tompkins;
T.R.E. Kressman and J.A. Kitchener; R. Kunin and R.J. Myers; E. Glueckauf and
associates; and S.M. Partridge) may be found in the 1949 conference report of the
Faraday Society, UK [6b], a collection of early IEC papers [7], and followed by other
books in the 1950s and 1960s [8].
The 19401941 advent of World War II led many governments and scientists to
develop new weapons and defenses: explosives, land mines, war gases, particularly the
nerve gases, radar, and last, but not least, the atomic bombs with their escalation of
destruction, along with advances to deliver these weapons. The then secret Manhattan
Project undertook major research to develop the atomic bomb and to identify both
the metallic ions and the radiations emitted during the stepwise radioactive decay. The
available, synthetic ion-exchangers the substituted polystyrene resins (the Dowex
series) and the substituted acrylic resins (the Amberlite series) were utilized for
separation of these nuclides. The key investigators of IEC at the Oak Ridge National
Laboratory, Oak Ridge, Tennessee, USA were Waldo E. Cohn, Kurt A. Kraus and
Edward H. Tompkins [9].
W.E. Cohn (19101999) earned his B.Sc., M.Sc. and Ph.D. degrees (1938, with
the senior biochemist, David M. Greenberg) at the University of California, taught at
Harvard Medical School (19391942), and then became a group leader of the Plutonium
Project, University of Chicago and Manhattan Project, Oak Ridge National Laboratory
(19421947). During these years, he worked on the ion-exchange separation of rare
earth elements and fission products [10]. In post-World War II years, he did research
to develop ion-exchange methods for the isolation (and analysis) of the purine and
pyrimidine bases and the mononucleotides of the nucleic acids (DNA and RNA) (about
40 research papers and 5 reviews in the 1948 to 1967 period (from his resume by
ORNL)) [cf. 1113]. He was an early scientist in the 1950s to organize and promote the
distribution of radioactive isotopes for use in medical research and treatment. He was
the initial editor for 8 volumes of the annual series, Progress in Nucleic Acid Research
(19631968), chair of the Oak Ridge Town Advisory Council (19531955), and an
amateur cellist; he retired in 1975. Not surprisingly, Cohn was the third recipient of the
National Chromatography Award of the American Chemical Society (1963).
See Chapter 5B, c and A-2
To again step back in time, Kurt A. Kraus (19141995) was born in Windsheim,
Germany, came to the United States in 1935 and was naturalized as a citizen in 1941. He
19
received his B.Sc. at Harvard University (1938) and his Ph.D. degree at Johns Hopkins
University (1941). After two years at Tulane University, he joined the Metallurgical
Laboratory, Chicago, became a group leader at Oak Ridge National Laboratory (1945
1948), Tennessee [9], and then their Director of the Water Research Program of ORNL
(19621971). His early research focused on inorganic chemistry and ion-exchange of
alkali metal ions [1416]. Later he conducted research on hydrous oxides, properties
of solutions, adsorbent studies, inorganic polymers, desalination, hyperfiltration studies,
and pollution control, that were described in many papers in the open literature, contract
reports and 9 patents (19651971). Kraus was the 1966 recipient of the National
Chromatography Award of the American Chemical Society.
See Chapter 5B, c and A-2
Information on Edward R. Tompkins (1998) an ORNL scientist is difficult
to find. Four of his significant papers are cited [9,1719]. Other investigators and related
IEC findings are described in the review by L.S. Ettre [9].
See Chapter 5B, c
Frank H. Spedding (19021984) was the chemist who made distinct early contributions for IEC. He was born in Ontario, Canada, earned his B.Sc. (1925) and M.Sc.
(1926) at the University of Michigan and his Ph.D. in chemistry at the University of
California (1929). After several short appointments elsewhere, he joined Iowa State
College (1937) (now Iowa State University), serving there as Professor (19411973),
Director of their Atomic Project (part of the Manhattan Project) (19421948), and
then became Director of the Ames Laboratory, United States Department. of Energy
(19471968). He was a member of the National Academy of Sciences and has several
awards other than in chromatography.
His Ames group, as a part of the Metallurgical Project within the overall Manhattan
Project (World War II), focused on the pilot plant production of high grade uranium;
1000 tons of pure uranium metal were isolated at the Ames pilot plant with a dozen
large IEC columns (40 inch in diameter and 10 ft. in height), 12 to 18 day runs and
collecting 45 liters per 12 hours [2023]. This role of IEC in World War II has been
thoroughly reviewed by L.S. Ettre [9]. Speddings et al. research examined the isolation
and properties of the rare earth elements (particularly the lanthanide series by IEC),
atomic and molecular spectra, metallurgy of uranium, thorium and other rare metals,
plutonium chemistry, atomic energy chemistry, and absorption spectra of solids at low
temperatures. His research papers may be identified in several books [2022]. The
references for the early investigation and properties of the rare earths are available
[9,2126a].
See Chapter 5B, c and A-2
Another investigator, Olof Samuelson (19142000) conducted research on ionexchange chromatography during the above early time period. He published about 27
20
Chapter 1
research papers in the 1939 to 1960 period in Scandinavian journals and completed
his thesis in 1944. Subsequently he has served as Professor of Engineering Chemistry,
Chalmers University of Technology, Goteborg, Sweden. His early research focused on
the IEC separation of organic acids, sugars, aldehydes and ketones as their bisulfite
addition products, Fe3C and AI3C from other metal ions. His two books (1st ed. in
1953, 2nd ed. in 1963) have a thorough discussion on the concepts and applications
of IEC and the cited references prior to 1963 [26b]. His post-1963 research (about
240 papers) relied on anion-exchange chromatography to examine uronic acids, aldonic
acids, aldouronic acids and other organic acids, bleaching of kraft pulp without chlorine
and cellulose degradation in bleaching by oxygen or nitrogen dioxide.
See Chapter 5B, c
Eugen Glueckauf (19061981) also made contributions to IEC. He was born in
Germany with parents from Jewish origin, and owners of a textile manufacturing
business. His studies began at the University of Berlin, but soon changed to the
Technische Hochschule at Charlottenburg (Dipl. Ing., 1930), and went on then to
study surface adsorption and surface reactions (Dr. Ing., 1932). With the political
developments then in Germany, he migrated to England in 1933 and accepted an
assistant position with F.A. Paneth (F.R.S.) at the Royal College of Science (Imperial
College), South Kensington. His research focused on helium analysis to determine
the age of meteorites; since neon interfered with the helium analysis, he developed
a 12-stage adsorptiondesorption cascade with charcoal cooled in liquid nitrogen as
adsorbent that separated He and Ne. For several years, he examined the production of
He after bombardment of boron with neutrons, and beryllium with -rays. In 1937,
he was appointed Professor of Chemistry at Durham College (later the University of
Durham). With the outbreak of World War II, he was interned for 5 months in 1940, but
released by the efforts of F.A. Paneth. In 1944, he was invited to join the extramural
work of the Department on Tube Alloys (the code name for atomic energy research).
Early research dealt with separation of LiC isotopes by IEC and Ne isotopes by low
temperature (196C) adsorption columns [27]. In 1947, he transferred to the newly
created Harwell Laboratories, and was stepwise promoted to Deputy Chief Scientist
in 1952. In the mid-1950s, he achieved separation of the hydrogen isotopes on a
Pd-asbestos column. He developed nine patents and retired in 1971. During this later 19
years, he focused on radioisotope chemistry, solvent extraction, concentrated electrolyte
theory, membrane science and chromatography. Several of Glueckaufs papers dealt
with the principles of IEC, though the equations apply to all forms of chromatography.
A memorial biography provides many additional details and his IEC references [28].
See Chapter 5B, a, c, d, s and A-2
Once the above basic knowledge for the ion-exchange resins was developed, use of
this method spread rapidly to the separation of carbohydrates as their borate derivatives,
amino acids, nucleic acid derivatives, antibiotics, alkaloids and more complex biological
fluids [24,68].
21
F. CHROMATOGRAPHY OF PETROLEUM
As a consequence of the exploration, fractionation, processing and utilization of oil,
gasoline, kerosene, organic gases and related products, the analysis and chemistry of
these hydrocarbon mixtures occurred more recently more or less parallel to the rise
of the internal combustion engine and the post-1900 rise of the modern automobile.
Since these developments are described elsewhere, they are briefly mentioned here to
place in perspective the rapid developments of the chromatography of petroleum in the
1940s to 1950s.
Hydrocarbons in gas form may arise from (1) anaerobic bacterial fermentation
producing methane or marsh gas (about 109 tons per year for the earth), (2) coal
mining leading to a methane-rich mine drainage gas, or (3) landfill gas from human
waste. Natural gas, like fossil-based oil and coal from deep, rich accumulations, is
mainly methane with low concentrations of He, N2 , CO2 , ethane and higher alkanes
[1]. Gases from petroleum refineries are more complex. Regardless of source, hydrogen
sulfide is removed due to its toxicity and corrosive nature in an amine scrubbing
plant; carbon dioxide is separated by an alkali scrubbing process; water is deleted by a
glycol scrubbing tower and possible hydrocarbon liquids are eliminated by chilling or
adsorption. Such natural gases are widely used as fuels in residences and industries, and
as feedstock in the chemical industries [1,2]. The many components and biogenesis of
petroleum is highly complex [3].
22
Chapter 1
TABLE 1.1
MAJOR VARIANTS OF CHROMATOGRAPHY
From J.C. Giddings, Unified Separation Science, 1991, Chapter 10, p. 232.
Building on the earlier research of M.S. Tswett, L.S. Palmer, C. Dhere, A.J.P.
Martin and A.T. James, the merits of gas chromatography for separation and analysis of
petroleum products were very clear, due to its volatile, heat-stable, organic compounds
found in petroleum. After the 1859 drilling of the first oil well at Titusville, PA,
USA, by Edwin Drake, oil production increased in the United States and many other
countries to meet the demands of industrial growth, plus the later needs of automobiles,
trucks and diesel engines. The United States Geological Survey, that commenced in
1879, began a major survey of petroleum components under the leadership of David
Talbot Day (18591915); he did not know the complexity of petroleum components
[4]. During and after his graduate studies at the University of Maryland, he worked
at the United States Geological Survey, starting full time in 1895 and held a variety
of administrative positions [4]. In several lectures (1897, 1900), Day proposed that
primary oil migrated through rock formations by diffusion, not the earlier distillation
mechanism; his theory called filtration hypothesis was never followed with written
data nor methods. (His later emphases focused on utilization of oil shales, cracking
23
heavier oils to gasoline and private consultation.) Days work was continued by Joseph
E. Gilpin (18661924), a Professor of Chemistry at John Hopkins University, and his
students who tested the filtration hypothesis by allowing oil to diffuse down, and later
upwards through a column of fullers earth [4]. Gilpins four papers (19091913 after
Tswetts earlier papers) reported some fractionation of oil, but not complete separations.
Carl Engler (18421925), a German organic chemist at the University of Halle and
later the Technical University at Karlsruhe, heard Days 1902 lecture, set out to test the
filtration hypothesis and relied mainly on Day and Gilpins conditions; they did not
show separation. L.S. Ettre concluded that the methodology of Day, Gilpin and Engler
can be considered as precursors of the chromatographic technique; however, it should
not be envisaged as the beginnings of chromatography [4]. (L.S. Ettres article [4] has
many other details and references on these three scientists.)
Fractional distillation of the petroleum volatiles was the main earlier method of
analytical approach, but slowly in the 1940s, fractional desorption from an adsorbent
developed in the early investigations of S. Claesson [5] and C.S.G. Phillips [6], who
used columns (2, 8 or 15 mm ID, 30 cm long) of activated coal or coconut charcoal
and 4 levels of temperature between 7 and 127C to separate low molecular weight
hydrocarbons. Briefly, another early report by W.M. Smit explored what he called
adsorptive percolation of petroleum hydrocarbons on silica gel [7]. A.S.C. Lawrence
and D. Barby used powdered coke or alumina and successive solvent elutriation of fuel
oil [8].
A turning of direction, or inflection point, was the pioneering work of A.T. James
and A.J.P. Martin in 1952 [9]. It is interesting to note that some of the GC research
by E. Cremer [10], G. Hesse, and J. Janak [11] preceded that of A.T. James and A.J.P.
Martin [12,13].
Note: Most readers are aware of the overlap in the leading GC investigators and
the petroleum chromatographers. Deceased chromatographers who explored hydrocarbon mixtures include D.H. Desty, A. Zlatkis and others; the living chromatographers
who have been active contributors to petroleum chromatography are identified in the
Author=Scientist Index (with the code letter j see Table 1.2 for description of these
code letters). Since this chapter is an introduction, the reader is referred to the many,
more detailed books=reviews (see earlier C-1C, S-9A and Appendices 2, 4-A, 4-E, 5ABCDE, and several in 7). The outstanding recent book on petroleum chromatography,
edited by E.R. Adlard [2] reviews the quantitative analytical procedures, waxes, hydrodynamic chromatography of polymers, petroleum geochemistry, several detectors,
multi-column GC systems, SFC, HPLC, data handling and capillary electrophoresis.
24
Chapter 1
Seminal Concepts/
Subject areas
(See Chapter 5, 6 and S-9)
Experimental Investigations
and Instrumentation/
Automation
Research Publications
(See Chapters 5, 6 and S-9,
Appendices 4, 5 and 6)
Scientific Organizations
Emerging Technologies
Fig. 1.2. Driving forces in modern chromatography. This overall figure summarizes the known relationships
of chromatography (or science in general) and will be expressed in greater detail in the stated chapters
or appendices. The arrows highlight the connections, or the flow of thought, experiments, and the needed
process of communication that leads to emerging applications in new scientific industries.
nature of and the interactions with chromatography at the turn of this millennium. Only
the partially linear and main pattern of driving forces in chromatography is presented
in Fig. 1.2, in the connections to the chapters and appendices of this book. Other
cross-connections exist and are more subtle and variable.
This chapter a sketch of the history of chromatography is an introduction for
the chapters to follow. Chapter S-8 by L.S. Ettre provides a bibliography of references
for books, chapters, journal articles relevant to this chapter and this book; the interested
reader is encouraged to examine further these sources.
As stated earlier, one goal of this book is to highlight the significant research contributions, discoveries and personal recollections of over 100 chromatography awardees
[1]. Another goal is to emphasize the role of the scientists, their seminal concepts, the
science of chromatography, the research publications, scientific societies, institutions
and companies, the developing technologies and new scientific industries and their
interactions as shown in Fig. 1.2.
Notes: The seven appendices provide supplementary information on mainly books
and also overlap with many chapters. An excellent early reference to peruse is the
1949 Faraday Society Discussions [1], which provides a dramatic contrast of the state
of chromatography knowledge in 1949 with that of 2000 [2]. However, a recognized
imbalance of limited references to journal articles is corrected by the references cited
25
in other books. For instance, I.M. Hais and K. Macek made valiant efforts to collate
and publish the accumulating papers on paper and thin-layer chromatography in the
1950s to 1960s [3]. E. Lederer and M. Lederer cited 1879 references in their 1954
book on Chromatography [4]. Similarly, Z. Deyl (Ed.) in his 1984 book, Separation
Methods [5], has 512 journal references for gas chromatography, 145 references for
adsorption and partition chromatography, 169 for gel chromatography, 230 for affinity
chromatography, 176 for planar chromatography, and 301 references for electromigration techniques. L.S. Ettre in his 1980 review, Evolution of Liquid Chromatography
A Historical Overview [6], has 296 references on adsorption chromatography, partition
chromatography (paper- and TLC), IEC, gel chromatography, affinity chromatography
and HPLC. Cs. Horvath, editor of his 5-volume series, 19801988 book, High-Performance Liquid Chromatography [7] has hundreds of references on HPLC. J.C. Giddings
in his book, Unified Separation Science [8], and many other authors show a similar
thoroughness for references of their stated subject area.
Another excellent source to find reviews and journal articles is Chemical Abstracts,
Vol. 1, 1907 to Vol. 132, 2000, published by the American Chemical Society, Washington, DC, USA, which covers the worlds chemical literature with a very broad scope;
its earlier Collective Decennial Indexes and now Collective Quinquennial Year Indexes
enable a scientist to make a faster search through the thousands of citations. Chemical
Abstracts has some 241 CA SELECTS as a biweekly, current awareness bulletins,
that includes GC, GPE, HPLC, IEC, ion chromatography, paper chromatography and
TLC, as well as specific chemical groups, such as amino acids, peptides and proteins,
enzymes, prostaglandins, natural products, steroids, etc. However, when ones intent
is focused on chromatography, the frequently prepared Bibliography Section of the
Journal of Chromatography A (edited by Z. Deyl, J. Janak, V. Schwarz and K. Macek
and published by the Elsevier Science Publishers, Amsterdam, The Netherlands) is
valuable in content and organization [9]. This Bibliography has major sections on liquid
column chromatography, gas chromatography, planar chromatography, gel electrophoresis and capillary electrophoresis=electrokinetic chromatography with each having some
38 subsections plus other subdivisions; this structure of literature organization facilitates
quick searches. Chromatography Abstracts, 19861999 under the current guidance of
the (British) Chromatographic Society and the Royal Society of Chemistry is another
reference source [10]; it started in 1958 under another name, Gas Chromatography
Abstracts. However, in this day of computers, many scientists may prefer seeking the
desired reference information by the on-line approach.
Professional societies have had considerable input into the advance of chromatography through their journals and research conferences. The latter provide an opportunity
to present research papers, overall or review papers, presentation of research awards
and frequently a related symposium. Furthermore, such conferences provide the desired
training and retraining. Two older societies, Society for Analytical Chemists of Pittsburgh (SACP) and the Spectroscopy Society of Pittsburgh (SSP), combined strengths in
1949 to plan the Pittsburgh Conference on Analytical Chemistry (hereafter PITTCON).
PITTCON celebrated its 50th birthday in 1999 [11]. Leslie S. Ettre presents a longer
discussion of PITTCON and other chromatography societies (see C-3 and C-8).
26
Chapter 1
TABLE 1.2
INTEGRATION OF SEMINAL CONCEPTS WITH CHROMATOGRAPHY LEADERS
Code
Chapter locations
a.
b.1
b.2
b.3
b.4
c.
d.
e.
f.
g.
h.
i.
6-ABCE
1-B, 6-BE, 8-E, 9-AB,
1-C, 5, 6-BE, 8-G, 9-AB
1-D, 5
1-D, 5
1-E, 3-CD, 5, 9-A
1-3, 3-CD, 5, 6-ABCDE, 8-H,
9-AB, 10-A
5, 6-AB, 11, 14
5, 6-ADE, 9-E
5, 6-AE, 9-E, 14
4-E, 5, 6-ABCDE, 9-B, 9-E, 11
5, 6-A, 9-D
j.
k.
l.
m.
n.
o.
p.
q.
r.
s.
t.
1-F, 5, 6-BD
5, 6-ADE, 9-D, 10-A
5, 6-ACDE, 9-A, 14
5, 6-A, 14
5
5, 6-A, 6-ADE, 9-D, 14
5, 6-ADE, 9-E, 14
5, 6-A, 9-D, 11-C, 14
5, 6-ACD, 11, 12-E, 14
4-B, 5, 6-ACD, 14
4-D, 5, 14
Chapter locations are indicated by a number (115) and subsections by a letter; chapters with a number
higher than 7 are in the Supplement.
27
28
Chapter 1
TABLE 1.3
CHROMATOGRAPHIC MILESTONES OR PARADIGM SHIFTS
Date
Chapter
locations
19011903
M.S. Tswett
1-A
19031906
19121922
19311938
1-A
1-B
1-A, 9-B
19381960s
Thin-layer chromatography
1941
A.W.K. Tiselius
9-A
1940s
M.S. Tswett
L.S. Palmer and C. Dhere
R. Kuhn, E. Lederer, P. Karrer,
H.H. Strain and L. Zechmeister
N.A. Izamilov, J.G. Kirchner, M.S.
Shraiber, and E. Stahl
A.J.P. Martin and R.L.M. Synge
1-E, 5
1944
Paper chromatography
1952
Mid-1940s1960s
Gasliquid chromatography
Gassolid chromatography
Mid-1950s
19591960s
Gel filtration=molecular
sieve=size-exclusion chromatography
HPLC developed and established
1940s
1960s1970s
1960s1970s
19661980s
Chiral chromatography
1968
1990s
Affinity chromatography
Instrument development, process
design and process chromatography
Chromatography-on-a-chip
1990s
1-D
9-A
1-D
1-C
1-E, 5,
9-A
5, 9-E
5, 9-E
9-D
9-D, 10
5, 9-F
5, 9-D
29
TABLE 1.4
OTHER EARLIER CHROMATOGRAPHY LEADERS 1,2
Name
Institution 3 , country 4
Subject
areas(s) 5
Ettre=Zlatkis book
(see pages below)
Adlard, Edward R. 6
Boer, Hendrik
Dijkstra, Greult
Grant, David W.
Heftmann, Erich
Horning, Marjorie G.
James, Anthony T. 6
Kaiser, Rudolph E. 7
Karmen, Arthur 6,8
Kirchner, Justus G.
Kovats, Ervin sz. 6
Lederer, Michael
Liberti, Arnoldo 6
Patton, Hugh W.
Phillips, Courtenay S.G. 6
Ray, Neil H.
Rohrschneider, Lutz
Schwartz, Robert D.
Scott, Charles D.
Stross, Fred H.
Teranishi, Roy
Van Deemter, Jan J.
d, f, s
d, k
d, k
d, j
b, r
d, r
a, d, l, r
a, b, d, s
d, f
b
a, d, e
a
d, f
d, f
a, d, f
d, f, j
d
d, f, g, j
h, r
d, f, j
d
a, d
110
1119
4351
115123
125130
142150
167172
187192
193200
201208
231236
247253
255263
309313
315322
345350
351360
381390
391395
443446
453460
461465
For deceased, earlier Chromatography Leaders and their page reference in the Ettre and Zlatkis 1979 book,
see Appendix 2.
2 An exception for Table 1.4 should be noted. Some of the 1979 living and deceased contributors are
omitted here, as they are mentioned in subsequent chapters and located in the Author=Scientist Index.
Thus, Table 1.4 complements these chapters and Appendix 2 that covers deceased chromatographers. These
chromatographers were active during the 1930s to 1980s; many have retired; those who have passed away
may be found in A-2. Most of the chromatography awards had not been established for these earlier decades.
3 The institutional and country affiliations correspond to their 1979 listings; some may have moved.
4 For country abbreviations, see the Author and Scientist Index.
5 The Subject Area(s) for their research are described in Table 1.2.
6 These investigators have received one or two of the awards.
7 W. Bertsch, R.E. Kaiser decorated by German president, J. High Resolut. Chromatogr., 19 (1996) 710.
8 L.S. Ettre and G. Malikin, Editorial on A. Karmen, Chromatographia, 51 (5=6) (2000) 260261.
30
Chapter 1
Made significant laboratory discoveries and seminal ideas that have led to an original
concept or new experimental approaches.
Published a trail of research papers that documented and extended these approaches
or concepts.
Received recognition by peer review of their colleagues in the appropriate scientific
society, forum, or symposia.
Though most scientists are familiar with peer-review, others in different disciplines
and the lay community are not fully aware of the term. This communication gap between
scientists in their laboratories or ivory tower(?), with citizens at large and policy
makers in key positions is a major consideration and requires additional comment. While
there are many exceptions, the same comment applies also to the limited interaction of
scientific societies, the media and officials in national and international governments.
Peer review in the scientific community applies to the careful evaluation and
detailed consideration of: (a) research grant applications to government agencies or
private foundations; (b) original research papers for professional scientific journals,
whether sponsored by scientific societies or private publishers; (c) or a review of
nominations for scientific awards. Peer review refers to the deliberate, studied,
in-depth evaluation by ones colleagues to accept, reject, or recommend modifications
of a grant application or a scientific paper. Peer review is conducted on an anonymous
basis and has frequently led to improvement in the grant application or scientific paper.
With some modifications, the same qualities are included in the behind the scenes steps
for the peer review of nominations for the chromatography awards. These awards and
their peer-reviewed awardees represent the collective best in the chromatographic
sciences. The social=intellectual organization of peer review is performed by scientific
societies, which, of course, have other responsibilities in the communication of science.
Note: Further information on the awardees is described in C-2, 5, and S-9A and 9B
and the related scientific societies in Chapters 1G, 2, and 3.
SUMMARY
Chromatography has grown as a branch of science, and is now a powerful research
tool ranging across the sciences. The genius of Mikhail S. Tswett, the Father of
Chromatography, in the 1900s has had a profound subsequent impact in the sciences; he
was a true inventor, whose ideas have grown after his death to become the most widely
used laboratory separation method of all time. Chromatography has grown over the last
century to be a vigorous enterprise of scientists; plus societies with the background
of their patrons (or support) from government, academia, and research institutions; and
the corporate sector and private foundations. The scientific community and public
at large has benefited from these interactions, as presented by the awardees in other
chapters by:
Professional interactions of scientists among universities, industry, and across the
semi-artificial boundary lines of cultures and nations.
Personal knowledge and frequent long-standing friendships of scientists, despite such
possible barriers as race, religion, patriotism and language.
31
32
Chapter 1
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Chapter 1
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35
19. American Society for Testing and Materials (ASTM), Annual Book of ASTM Standards, ASTM, West
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NY, 1961, 3 Vols., pp. 13661500.
4. M.S. Shraiber, The beginnings of thin-layer chromatography, J. Chromatogr. Sci., 73 (1972) 367370;
M.S. Shraiber and N.A. Izmailov, Spot chromatographic adsorption analysis and its application in
pharmacy communication, J. Planar Chromatogr., 8 (1995) 402405; transl. from original Russian
Journal, Farmatsiya, 3 (1936) 17.
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6. J.G. Kirchner, Thin-layer chromatography Yesterday, today and tomorrow, J. Chromatogr. Sci., 11
(1973) 180183.
7. See Appendix 4-B for full citation to early books on TLC by K. Randerath (1962, 1966), E. Stahl
(19621967), G. Pataki (1966, 1971), J.G. Kirchner (1967, 1978), G.K. Macek (1972), A. Zlatkis and
R.E. Kaiser (1977).
8. See Appendices 5-BG and 7-BH for planar chromatography books in the 1990s.
9. V.G. Berezkin, The discovery of thin-layer chromatography, J. Planar Chromatogr., 8 (1995) 401402.
10. J. Sherma, Planar chromatography, Anal. Chem., 70 (12) (1998) 7R26R; ibid., Anal. Chem., 72
(2000) 9R25R.
11. S. Nyiredy, Planar chromatography Chapter 2, in: E. Heftmann (Ed.), Chromatography, Elsevier,
Amsterdam, 5th ed., 1992, pp. A110A150.
12. B. Fried and J. Sherma, Thin-Layer Chromatography, M. Dekker, New York, NY, 4th ed., 1999, 499
pp.
R. Kunin and R.J. Myers, Ion-Exchange Resins, Wiley, New York, NY, 1st ed. in 1950, 2nd ed. in
1958, 466 pp.
2. J.A. Kitchener, Ion-Exchange Resins, Methuen, London; or Wiley, New York, NY, 1957, 109 pp.
3. C. Calmon and T.R.E. Kressman (Eds.), Ion-Exchangers in Organic and Biochemistry, Interscience
Publishers, New York, NY, 1957, 761 pp.
4. F. Helfferich, Ion-Exchange, McGraw Hill, New York, NY, 1st ed. in 1959, 2nd ed. in 1962, 624 pp.
5. B.A. Adams and E.L. Holmes, Adsorptive properties of synthetic resins, J. Soc. Chem. Ind., London,
54 (1938) 1 (T).
6a. E.R. Tompkins and 14 other authors, Ion-exchange as a separations method and other topics, J. Am.
Chem. Soc., 69 (1947) 27692881.
6b. A. Tiselius and others, Chromatographic analysis 42 papers presented, of which 11 concerned
ion-exchange chromatography, Discuss. Faraday Soc., 7 (1949) 1336.
7. H.F. Walton (Ed.), Ion-Exchange Chromatography, Benchmark Papers in Analytical Chemistry (early
papers reprinted), Dowden, Hutchinson Ross, Stroudsburg, PA, 1976, 440 pp.
8. See Appendix 4-D for additional early IEC books by O. Samuelson, S. Blasius, R. Kunin, W. Rieman
and H.F. Walton, J.-X. Khym, and J.A. Marinsky and Y. Mana.
36
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26a.
26b.
27.
28.
29.
30.
31.
32.
33.
Chapter 1
L.S. Ettre, Preparative liquid chromatography and the Manhattan project, LC GC North America, 17
(12) (1999) 11041108.
W.E. Cohn, The nature and production of artificial radioactivity, Adv. Biol. Med. Phys., 1 (1948)
118149.
W.E. Cohn, Nucleic acid derivatives, in: C. Calmon and T.R.E. Kressman (Eds.), Ion-exchangers in
Organic and Biochemistry, Interscience Publications, New York, NY, 1957, pp. 345359.
W.E. Cohn, Column chromatography of nucleic acid derivatives and related substances, in: E. Heftmann (Ed.), Chromatography A Laboratory Handbook of Chromatographical and Electrophoretic
Methods, Reinhold, New York, NY, 2nd ed., 1967, pp. 627660.
W.E. Cohn, Paper 32, 1950, in: H.F. Walton (Ed.), see above Reference 7.
M. Lederer, Kurt A. Kraus Obituary, J. Chromatogr., 738 (1996) 155156.
F. Nelson, D.C. Michelson, H.O. Phillips and K.A. Kraus, Ion-exchange procedures. VII. Separation of
alkali metal ions, J. Chromatogr., 20 (1965) 107121.
K.A. Kraus, Papers 16 to 19 and 28, 19511958, in: H.F. Walton (Ed.); see above Reference 7.
E.R. Tompkins, Discuss. Faraday Soc., 7 (1949) 232237; see Reference 6b.
S.W. Mayer and E.R. Tompkins, J. Am. Chem. Soc., 69 (1947) 28662874.
E.R. Tompkins, Paper 2, 1947, in: H.F. Walton (Ed.), see above Reference 7.
F.H. Spedding, Metallurgy of Uranium and its Alloys, U.S. Atomic Energy Commission, National
Nuclear Energy Series, Vol. 12A, Washington, DC, 1963, 1977, 208 pp.
F.H. Spedding and A.H. Daane (Eds.), The Rare Earths, Wiley, New York, NY, 1961, 641 pp.; R.E.
Kreiger Publisher, 1971 reprint.
F.H. Spedding, Papers 5, 8, 13, 1947 to 1955; in: H.F. Walton (Ed.); see above Reference 7.
T. Moeller, The Chemistry of the Lanthanides, Reinhold Publishing, New York, NY, 1963, 117 pp.
N.E. Topp, The Chemistry of the Rare Earth Elements, Elsevier, Amsterdam, 1965, 164 pp.
H.F. Walton, Ion-exchange chromatography, Chapter 5, in: E. Heftmann (Ed.), Chromatography, Part
A: Fundamentals and Techniques, Elsevier, Amsterdam, 5th ed., 1992, pp. A227A265.
See also the eight recent IEC books cited in the Appendices 5-A, 5-E, and 5-G.
O. Samuelson, Ion Exchangers in Analytical Chemistry, Almqvist and Wiksell, Stockholm; Wiley, New
York, NY, 1st ed., 1953; ibid, Ion Exchange Separations in Analytical Chemistry, same publishers, 2nd
ed., 1963, 474 pp.
E. Glueckauf, K.H. Barker and G.P. Kitt, Theory of chromatography VIII. The separation of lithium
isotopes by ion exchange and of neon isotopes by low temperature adsorption columns, Discuss.
Faraday Soc., 7 (1979) 199213.
D.H. Everett, Eugen Glueckauf, Biogr. Mem. Fellows R. Soc., 30 (1982) 193274.
H.A. Sober and E.A. Peterson, Chromatography of proteins on cellulose ion-exchangers, J. Am. Chem.
Soc., 76 (1954) 17111712.
E.A. Peterson and H.A. Sober, Chromatography of proteins. I. Cellulose ion-exchangers, J. Am. Chem.
Soc., 78 (1956) 751755.
J. Porath and E.B. Lindner, Separation methods based on sieving and ion exclusion, Nature, 191 (1961)
6970.
J. Porath, T. Laas and J.-Ch. Janson, Agar derivatives for chromatography, electrophoresis and
gel-bound enzymes. III. Rigid agarose gels cross-linked with divinylsulfone, J. Chromatogr., 103
(1975) 4962.
O. Mikes, Ion-exchange chromatography, Chapter 45, in: Z. Deyl (Ed.), Separation Methods, Vol. 8,
1984, pp. 205270 with 422 references; in: A. Neuberger and L.L.M. van Deenen (General Editors),
New Comprehensive Biochemistry, Elsevier, Amsterdam, Vol. 1 in 1981 to Vol. 38 in 1999.
D.H. Desty and A. Goldup, Chromatography of hydrocarbons, in: E. Heftmann (Ed.), Chromatography
A Laboratory Handbook of Chromatographic and Electrophoretic Methods, 3rd ed., Van Nostrand
Reinhold, New York, NY, 3rd ed., 1975, pp. 915955.
10.
11.
12.
13.
37
E.R. Adlard (Ed.), Chromatography in the Petroleum Industry, Vol. 56 in the Journal of Chromatography Library Series, Elsevier, Amsterdam, 1994, 430 pp.
R.P. Philip, Geochemistry in the search for oil, Chem. Eng. News, 64 (6) (1986) 2843.
L.S. Ettre, Early petroleum chemists and the beginnings of chromatography, Chromatographia, 40
(314) (1995) 207216.
S. Claesson, Studies on adsorption and adsorption analysis with special reference to homologous
series, Arkiv. Kemi, Min. Geol. A, 23 (1) (1946) 123.
C.S.G. Phillips, The chromatography of gases and vapors, Discuss. Faraday Soc., 7 (1949) 241248.
W.M. Smit, Chromatography of petroleum hydrocarbons, Discuss. Faraday Soc., 7 (1949) 248255.
A.S.C. Lawrence and D. Barby, Chromatographic fractionation of black oils, Discuss. Faraday Soc., 7
(1949) 255258.
A.T. James and A.J.P. Martin, Gasliquid partition chromatography; The separation and microestimation of volatile fatty acids from formic acid to dodecanoic acid. Biochem. J., 50 (1952) 679
690.
For References on Erika Cremers early GC research, see Appendix 2.
For References on Gas Chromatography and Petroleum Chromatography, see L.S. Ettre in S-8IJ.
E. Lederer and M. Lederer, Chromatography A Review of Principles and Applications, Elsevier,
Amsterdam, 2nd ed., 1955, 460 pp.
D.H. Desty and A. Goldup, Chromatography of hydrocarbons, in: E. Heftmann (Ed.) Chromatography,
Reinhold Publishing, New York, NY, 1961, 753 pp.
L.S. Ettre, Chromatography: The separation technique of the 20th century, Chromatographia, 51 (2000)
717.
38
2.
Chapter 1
E. Smolkova-Keulemansova, A few milestones on the journey of chromatography, J. High Resolut.
Chromatogr., 23 (2000) 497501.
C.S.G. Phillips, Chromatography and the discovery process, J. Chromatogr., 468 (1989) 3542.
A.D. Baxevanis and B.F.F. Ouellette (Eds.), Bioinformatics A Practical Guide to the Analysis of
Genes and Protein, Methods of Biochemical Analysis, Vol. 39, WileyInterscience, New York, NY,
1998, 370 pp.
39
CHAPTER 2
CONTENTS
A.
B.
C.
D.
E.
F.
G.
H.
I.
J.
K.
L.
M.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Nobel prize in Chemistry by the Nobel Foundation (19481999) . . . . . . . . . . . . .
National Award in Chromatography of the American Chemical Society (19612001) . . . .
National Award in Separations Science and Technology of the American Chemical Society
(19842001) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
A.J.P. Martin Award of the Chromatographic Society (19782000) . . . . . . . . . . . .
M.S. Tswett Chromatography Award of the International Symposia on Advances in Chromatography (19741988) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
M.J.E. Golay Award in Capillary Chromatography of the International Symposia on Capillary
Chromatography (19892000) . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Stephen Dal Nogare Award in Chromatography of the Chromatographic Forum of the
Delaware Valley (19722000) . . . . . . . . . . . . . . . . . . . . . . . . . . . .
The Keene P. Dimick Award in Chromatography by the Society for Analytical Chemists of
Pittsburg (19882000) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Silver Jubilee Award of the Chromatographic Society (19822000) . . . . . . . . . . . .
Award for Achievements in Separation Science of the Eastern Analytical Symposium (1986
2000) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
COLACRO Medal (19862000) of the Congresso Latino Americano de Cromatografia . . .
Leroy S. Palmer Award of the Minnesota Chromatography Forum (19802000) . . . . . .
M.S. Tswett Chromatography Memorial Medal of the All-Union Scientific Council on
Chromatography, Academy of Sciences of the U.S.S.R. (19781979) . . . . . . . . . . .
Mailing address: P.O. Box 6274, Beardsley Station, Bridgeport, CT 06606-0274, USA
40
41
43
43
43
44
44
47
48
49
49
50
51
52
40
Chapter 2
We all stand on the shoulders of our predecessors; thus is it not conspicuous that
we can see further than they could?
Friedrich A. Kekule (18291890)
INTRODUCTION
A number of national and international awards honor scientists active in the field
of chromatography. Obviously, we should start with the Nobel prizes in this listing:
in the past three prizes were awarded specifically for achievements in chromatography.
The two principal chromatography awards are the National Award in Chromatography
of the American Chemical Society, and the A.J.P. Martin Award of the (British)
Chromatographic Society. A further major award is the National Award in Separations
Science and Technology of the American Chemical Society; although many of its
recipients received it for achievements other than chromatography, some were honored
specifically for activities related to the various chromatographic techniques.
Other major national and international recognitions in chromatography are the
M.S. Tswett Chromatography Award which has been presented between 1974 and
1988 by the International Symposia on Advances in Chromatography, the M.J.E.
Golay Award in Capillary Chromatography presented by the International Symposia
on Capillary Chromatography, the Stephen Dal Nogare Award of the Chromatography
Forum of the Delaware Valley and the Keene P. Dimick Award administered by
the Society for Analytical Chemists of Pittsburgh; both are presented at the yearly
Pittsburgh Conferences on Analytical Chemistry and Applied Spectroscopy. Further
major awards are the Silver Jubilee Award of the Chromatographic Society, the
Award for Achievements in Separations Science of the Eastern Analytical Symposium,
the COLACRO Medal presented by the biannual chromatography symposia held in
Latin America, and, finally, the Leroy Sheldon Palmer Award of the Minnesota
Chromatography Forum.
The Builders of Chromatography Major Chromatography Awards and the Award Winners 41
Awardee=Affiliation=Country
1948
1952
1972
42
Chapter 2
advancement of chromatography; they only used the methods. These Nobelists relied
on the chromatographic procedures along with other research methods, but in so doing,
showed the versatility, selectivity and sensitivity of the chromatography approach;
hence, their contributions are described in Chapters 1 and=or S-9.
TABLE 2.2
RECIPIENTS OF THE NATIONAL AWARD IN CHROMATOGRAPHY OF THE A.C.S.
Year
Awardee=Affiliation=Country
1961
1962
1963
1964
1965
1966
1967
1968
1969
1970
1971
1972
1973
1974
1975
1976
1977
1978
1979
1980
1981
1982
1983
1984
1985
1986
1987
1988
1989
1990
1991
1992
1993
1994
1995
1996
1997
1998
1999
2000
2001
The Builders of Chromatography Major Chromatography Awards and the Award Winners 43
44
Chapter 2
TABLE 2.3
RECIPIENTS OF THE AWARD IN SEPARATIONS SCIENCE AND TECHNOLOGY OF THE A.C.S.
Year
Awardee=Affiliation=Country
1984
1985
1986
1987
1988
1989
1990
1991
1992
1993
1994
1995
1996
1997
1998
1999
2000
2001
The Builders of Chromatography Major Chromatography Awards and the Award Winners 45
TABLE 2.4
RECIPIENTS OF THE A.J.P. MARTIN AWARD
Year
Awardee=Affiliation=Country
1978
1980
1982
1984
1985
1986
1988
1989
1990
1991
1992
1993
1994
1995
1996
1997
1998
1999
2000
1990 on, the financial sponsorship of the award was taken over by the Perkin-Elmer
Corporation. The award consists of a honorarium (presently $5000 per year) and a
medal.