Chromatography E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 800

Veröffentlichungsjahr: 2011

Beschreibung

Leading researchers discuss the past and present of chromatography

More than one hundred years after Mikhail Tswett pioneered adsorption chromatography, his separation technique has developed into an important branch of scientific study. Providing a full portrait of the discipline, Chromatography: A Science of Discovery bridges the gap between early, twentieth-century chromatography and the cutting edge of today’s research.

Featuring contributions from more than fifty award-winning chromatographers, Chromatography offers a multifaceted look at the development and maturation of this field into its current state, as well as its importance across various scientific endeavors. The coverage includes:

• Consideration of chromatography as a unified science rather than just a separation method

• Key breakthroughs, revolutions, and paradigm shifts in chromatography

• Profiles of Nobel laureates who used chromatography in their research, and the role it played

• Recent advances in column technology

• Chromatography’s contributions to the agricultural, space, biological/medical sciences; pharmaceutical science; and environmental, natural products, and chemical analysis

• Future trends in chromatography

With numerous references and an engaging series of voices, Chromatography: A Science of Discovery offers a diverse look at an essential area of science. It is a unique and invaluable resource for researchers, students, and other interested readers who seek a broader understanding of this field.

Leseprobe

CONTENTS

COVER

HALF TITLE PAGE

TITLE PAGE

COPYRIGHT

DEDICATION

PREFACE

ACKNOWLEDGMENTS

EDITORS/AUTHORS

CONTRIBUTORS

1: CHROMATOGRAPHY—A NEW DISCIPLINE OF SCIENCE

1.A. INTRODUCTION

1.B. LITERATURE ON CHROMATOGRAPHY

1.C. WHAT IS CHROMATOGRAPHY?—A DEFINITION

1.D. EVALUATIONS OF DEFINITIONS

1.E. PATHWAYS OF MODERN CHROMATOGRAPHY

1.F. SOME THOUGHTS ON THE CHROMATOGRAPHIC PROCESS

1.G. CHROMATOGRAPHY AS A SCIENTIFIC DISCIPLINE—ATTRIBUTES

1.H. RELATION OF SEMINAL CONCEPTS IN CHROMATOGRAPHY AND THE AWARDEES AND CONTRIBUTORS

1.I. SUMMARY

REFERENCES

2: CHROMATOGRAPHY—A UNIFIED SCIENCE

2.A. INTRODUCTION

2.B. MOBILE PHASES

2.C. STATIONARY PHASES

2.D. SOLUTE DERIVATIZATION

2.E. OPTIMIZATION

2.F. CONCLUSION

REFERENCES

3: PARADIGM SHIFTS IN CHROMATOGRAPHY: NOBEL AWARDEES

3.A. INTRODUCTION

3.B. NOBEL AWARDEES WHO ADVANCED CHROMATOGRAPHY

3.C. NOBEL AWARDEES WHO USED CHROMATOGRAPHY

3.D. NATURE OF PARADIGM SHIFTS

3.E. PARADIGM SHIFT FOR ONE NOBEL AWARDEE

3.F. SUMMARY

REFERENCES

4: THE TRAILS OF RESEARCH IN CHROMATOGRAPHY

4.A. INTRODUCTION

4.B. CAROTENOIDS BY CHROMATOGRAPHY

4.C. PARADIGM SHIFTS FOR OTHER NATURAL PRODUCTS AND CHROMATOGRAPHY

4.D. PARADIGM SHIFTS IN AMINO ACIDS, PEPTIDES, AND PROTEINS

4.E. AFFINITY CHROMATOGRAPHY

4.F. CHIRAL CHROMATOGRAPHY

4.G. SUPERCRITICAL-FLUID CHROMATOGRAPHY (SFC)

4.H. SIZE-EXCLUSION CHROMATOGRAPHY

4.I. HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY

4.J. DETECTORS AND SCIENTIFIC INSTRUMENTS IN CHROMATOGRAPHY

4.K. HYPHENATED/COUPLED/TANDEM TECHNIQUES IN CHROMATOGRAPHY

4.L. WOMEN SCIENTISTS IN CHROMATOGRAPHY

4.M. SUMMARY

REFERENCES

5: TODAY’S CHROMATOGRAPHERS AND THEIR DISCOVERIES (2000–2008)

5.A. INTRODUCTION

5.B. PROFESSIONAL SOCIETIES PRESENTING AWARDS

5.C. PROMINENT CHROMATOGRAPHERS (AWARDEES)

6: HISTORY AND DEVELOPMENTS IN CHROMATOGRAPHIC COLUMN TECHNOLOGY AND VALIDATION TO 2001

6.A. INTRODUCTION (Ernst Bayer)

6.B. SUPPORTS, STATIONARY AND BONDED PHASES

6.C. CONTRIBUTIONS BY OTHER CHROMATOGRAPHERS

6.D. SPECIAL TOPICS

6.E. CHROMATOGRAPHY COLUMN VALIDATION [1]

6.F. DEVELOPMENTS IN LC COLUMN TECHNOLOGY DURING 2006–2008 (Ronald E. Majors)

7: CHROMATOGRAPHY—ADVANCES AND APPLICATIONS IN ENVIRONMENTAL, SPACE, BIOLOGICAL, AND MEDICAL SCIENCES

7.A. EARLY YEARS OF AUTOMATED CHEMISTRY [1] (Charles W. Gehrke)

7.B. CHROMATOGRAPHY IN ENVIRONMENTAL ANALYSIS SINCE THE 1960s

7.C AMINO ACSD ANALYSIS BY GAS-LIQUID AND ION-EXCHANGE CHROMATOGRAPHY—30 YEARS (Charles W. Gehrke)

7.D. CHROMATOGRAPHY IN SPACE SCIENCES—GLC AND IEC OF APOLLO MOON SAMPLES [1] (Charles W. Gehrke)

7.E. CHROMATOGRAPHY OF NUCLEOSIDES—CANCER BIOMARKERS AND STRUCTURAL CHARACTERIZATION (Charles W. Gehrke)

7.F. CHROMATOGRAPHY IN CLINICAL STUDIES—SELECTED ABSTRACTS PRESENTED AT THE 2008 PITTSBURGH CONFERENCE (Charles W. Gehrke)

7.G. AFFINITY MONOLITHIC CHEMISTRY

8: CHROMATOGRAPHY ADVANCES AND APPLICATIONS IN PHARMACEUTICAL ANALYSIS IN THE CORPORATE SECTOR

8.A. ANALYSIS OF PHARMACEUTICALS FOR NEW DRUG REGISTRATION (Pat Noland and Terry N. Hopper)

8.B. ULTRA-HIGH-PRESSURE LC IN PHARMACEUTICAL ANALYSIS: BENEFITS, IMPACTS, AND ISSUES (Michael W. Dong)

8.C. HYDROPHILIC INTERACTION CHROMATOGRAPHY (HILIC) IN PHARMACEUTICAL ANALYSIS (Yong Guo)

8.D. SMALLER PARTICLES, HIGHER PRESSURES, AND FASTER SEPARATIONS: THE CURRENT STATUS OF PHARMACEUTICAL METHOD DEVELOPMENT 5 YEARS LATER (Todd D. Maloney)

8.E. THE USE OF MONOLITHIC MATERIAL AS ONLINE EXTRACTION SUPPORT FOR HIGH-THROUGHPUT BIOANALYTICAL APPLICATIONS (Raymond Naxing Xu1, Matthew J. Rieser, and Tawakol A. El-Shourbagy)

9: CHROMATOGRAPHY—ADVANCES IN ENVIRONMENTAL AND NATURAL PRODUCTS, CHEMICAL ANALYSIS AND SYNTHESIS

9.A. CHROMATOGRAPHY—ADVANCES IN TECHNOLOGY FOR AGRICULTURAL, ENVIRONMENTAL AND NATURAL PRODUCTS, CHEMICAL ANALYSIS AND SYNTHESIS (Del Koch and Charles W. Gehrke)

9.B. SOLVING THE BELGIAN DIOXIN CRISIS BY ANALYZING PCBs IN FATTY MATRICES (P. Sandra, F. David, and T. Sandra)

9.C. DEVELOPMENT OF LIQUID CHROMATOGRAPHY-MASS SPECTROMETRY AND APPLICATIONS TO NATURAL PRODUCTS RESEARCH (Richard van Breeman)

10: THE CHROMATOGRAPHY STORY UNFOLDS

11: CHROMATOGRAPHY IN THE MILLENNIUM—PERSPECTIVES

11.A. FIFTY YEARS OF PITTCON—CHROMATOGRAPHY INNOVATION (John A. Varine)

11.B. TWENTY-FIVE YEARS OF CHEMICAL HERITAGE FOUNDATION—VOYAGES OF DISCOVERY (Thomas R. Tritton and Robert L. Wixom)

11.C. CHROMATOGRAPHY IN THE EXTREMES (Mitch Jacoby)

11.D. ANALYTICAL SEPARATIONS AS MOLECULAR INTERACTION AMPLIFIERS (Apryll Stalcup)

11.E. PERSPECTIVES BY AWARDEES AND CONTRIBUTORS

11.F. SYSTEMS BIOLOGY, GENOMICS, AND PROTEOMICS (Robert L. Wixom and Charles W. Gehrke)

11.G. OVERALL CONCLUSIONS—THE EDITORS

AUTHOR/SCIENTIST INDEX

SUBJECT INDEX

COVER PHOTOGRAPHS KEY

CHROMATOGRAPHY

The evolution of chromatography: The bridge to the sciences and 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 the earlier book, Chromatography: A Century of Discovery (1900-2000)—the Bridge to the Sciences/Technology, Vol. 64, Elsevier, Amsterdam, 2001; see Chapters 1, 2, 5, and 6 therein and the present Chapters 3, 4, 5, and 11. What are the common features of their discoveries?

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Library of Congress Cataloging-in-publication Data:

Chromatography : a science of discovery / edited by Robert L. Wixom, Charles W. Gehrke.p. cm.Includes bibliographical references and index.ISBN 978-0-470-28345-5 (cloth)1. Chromatographic analysis–History–20th century–21st century. I. Wixom, Robert L. II. Gehrke, Charles W.QD79.C4C48376 2010543′.8–dc222009020801

DEDICATION

To Professor Emeritus Charles W. Gehrke (deceased February 10, 2009), who employed his clarity, resourcefulness, and organizational skills in the demanding task as senior editor of this book; and who will be remembered by faculty, students, and administration for his friendliness, persuasiveness, and integrity (see Editors/Authors section of this book).

To Professor Emeritus Robert L. Wixom (deceased July 8, 2009), who was determined to share with the new scientists of today, the rich history and fundamentals of thought and action which brought us to the chromatography of today and point us toward the future;and who will be remembered academically for his quest for truth and willingness to take the extra time and go the extra mile so that one might learn something new (see Editors/Authors section of this book).

To Professor Ernst Bayer (deceased 2001), who made significant contributions as co-editor of the earlier book, Chromatography: A Century of Discovery (1900-2000)—The Bridge to the Sciences/Technology, Vol. 64, Elsevier, Amsterdam, 2001 (see his biography therein), and who has made outstanding multiple research contributions in chromatography.

To our scientific colleagues, who have contributed significantly to the advances of chromatography and then described their research in this volume; and who have contributed scientific thoughts, ideas for experiments, and means for communication.

To our relevant research institutions, whether university, professional societies, or corporate/government agencies that have supported related research endeavors.

To our respective family members, who have been both patient and helpful as we moved through the writing process.

Our thanks are also extended to the editors of John Wiley & Sons, Inc.

PREFACE

The frontispiece illustration depicts the aim of this book: to capture the coherent message of our earlier chromatography book [1] and the present one—namely, to bridge, or to provide the connection of, the earlier chromatography (1900-2000) with the chromatography of the present book (2000-2008) and today’s science. Those multifaceted messages are based on connecting the pioneers of chromatography—Mikail S. Tswett, Leroy S. Palmer, and several others [1], the early builders of chromatography—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 (see [1] and Chapters 3 and 5 of this book). The bridge or the connections to later and wider facets of chromatography leads to examples of the science of discovery.

Now, a hundred years after M. S. Tswett, his robust infant of chromatography has grown to be a major subject with dozens of references for each chapter in the 2001 chromatography book [1], >50 pages in the appendixes of the 2001 online supplement [2], and this book. This expanding amplitude of chromatography and the scientific literature makes journal and/or book reading slower and perhaps tedious in the drive to be thorough. Fortunately, the recent electronic revolution has delivered the tools to resolve that dilemma—namely, journals online, abstract journals online, and search engines. Consequently, the appendixes in the online version of Chromatography [2] are not being updated for this volume. To summarize, turn on the power for the Internet.

Chromatography has observed the classical flow of many sciences—to question, to undertake related experiments, to probe the subject, to build on recent observations and hypotheses, to interpret the experiments, and when sufficient evidence has accumulated, to develop theories.

Some unique aspects of this book follow: Chapter 1 introduces the evidence for chromatography to be more than a method of separation, but is now a discipline of science. While some view chromatography as comprising multiple areas, Chapter 2 presents the case for chromatography as a unified science. After introducing the early “pioneers” and “builders” of chromatography in Chapter 3, an additional 25 Nobel Prize awardees (1937-1999) and 19 in (2000-2007) relied on chromatography as a method in their overall research. This review led to a discussion of “sharp turns,” “break-throughs,” “scientific revolutions,” and “paradigm shifts.” The multiple branches of chromatography known in the 1960s have continued to grow over the subsequent decades to now be recognized as “trails of research” (Chapter 4). Our key Chapter 5 presents the 2000-2007 awardees and key contributors along with a description of their research.

In Chapter 6, several invited scientists describe recent advances in column technology and its validation. Chapters 7, 8, and 9 examine the contributions of chromatography in subject areas: agricultural, space, and biological/medical sciences; pharmaceutical science; and the environment, natural products, and chemical analysis and synthesis. Chapter 10 provides a comprehensive compilation of references on the history of chromatography. Chapter 11, first describes three institutions that have contributed over the decades to chromatography: the Pittsburgh Conference on Analytical Chemistry and Applied Spectrometry (PITTCON); the Chemical Heritage Foundation, and the American Chemical Society. Next is a section on recognizing and using chromatographic separations as molecular interaction amplifiers. Perspectives for the future are given by awardees and significant contributors to the field of chromatography. Finally, the book concludes with how chromatography has contributed to the advances in systems biology, genomics, and proteomics along with the initial reliance on other methods and theory in order to advance these new areas of science. The continuous theme throughout this book portrays chromatography as “the science of discovery.”

This book is recommended for students in the sciences and research chromatographers at all levels of experience: professional scientists; research investigators in academia, government, and industry; science libraries in academia, government, industry, and professional societies; and historians and philosophers of science and educators and their advanced students. This book builds on its 2001 predecessor [1] to identify the additional more recent (2000-2008) major advances in chromatography and the discoveries that will influence many sciences in this ongoing twenty-first century. Science has the goal of discovery and hence “the science of discovery” is implicit in many of the following chapters.

This book describes chromatography as the “bridge”—as a central science—a key foundation built on the twentieth century for major advances and discoveries yet to come across many sciences of the twenty-first century.

REFERENCES

1. C. W. Gehrke, R. L. Wixom, and E. Bayer, (Eds.), Chromatography: A Century of Discovery (1900-2000)—The Bridge to the Sciences/Technology, Vol. 64, Elsevier, Amsterdam, 2001.

2. C. W. Gehrke, R. L. Wixom, and E. Bayer, (Eds.), Chromatography: A Century of Discovery (1900-2000)—The Bridge to the Sciences/Technology, Chromatography—A New Discipline of Science, Internet Chapters, Appendixes, and Indexes, 2001. [See Internet at Chem. Web Preprint Server (http://www.chemweb.com/preprint)].

ACKNOWLEDGMENTS

We, the Editors, have had many helpful conversations with and advice from V. G. Berezkin, P. R. Brown, T. L. Chester, V. A. Davankov, W. G. Jennings, J. Janak, and P. Sandra and the awardees. We have had the benefit of many helpful discussions with other chromatographers, particularly at the national meeting of PITTCON and the American Chemical Society (ACS). Many of these scientists have contributions in the text. We have appreciated the valuable comments and insights of Dr. Leslie S. Ettre.

We have appreciated the many contributions of valuable librarians at the University of Missouri: Kate Anderson, Rachel Brekhaus, Brenda Graves-Blevins, Janice Dysart, Rebecca S. Graves, E. Diane Johnson, Amanda McConnell, Rachel Scheff, 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, PA) and Chemical Abstracts (published by ACS, Columbus, OH). Preparation of copy for this book is due in large part to the excellent secretarial skills plus accuracy and patience of Rosemary Crane, Tina Jenkins, and Cynthia Santos at the University of Missouri, Columbia.

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.

The research for and the preparation, writing, and editing of this book were supported by the University of Missouri, Columbia (USA):

Chancellor, Brady Deaton, Vice Provost for Research, Jim Coleman and their Office of ResearchSchool of Medicine and Dean William CristCollege of Agriculture, Food and Natural Resources, and Dean Thomas PayneDepartment of Biochemistry and Chair Gerald HazelbauerExperiment Station Chemical Laboratories (Agriculture), and Director Thomas P. MawhinneyAnalytical Biochemistry Laboratory (ABC Labs), Columbia, Missouri, USA and CEO Byron Hill

Postscript. Unfortunately, the editors/authors of this book were unable to see its publication as they passed away before the final copy was completed. Thinking ahead, as good scientists must, Dr. Wixom enlisted the assistance in final editing of this manuscript of two University of Missouri colleagues and fellow chromatographers: Deborah L. Chance, Research Assistant Professor in the Departments of Molecular Microbiology & Immunology and Child Health, and Thomas P. Mawhinney, Professor in the Departments of Biochemistry and Child Health and current Director of the Missouri Agricultural Experiment Station Chemical Laboratories.

We thank Dr. Wixom and Dr. Gehrke for their grand contribution to the field in the assembling of this historical and prospective document, and the staff of John Wiley & Sons for their assistance in seeing that this work is published.

DEBORAH L. CHANCE and THOMAS P. MAWHINNEYAssociate Editors

EDITORS/AUTHORS

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 in 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, receiving his Ph.D. in 1947. In 1949, he joined the College of Agriculture at the University of Missouri-Columbia (UMC), retiring in Fall 1987 from positions as Professor of Biochemistry, manager of the Agricultural Experiment Station Chemical Laboratories, College of Agriculture, Food and Natural Resources, 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 from 1989 to 1997.

Gehrke is the author of over 260 scientific publications in analytical chemistry 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 carcinogen-RNA/DNA adducts; and automation of analytical methods for nitrogen, phosphorus, and potassium in fertilizers. He developed automated spectrophotometric methods of lysine, methionine, and cystine.

He has lectured on gas-liquid chromatography of amino acids in Japan, in China, and at many universities and institutes in the United States and Europe. In the 1970s, Gehrke analyzed all the lunar samples returned by Apollo flights 11, 12, and 14-17 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, Maryland.

Awards and Honors. In 1971, Dr. Gehrke 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 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 the chromatographic analysis of amino acids at the Central American Research Institute for Industry in Guatemala in 1975.

Gehrke was elected to Who’s Who in Missouri Education and was a 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 from 1979 to 1980. He received the Tswett Chromatography Memorial Medal from the Scientific Council on Chromatography, Academy of Sciences of the USSR, Moscow in 1978 and the Sigma XI Senior Research Award by the UMC Chapter in 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, the People’s Republic of China, Taiwan, the Philippines, and Hong Kong (in 1982 and 1987). He was elected to the Board of Directors and Editorial Board of the AOAC, 1979-1980; was President-Elect of the Association of Official Analytical Chemists International Organization, 1982-1983; and was honored by election as their Centennial President from 1983 to 1984. He developed an article, “Libraries of Instruments,” to describe interdisciplinary research programs on strengthening research in American Universities.

Gehrke was founder, board member, and former Chairman of the Board of Directors (1968-1992) of the Analytical Biochemistry Laboratories, Inc., a private corporation, in Columbia, MO, of 300 scientists, engineers, biologists, and chemists specializing in chromatographic instrumentation, and addressing worldwide problems on environmental and pharmaceutical issues to the corporate sector. He was 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, transfer RNA (tRNA), and messenger RNA (mRNA), and then applied these methods in collaborative research with scientists in molecular biology across the world (1970s-1990s). At the 1982 International Symposium on Cancer Markers, Freiburg, German Federal Republic, E. Borek, Professor of Biochemistry, Columbia University, stated that “Professor Gehrke’s 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 gas chromatographic (GC) methods for fatty acid analysis. Gehrke is widely known for developing a comprehensive quantitative GC method for the analysis of amino acids in biological samples and ultramicroscale methods for life molecules in moon samples in the 1970s. 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 toward the development of quantitative high-performance liquid chromatographic (HPLC) methods for the analysis of various important substances in biological samples, especially the modified nucleosides in tRNA as biomarkers in cancer research.

Major Research Contributions and Publications. Dr. Gehrke

Developed eight methods adopted as official methods by AOAC International (formerly Association of Analytical Chemists), sampling Ca, Mg, K, P, and N.Was the first to develop and automate AOAC Official Chemical Methods for fertilizers (1950s-1980s).Was the first to discover quantitative GLC of total protein amino acids (1960s-1970s), 45 publications.Was the first to develop quantitative HPLC of total nucleosides in tRNA, mRNA, rRNAs, and DNAs (1970s-1990s), 31 publications.Was the first to use HPLC-MS nucleoside chromatography in molecular biology (1987-1994), 23 publications.Was the first to use GLC and HPLC methods for metabolites in body fluids as potential biological markers (1971-1994), 54 publications.Was the first to use GLC in analysis of Apollo 11, 12, and 14-17 moon samples at ultrahigh sensitivity levels (1969-1974), 10 publications.Was the first to propose a lunar/Mars-based analytical laboratory (1989-1990 and 1995).

Dr. Gehrke was the author, co-author, or editor of the following books:

1979—author of a chapter in L. S. Ettre and A. Zlatkis (Eds.), 75 Years of Chromatography—a Historical Dialogue, pp. 75-86 (Elsevier Science Publishers BV, Amsterdam, The Netherlands).1987—C. W. Gehrke (CWG), K. C. Kuo, and R. L. Zumwalt (Eds.), Amino Acid Analysis by Gas Chromatography, in three volumes (CRC Press, Boca Raton, FL), 19 chapters by 29 authors (5 chapters by CWG).1990—C. W. Gehrke and K. Kuo (Authors/Eds.), Chromatography and Modification of Nucleosides, a three-volume, 1206-page treatise published by Elsevier in the Journal of Chromatography Library Series addressing the topics (1) analytical methods for major and modified nucleosides, (2) biochemical roles and function of modification, (3) modified nucleosides in cancer and normal metabolism, and (4) a comprehensive database of structural information on tRNAs and nucleosides by HPLC, GC, MS, NMR, UV, and FT-IR combined techniques.1993-C. Ponnamperuma and C. W. Gehrke (Eds.), Proceedings of the Ninth College Park Colloquium—A Lunar-Based Chemical Analysis Laboratory (A. Deepak Publishing, Hampton, VA).1997—C. W. Gehrke, Mitchell K. Hobish, Robert W. Zumwalt, Michel Prost, and Jean Degrés, A Lunar-Based Analytical Laboratory, C. Ponnamperuma memorial volume (A. Deepak Publishing, Hampton, VA).1954-1995—nine additional chapters and reviews in other scientific journals and books.260 research papers on analytical biochemistry and chromatography (1950-2000).

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 concerns of placing a chemical laboratory on the moon that would be automated, miniaturized, and computer robotic-operated and would support NASA programs in the study of five aspects of the exploration of space: (1) astronaut health, (2) closed-environment life support, (3) lunar resources, (4) exobiology, and (5) planetology.

Awards. Gehrke received the American Chemical Society National Award in Separations Science and Technology in 1999 and the American Chemical Society National Award in Chromatography in 2000.

His latest published book with Dr. Robert L. Wixom and Dr. Ernst Bayer, co-editors, was Chromatography: A Century of Discovery (1900-2000), published by Elsevier Sciences, B.V., Vol. 64, in 2001 (709 pages). The present book on chromatography builds on that 2001 book.

Postscript. After 91 years of life and 62 years as a vigorous scientist, Dr. Gehrke passed away on February 10, 2009. Some recent comments heard on his character are: “A great man has fallen, but left many seeds for his students and colleagues who will carry on,” “enthusiastic supporter of life sciences,” “never took shortcuts,” “dedicated teacher,” “an entrepreneur who was always moving on,” and “a devoted husband, father, and grandfather” (addition by Robert L. Wixom, co-editor).

Robert L. Wixom, co-editor of this book, was born on July 6, 1924 in Philadelphia. In 1947, he graduated with a B.Sc. in Chemistry from Earlham College, Richmond, IN. His graduate studies and thesis were at the University of Illinois under the guidance of Professor William C. Rose, and he received his Ph.D. in Biochemistry in 1952.

Wixom held teaching/research faculty appointments in the Department of Biochemistry, School of Medicine, University of Arkansas (1952-1964) and the Department of Biochemistry, School of Medicine/College of Agriculture, UMC (1964-1992). He took year-long sabbatical/research leaves at Oxford University (1961-1962), the University of Wisconsin, Madison, WI (1970-1971), the Massachusetts Institute of Technology (MIT), Cambridge, MA (1978-1979), and the Fox Chase Institute for Cancer Research, Philadelphia (1985-1986). His 40 years of research (45 peer-reviewed papers, two reviews) and graduate teaching focused mainly on amino acid and protein metabolism. He taught intermediate and advanced biochemistry to medical students, graduate students in diverse departments, and undergraduate students with a variety of majors. Wixom guided the Advanced Biochemistry Laboratory course at UMC for 20 years, which covered several experiments in chromatography, and for 15 years taught a course on biochemical information retrieval. He has received three teaching awards. He served as a Departmental Representative to the Graduate Faculty Senate (1980-1993) and its Chair (1989-1992); this included a key role in three major new university programs. He officially retired in 1992 as Professor Emeritus of Biochemistry, but continued many similar activities.

Reflecting other earlier interests, Wixom was the co-initiator of the UMC Environmental Affairs Council and served as their first chair for 3 years (1991-1994). He initiated and served as senior editor of the 1996 book, Environmental Challenges for Higher Education: Integration of Sustainability into Academic Programs. The preceding experiences served as the educational background for his role as co-editor of the 2001 book, Chromatography: A Century of Discovery (1900-2000)—The Bridge to the Sciences/Technology and now its sequel, Chromatography: A Science of Discovery, John Wiley & Sons, Inc., 2010.

Postscript. After celebrating 85 years of life, much of it as a teacher and seeker of knowledge in life as well as in the laboratory, Dr. Wixom passed away on July 8, 2009. “Distinguished as a scientist, educator and outdoorsman,” “energetic,” “courageous,” “passionate,” “dedicated to service,” and “persistent,” were among the many comments about this “always the teacher,” “family man,” Bob Wixom (addition by Deborah L. Chance and Thomas P. Mawhinney, associate editors and University colleagues of the editors).

CONTRIBUTORS

Armstrong, Daniel W. Professor and Chair, Department of Chemistry and Biochemistry, University of Texas at Arlington, Arlington, TX 76019-0065, USA

Bayer, Ernst Professor Emeritus, Research Center for Nucleic Acid and Peptide Chemistry, Institüt für Organische Chemie, Universität Tübingen, 72076 Tübingen, Auf der Morgenstelle 18, Germany

Berezkin, Viktor G. Doctor of Sciences (Chemistry), Professor, A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Lenin Av. 29, Moscow, 11991, Russia

Berger, Terry Department of Chemistry, AccelaPure Corporation, Princeton University, 9435 Downing St., Englewood, FL 34224, USA

Brown, Phyllis R. Professor Emeriti, University of Rhode Island, Kingston, RI 02881, USA

Burger, Barend (Ben) Victor Professor Emeritus, Department of Chemistry and Polymer Science, Stellenbosch University, Private Bag XI, 7602 Matieland, South Africa

Butters, Terry D. Department of Biochemistry, Oxford University, Glycobiology Institute, South Parks Road, Oxford OX1 3QU, UK

Chester, Thomas L. Adjunct Research Professor, Department of Chemistry, University of Cincinnati, PO Box 210172, Cincinnati, OH 45221-0172, USA

Cussler, Edward L. Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, MN 55455, USA

Davankov, Vadim Nesmeyanov-Institute of Element-Organic Compounds, Moscow, 119991, Russia

Dong, Michael W. Senior Scientist in Analytical Chemistry, Genetech, Small Molecule Pharmaceutical Sciences, South San Francisco, CA, USA

Engelhardt, Heinz Professor Emeritus, Fachrichtung 12-6 Instrummentelle Analytik/Umweltanalytik, Univesität Des Saarlandes Im Stadtwald; Bau 12, D-66123 Saarbrücken, Germany of Illinois, College of Pharmacy, 833 South Wood Street, Chicago, IL 60612, USA

Varine, John Department of Chemistry, University of Pennsylvania, and President, PITTCON 2008

Vega, Mario Professor, Facultad de Farmacia, University of Concepción, Casilla 237, Correo 3, Concepcion, Concepción, Chile

Welch, Christopher J. Process Research Laboratory on Automation & Robotics, Merck & Co., Inc., PO Box 2000, RY800-C362, Rahway, NJ 07065, USA

Wixom, Robert L. Professor Emeritus, Department of Biochemistry, University of Missouri, Columbia, MO 65212, USA

Wren, Stephen Principal Scientist, Pharmaceutical and Analytical R&D Group, AstraZeneca, Silk Court, Hulley Road, Silk Road Business Park, Macclesfield, Cheshire, UK

Xu, Raymond N. Associate Research Investigator, Abbott Laboratories, Department R46W, Building AP13A, 100 Abbott Park Road, Abbott Park, IL 60064, USA

Yeung, Edward Iowa State University, Ames Laboratory—USDOE and Department of Chemistry, Iowa State University of Science and Technology, College of Liberal Arts and Sciences, Ames, IA 50011, USA

ASSOCIATE EDITORS POSTSCRIPT

Chance, Deborah L. Research Assistant Professor, Departments of Molecular Microbiology & Immunology, and Child Health, University of Missouri, Columbia, MO 65212, USA

Mawhinney, Thomas P. Director, Missouri Agricultural Experiment Station Chemical Laboratories, Professor, Departments of Biochemistry, and Child Health, University of Missouri, Columbia, MO 65211, USA

1

CHROMATOGRAPHY—A NEW DISCIPLINE OF SCIENCE

Robert L. Wixom

Department of Biochemistry, University of Missouri, Columbia

Charles W. Gehrke

Department of Biochemistry and the Agricultural Experiment Station Chemical Laboratories, College of Agriculture, Food and Natural Resources, University of Missouri, Columbia

Viktor G. Berezkin

A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow

Jaroslav Janak

Institute of Analytical Chemistry, Academy of Sciences of the Czech Republic, Brno

An essential condition for any fruitful research is the possession of suitable methods. Any scientific progress is progress in the method.

—M. S. Tswett [3]

Science has been defined in different ways at different times. Nowadays it typically involves forming an idea of the way something works, and then making careful measurements, experiments or observations to test the hypothesis. If the evidence keeps agreeing, the hypothesis grows more believable. If even one observation contradicts it, the entire hypothesis is falsified and the search begins again. Gradual refinements of hypotheses leads to the development of a theory …. A theory is a set of hypotheses that have stood the test of time, so far at least have not been contradicted by evidence and have become extremely trustworthy….

—C. Suplee, Milestones of Science, 2000

CHAPTER OUTLINE

1.A. Introduction

1.B. Literature on Chromatography

1.C. What is Chromatography?—A Definition (by Viktor G. Berezkin)

1.D. Evaluations of Definitions

1.E. Pathways of Modern Chromatography (by Jaroslav Janak)

1.F. Some Thoughts on the Chromatographic Process (by Jaroslav Janak)

1.G. Chromatography as a Scientific Discipline—Attributes (by Robert L. Wixom and Charles W. Gehrke)

1.H. Relation of Seminal Concepts in Chromatography and the Awardees and Contributors (by the Editors)

1.I. Summary (by the Editors)

References

1.A. INTRODUCTION

Chromatography has developed over the past century [1,2] and has major input into many areas of modern science [1,2]. The main original work of M. S. Tswett was published in the book Chromatographic Adsorption Analysis [3]. For a review of the beginnings of chromatography, see the description of the “pioneer of chromatography,” Mikhail Semenovich Tswett, born of an Italian mother and Russian father in Italy (1872), educated in Switzerland in botany, and his later research on plant pigments—all of which led to his fundamental development of adsorption chromatography [1,3]. K. I. Sakodynskii made also a great contribution to the research and description of M. S. Tswett’s life [4,5]. A special reference is made to the book Michael Tswett—the Creator of Chromatography, published by the Russian Academy of Sciences, Scientific Council on Adsorption and Chromatography (2003) [6]. The book was released on the occasion of the 100th anniversary of the discovery of chromatography and is consulted by a wide range of readers interested in the history of science and culture. The book is a study of the famous Russian researcher Michael Tswett (1872-1919)—the creator of the method of chromatography, which is now widely used both in science and technology. Finally, it was the merit of Eugenia M. Senchenkova, an associate of the S. I. Vavilov Institute of the History of Science and Technology of the Academy of Science in Moscow, who compiled the life story of Tswett into a book [6].

Later contributions in adsorption chromatography were made by the pioneers: Leroy S. Palmer (1887-1944) at the University of Missouri, Gottfried Kränzlin (1882), Theodor Lippmaa (1892-1944), and Charles Dhére (1876-1955) [1, Chaps. 1, 2]. Later three Nobel Prizes in Chemistry were awarded to five Nobel Laureates in Chemistry for their research in chromatography; these discoverers of chromatography in science were Arne W. Tiselius, Archer J. P. Martin, Richard L. M. Synge, Stanford Moore, and William H. Stein (see Chapter 3). The subsequent advances by Richard Kuhn and several other Nobel awardees are also described in Chapter 3.

Most readers are familiar with the subsequent development of partition chromatography (liquid-liquid partition chromatography and gas-liquid partition chromatography), paper chromatography, thin-layer chromatography, and ion-exchange chromatography [1, Chap. 1]. This detailed knowledge led to the sketch of historical relationships (shown in Fig. 1.1).

Figure 1.1. Outline of the historical flow of scientific thought in chromatography (1900-1960s). The later developments in the 1970s-1980s led to UHPLC, HTLC, and associated hyphenated techniques with chromatography including MS/MS, NMR, IR and others (see Chapters 5-11). Also, it is understood that extrusion is not a chromatographic process or mode of development, but an older method of removing a developed chromatographic column. This figure will serve as a base outline for subsequent sections of this chapter. Partition chromatography and its sequential development occurred during the 1940s-1960s period.

[Note: Additional comments and references may be found later in Ref. 1, Chap. 1, and later in this present chapter and book.]

Over subsequent years, the subject of chromatography has become prolific with respect to the number and variety of papers published. A brief reference to the earlier seminal concepts (see Section 1.H) in the current report will assist in building the needed bridge of communication.

1.B. LITERATURE ON CHROMATOGRAPHY

Books, to be understandable, need to be written in a linear pattern—paragraph by paragraph, chapter by chapter. However, the complexity of history, whether for chromatography or other subjects, requires the depiction of overall relationships, such as shown in Fig. 1.2.

Such close coherence or limited association persists for multiple investigations, many institutions, many professional societies [1, Chap. 3], and the many journals of original papers, abstract journals, review journals, books, and trade journals. For a detailed guide to the now very extensive field of chromatography literature, see Section 1.G in Ref. 1, the Appendixes in Ref. 7, and Ref. 8.

Figure 1.2. Driving forces in modern chromatography. This flowchart summarizes the known relationships of chromatography (or science in general) and will be expressed in greater detail in the stated chapters. The arrows highlight the connections, or the flow of thought, experiments, and the needed process of communication that leads to the emerging applications in new scientific industries.

1.C. WHAT IS CHROMATOGRAPHY?—A DEFINITION

Figure 1.1 suggests that chromatography is a collection of methods. Yes, there is a considerable overlap and transfer of procedures, equipment, and instruments. Hence some scientists consider information on chromatography as a “branch of science” as described in Table 1.1 (definitions 1 and 2). Does that description suffice? No, as it does not answer the question of definition. A clear definition of the scientific content of any vigorously developing scientific field is an important condition for revealing its principal features, major results of its development and structural evolution, including delineation of its boundaries [9]. Solving this problem is complicated by the fact that chromatography, like most other scientific disciplines, is continuously evolving. The most widespread definitions of chromatography, unfortunately, are not adequate. Therefore, it is the principal task of this section to elaborate a new definition of contemporary chromatography.

TABLE 1.1.Definitions of Chromatography

Source: V. G. Berezkin [9].

DefinitionsSource of Definition

1. Chromatography is a physical method of separation in which the components to be separated are distributed between two phases, one of which is stationary (stationary phase) while the other (the mobile phase) moves in a definite direction [10].a

IUPAC, 1993, International Commission [10]

2. Chromatography is a:

(a)Science of intermolecular interactions and transport molecules or particles in a system of mutually immiscible phases moving relative to each other.

(b)Process of multiple differentiated repeated distribution of chemical compounds (or particles), as a result of molecular interactions, between mutually immiscible phases (one of which is stationary) moving relative to each other leading to formation of concentration zones of individual components of original mixtures of such substances or particles.

(c)Method of separation of mixtures of substances or particles based on differences in velocities of their movement in a system of mutually immiscible phases moving relative to each other [11].b

Scientific Council on Chromatography (Russian Acad. Sci.), 1997, National Commission [11], V. A. Davankov (Chair)

3. Chromatography is a scientific discipline (scientific field) that investigates formation, change, and movement of concentration zones of compounds (particles) of a studied sample in a flow of mobile phase, moving under conditions of interphase exchange relative to another (stationary) phase with sorption and/or sieve properties. A variant in separation is the use of selective influence on components of the analyzed mixture by one or a number of force fields [9].

V. G. Berezkin [9]

4. For a modified definition of chromatography by the Editors, see the text in Section 1.D.

The EditorsaHereinafter, we will refer to this as the “IUPAC definition.”bHereinafter, we will refer to this as the “SCChrom definition.”

Chromatography was realized for the first time as an analytical “technological” process over a hundred years ago, but only in the more recent decades, investigators have noticed that many natural processes are, in fact, chromatographic. However, up to now, there is no commonly accepted logically valid definition of chromatography, although, as Socrates noted, “Precise logical definitions of concepts are the most essential conditions of true knowledge” [9]. Figuratively speaking, a definition is the shortest and, simultaneously, the most comprehensive characteristic of a given concept. Therefore, the best answer to the question “What is chromatography?” is primarily its definition [9].

On the basis of recommendations for constructing definitions that had been long ago developed in logic, Berezkin analyzed the two best-known collective, but differing, definitions of chromatography (Table 1.1), namely, the definitions elaborated by the International Union of Pure and Applied Chemistry (IUPAC) [10] and the Scientific Council on Chromatography, Russian Academy of Sciences [11]. Indeed, the first definition considers chromatography as a “method”, the second one, as “science, process and method, simultaneously” [9].

It should be noted that the IUPAC definition practically repeats a definition of chromatography due to a well-known Dutch scientist, A. Keulemans [12], while the “triple” SCChrom definition is very close to a definition suggested by a well-known Russian scientist, M. S. Vigdergauz [13].

Earlier and even at the present time, one can hear an opinion that the elaboration of a more strict and precise definition of chromatography is not that important as a topical task for the development of the field. One can hardly agree with such a position, though supported by some respected chromatographers. It is hard to agree because of the lack of a precise (and commonly recognized) answer to the question “What is chromatography?” This lack of definition is undoubtedly a drawback in the development of this scientific discipline. The necessity has long been evident to provide a clear and logically based answer to this question, specifically, to elaborate a strict and sufficiently justified definition of chromatography.

Thus, a general definition of chromatography was formulated [9, p. 56]:

A. Chromatography is a scientific discipline (scientific field) that investigates formation, change, and movement of concentration zones of analyte chemical compounds of a studied sample in a flow of mobile phase with respect to solid or liquid stationary phases or particles.

B. With selective influence (contact) of one, or a number of, sorbent(s) on components of the analyzed mixture; or

C. Under selective influence of one or a number of force fields on components of the analyzed mixture.

1.D. EVALUATIONS OF DEFINITIONS

We, as the Editors, suggest that this definition can be described as: Chromatography is a scientific discipline (field of science) studying the formation, change, movement and separation of multiple concentration zones of chemical compounds (analytes) (or particles) of the studied sample in a flow of mobile phase relative to selective influence of one or a number of solid/liquid stationary phases or sorbents.

Separation may also be achieved with the influence of one or a number of force fields on components of the “centrifugal analyzed mixture” as in centrifuge sedimentation or in zone electrophoresis. The use of an external force field is not really chromatography, but a one-phase separation method that does not require movement of the mobile phase. Also, there is no stationary phase.

In Table 1.2, J. Janak presents possible variants of chromatography and discusses the theoretical aspects of the various chromatographics, as well as some thoughts on the process itself. The over 100 chromatography awardees and contributors in our 2001 book [1] and in this 2010 book [14] present the principles and applications of the chromatographic process.

TABLE 1.2.Principles and Methods of Chromatographya

In support of chromatography as a discipline of science, the Editors list the following 10 key attributes of chromatography in Section 1.G and describe seminal concepts of chromatography in Table 1.3 showing its widespread usage in science. Also, see Chapters 3 and 4 in this book on “paradigm shifts in chromatography” and the “trails of research”.

TABLE 1.3.Integration of Seminal Concepts with Chromatography Leaders

1.E. PATHWAYS OF MODERN CHROMATOGRAPHY

Chromatography presents one of the greatest methodical phenomenon of the twentieth century with an extremely fruitful output for the future. It has not only matured by a growing theoretical background but also significantly advanced the methodical level of chemical research and control. In this way, it has opened new horizons and broken through the limits of manipulations and sensitivity determinations for many experiments. The results of chromatography have influenced knowledge in many basic scientific disciplines as chemistry, biology, and medicine, and applied scientific tasks as environmental, food, drug, space, and similar problems sciences and technologies. It has solved many problems of industrial production, and, last but not least, it has led to the establishment of a new important industrial branch of scientific instruments.

Possible variants of chromatography and analogous techniques are classified in terms of flow and equilibria directions, phase systems, and format of experiments in Table 1.2.

The development of chromatography cannot be comprehended as an isolated process. Building on Tswett’s classical experiment, a series of column and flat-bed variants were performed contemporaneously with other improved separation methods, mainly electrophoresis. They “fertilized” each other (e.g., capillary gas chromatography → capillary zone electrophoresis) and also hybridized (electrochromatography).

All of the classical versions were performed on different adsorptive materials. Although they generated broad attention and represented a great deal of research and practice, they had the character of empirical improvements by trial and error.

The invention of the partition principle by A. J. P. Martin (1942) grew from his experimental work with fractional distillation and thinking about vapor – liquid equilibria. This invention, together with the concept of theoretical plates (TPs), had a major influence on the development of chromatography. The two-dimensional surface of any adsorbent used up to this time had been substituted by a three-dimensional space in the use of a liquid phase. This caused a far-reaching influence on linearization of the sorption isotherm of separated substances with extremely positive symmetrization of chromatographic curves on one hand and a broad spectrum of sorption media with tunable sorption properties on the other hand.

In the early 1950s, gas chromatography proved to be a real analytical method (1952). This variant of chromatography opened a rigorous theoretical treatment due to a more ideal behavior of the analyte in a gaseous state. The Dutch chemical engineers J. J. van Deemter, F. J. Zuiderweg, and A. Klinkenberg (1956) engaged in industrial gas flow processes and formulated the rate theory, which was accepted later as the so-called van Deemter equation describing the relationships among different types of diffusion and mass transfer phenomena and linear gas flow. This contribution was the second great impulse to further development in column technology by increasing the resolution power of columns from 102 TP of classical versions to 103 TP. Simultaneously, detection means have been improved in sensitivity limits from volume, molecular weight, and thermal conductivity measurements to flame ionization, mass spectrometry, and electron capture ionization means [1,8].

A further step was made by the American physicist, M. J. E. Golay. He applied his theoretical work on telegraph transport function to the gas flow in an open tube of small diameter, and thus introduced the capillary gas chromatography in practice [1]. This step increased the column resolution power to 106 TP.

These achievements illustrate how far from the optimum conditions the classical variants have been (phase ratios from, say, 2:1 up to 1:102).

In principle, this knowledge caused the rebirth of liquid chromatography in the 1970s. The Scottish physical chemist J. H. Knox (1983) had expanded the van Deemter equation to liquid–liquid system respecting three decimals in the diffusion coefficients values between gas and liquid and different mass transfer rate on gas–liquid and liquid–liquid interphases [1]. This resulted in greatly increased use and development of such columns and led to the beginnings of high-performance liquid chromatography (HPLC) and, later, high-performance thin-layer chromatography (HPTLC).

The theoretical background of chromatography had been profoundly influenced by the American theoretical chemist J. C. Giddings in the 1960s. His mathematical treatment of the dynamics of chromatography was later recognized as his unified theory of separation science (1991). His experimental work on high-density gas chromatography exposed the solvatization effect of compressed gas. This idea opened the use of supercritical fluids as the mobile phase by German analytical chemist, E. Klesper (1962). Supercritical-Fluid (SF) extraction by supercritical carbon dioxide and later by overpressured hot water was shown to be an extremely useful analytical means for trace analysis. Another goal by Giddings was the idea of dynamic sedimentation, known as field-flow fractionation, resulting in separation of particles, cells, and viruses. (It may be interesting to know that this idea was born during rafting on wild water by young sportsman, J. C. Giddings.)

1.F. SOME THOUGHTS ON THE CHROMATOGRAPHIC PROCESS

In addition to the components just described, modern chromatography has other key features:

Miniaturization is clearly a trend in column technology characterized by study of the optimal surface area, pore size, and their homogeneity. However, there is a gap—a field for study—between the surface area and pore size of molecular sieves and nanoparticles and/or present monolithic columns.Methodical and technical means of chromatography are able to open new approaches in knowledge of many further natural processes. I believe some of such new cases can be identified or be found in nature—formation of mineral water composition in sedimentary rocks is a good example. Really, ion-exchange chromatography has been identified and experimentally verified in free nature. It is a dominating process of water infiltrated into Mesozoic sediments (trias) is migrating through tertiary shells (sarmat) having sea-imprinted elements as Na and Mg. This situation is typical for Carpatian Mountains bow. The calcium bicarbonate and sulfate waters are changed continuously to natrium rich and magnesium enriched types without any change in anion composition. It is not a “sci-fi” idea, but a “science of discovery” result, valid with high probability elsewhere as well. Understanding the geochemistry of mineral water of many spas or other health resorts (not only in Slovakia) is a great help in hydrogeological boring for such natural sources.Following this idea, there is a good analogy between field-flow fractionation and flow of water in riverbeds or of blood in body channel systems. Phase equilibria form there, and mass transfer effects exist (as in liquid or gas chromatography) on kidney membrane and lung tissue surfaces. Both organs can be the object as well as the subject of scientific experimentation with a diagnostic value by chromatographic means. In particular, sorption on, and emission from, skin can be interesting, because skin diseases are objects of an empirical and insufficiently known area of medicine.Many interphases (liquid-imprinted solid, gas—liquid, etc.) have been studied in chromatography, but the area of separation by or on a membrane does not seem to have been sufficiently researched at this time, although the membrane is a crucial part of any living cell. Transfer of chromatographic knowledge seems to be a hopeful task.

1.G. CHROMATOGRAPHY AS A SCIENTIFIC DISCIPLINE—ATTRIBUTES

Time marches on. A century has passed since the introduction of chromatography by Mikhail Tswett [1,2]. Since chromatography has grown far beyond a collection of methods, an overall review of the attributes of modern chromatography in the twenty-first century follows here, based on our earlier book [1] and updated:

An organized path of study—see Refs. 1 and 7, as well as references cited therein and in this book.A broad and professional focus of research publications—original journals, review journals; see chapter references in Ref. 1 and appendixes in Ref. 7A considerable body of books, treatises, and handbooks; see the numerous chapter references in Ref. 1 and Apps. 4–7 in Ref. 7.A theoretical base that supports the methods and leads to further applications [1].A sense of direction and consistency within the subject area [1, Sec. 7.B].A comprehensive group of interacting professional societies with frequent meetings, seminars, conferences, and usually, but not always, an award for distinguished contributions [1, Chaps. 2, 3] (see also Chapter 11, below, this present volume).A strong core of excellent leaders in these societies and educators in major universities to actively seek new directions and continuous renewal and to impart new knowledge to students at several levels [1, Chaps. 5, 6] (see also Chapter 5, this volume).A set of detection instruments with accuracy, sensitivity, and selectively to meet the intellectual and laboratory challenges [7, Sec. S.10; 14] (see Chapter 6, this volume).A source of research funds: government agencies, research institutes, scientific industries, or private foundations [1].A broad outreach to other areas of science, industry, and society [1, 14].

To summarize, scientific societies and science itself evolve, merge, and mature. Further amplification of these characteristics will be presented in the subsequent chapters of this book [14]. Clearly, chromatography has the 10 key characteristics listed above and has become a major scientific discipline.

1.H. RELATION OF SEMINAL CONCEPTS IN CHROMATOGRAPHY AND THE AWARDEES AND CONTRIBUTORS

Consistent with the seven boxes shown in Fig. 1.2, Chapters 2–11 emphasize the contributions of the awardees and contributing scientists, their description of their research accomplishments (e.g., research publications), and the pertinent overall seminal concepts. Hence, in Table 1.3, the Editors have devised a scheme for characterizing these seminal concepts, expressed as lowercase superscript letters “a” to “z.” These letters will appear in many subsequent sections, particularly in Chapters 3–5, which present the awardees and contributors in alphabetic order; notation of these seminal concepts will facilitate the integration of subject areas. These features are related to the “Science of discovery,” discussed later especially in Chapter 11.

1.I. SUMMARY

Chromatography has grown over the past century to be the central separation science; it has become the “bridge” (or the common denominator) for analytical methods. The principles and methods of chromatography are listed in Table 1.2 and the seminal concepts, in Table 1.3. Instead of measurement of only one or several components in a sample, chromatography facilitates the separation, detection, identification, and quantitative measurement with selective detectors of usually all the components in a sample. Its characteristics of sensitivity, selectivity, versatility, and quantitative features on micro, macro, and preparative scales have led to its rapid expansion. The driving forces of chromatography include the persistence and creativity of scientists, their experimental investigations, their interrelated seminal concepts, their research journals and other publications, and the relevant scientific organizations. The aims of this book are to summarize the past achievements, to delineate the new chromatographic discoveries by recent awardees and contributors during 2000–2008, and to thereby demonstrate the key features of modern chromatography. Comments on these areas in the subsequent chapters will further amplify the meaning of the phrase “a science of discovery.”

REFERENCES

1. C. W. Gehrke, R. L. Wixom, and E. Bayer (Eds.), Chromatography: A Century of Discovery (1900–2000), Vol. 64, Elsevier, Amsterdam, 2001.

2. L. S. Ettre (2008) Chapters in the Evolution of Chromatography, Imperial College Press, London; see App. 2 for his milestone papers on LC/GC.

3. V. G. Berezkin (Compiler), M. S. Tswett, Chromatographic Adsorption Analysis, selected works, Transl. Ed. Mary R. Masson, Ellis Horwood, New York, 1990.

4. K. I. Sakodynskii and K. V. Chmutov, Chromatographia, 5, 471 (1972).

5. K. I. Sakodynskii, Mikhail Tswett, Life and Work, Viappiani, Milan, 1982.

6. E. M. Senchenkova (2003), Mikhail Tswett—the Creator of Chromatography, Russian Academy of Sciences, Scientific Council on Adsorption and Chromatography, Russia; Engl. transl. by M. A. Mayoroya and edited by V. A. Davankov and L. S. Ettre, 2003.

7. C. W. Gehrke, R. L. Wixom, and E. Bayer (Eds.), Chromatography: A New Discipline of Science (1900–2000), Apps. 3–7; For a supplement, see online at Chem. Web Preprint Server (http://www.chemweb.com/preprint/).

8. C. Horvath (Ed.), High-Performance Liquid Chromatography—Advances and Perspectives, Vol. 2, Academic Press, New York, 1980.

9. V. G. Berezkin, What is Chromatography? A New Approach Defining Chromatography, 1st ed., Nauka (Science), Moscow, 2003; later, published by The Foundation: International Organization for the Promotion of Microvolume Separations (IOPMSnyw, Kenneypark 20, B-8500, Kortrigk, Belgium, Engl, transl), 2004.

10. International Union of Pure and Applied Chemistry (IUPAC), Nomenclature for chromatography (recommendation), Pure Appl. Chem.65(4), 819 (1993).

11. V. A. Davankov (Chair), Chromatography—Basic Terms—Terminology, Commission of the Scientific Council on Chromatography, Russian Academy of Sciences National Commission, Issue 14, Moscow, 1997.

12. A. I. M. Keulemans, Gas Chromatography, Reinhold, New York, 1959.

13. M. S. Vigdergauz, in Uspekhi Gazovoi Khromatographil (Advances in Gas Chromatography), Iss 4, Part 1, Kazan Branch USSR Akad. Sci. and D. I. Mendelev, 1975, p. 2 (in Russian).

14. R. L. Wixom and C. W. Gehrke (Eds.), Chromatography: A Science of Discovery, John Wiley & Sons, Inc., New York, 2010 (the present volume).

Chromatography: A Science of Discovery. Edited by Robert L. Wixom and Charles W. Gehrke Copyright © 2010 John Wiley & Sons, Inc.

2

CHROMATOGRAPHY—A UNIFIED SCIENCE

Thomas L. Chester

Department of Chemistry, University of Cincinnati

CHAPTER OUTLINE

2.A. Introduction

2.B. Mobile Phases

2.C. Stationary Phases

2.D. Solute Derivatization

2.E. Optimization

2.F. Conclusion

References

Thomas L. Chester (Fig. 2.1) received his B.S. degree in Chemistry from the Florida State University in 1971. He then moved to Charleston, South Carolina, where he worked for the Verona Division of the Baychem Corporation (now Bayer) at their plant in Bushy Park. In Fall 1972, Tom enrolled in the graduate program at the University of Florida, where he earned the Ph.D. degree in 1976 under the direction of J. D. Winefordner. He then joined the Procter & Gamble Company, Cincinnati, Ohio, where he rose to Research Fellow in the Research & Development Department. He retired from P&G in 2007 and is now Adjunct Research Professor at the University of Cincinnati.

Figure 2.1. Thomas L. Chester.

Dr. Chester currently serves on the Editorial Advisory Boards of the Journal of Chromatography A and the Journal of Liquid Chromatography. He previously served on the A-page advisory panel for Analytical Chemistry. He was chair of the American Chemical Society (ACS) Subdivision of Chromatography and Separations Chemistry. He co-founded and served as President of Supercritical Conferences, the organization that produced the International Symposia on Supercritical Fluid Chromatography and Extraction, and served as Treasurer of the TriState Supercritical Fluids Discussion Group located in Cincinnati. Dr. Chester has authored over 70 publications and co-edited an ACS book, Unified Chromatography, 2001. His more recent research interests include chromatography modeling and optimization.

The Cincinnati Section of the American Chemical Society named Dr. Chester the 1993 Chemist of the Year. He was the recipient of the Keene P. Dimick Award in 1994 and the Chicago Chromatography Discussion Group Merit Award in 2007.

2.A. INTRODUCTION

In its broadest definition, unified chromatography is the simultaneous use of all parameters to accomplish a separation in the best manner possible. This definition broadens earlier concepts [1–7], but recognizes and builds on our history, opens the door to a practice of chromatography quite different from what we have done so far, and provides at least a glimpse at where we might be headed in the future. Our challenge in further developing chromatography is to abandon any perceived but unreal restrictions on what we can do, and then expand the scope of separations while keeping balance between practical utility and actual needs in the workplace. Let us explore some of our present limits and barriers while contemplating new possibilities.

2.B. MOBILE PHASES

From the early days of liquid chromatography (LC) and paper chromatography, mobile phases were fluids that could be easily handled. Chromatographers chose to use fluids that are well-behaved liquids at ambient temperature and pressure. They could not be so volatile that the compositions of mixed mobile phases would change in the course of generating a chromatogram. They could not be so viscous that mass transfer and capillary action were slow, or that inconveniently high pressure was required to generate flow through a packed column. There is a relatively small and well-known list of liquids that meet these requirements at ambient conditions, and the chief restriction preventing wider choices was the default condition of ambient temperature and pressure.

If we allow ourselves the ability to change the temperature and pressure (specifically, the outlet pressure in column LC or the gas pressure above a planar separation), many additional fluids become plausible [7]. For example, fluids that are normally gases at ambient conditions, such as CO2, butane, and propane, are well-behaved, low-viscosity liquids at ambient temperature if the pressure is elevated sufficiently. These are relatively weak solvents but are fine for high-speed LC separation of soluble solutes at relatively low temperatures. In addition, including one of these fluids as a component in a mixed mobile phase with a more traditional solvent will greatly lower the viscosity and the pressure differential required to achieve flow through a column [8]. Diffusion rates will also be increased when the mobile-phase viscosity is lowered, thereby improving mass transfer and lowering analysis times. The use of a really weak mobile-phase component along with a strong component in a binary mixture does not seriously compromise the overall mobile-phase strength.