Handbook of Microbial Iron Chelates (1991)

375 Pages·1991·24.576 MB·\375

by  Gunther Winkelmann (Author)

CRC Handbook
of
Microbial Iron
Chelates
Editor
Günther Winkelmann
Professor
Department of Microbiology and Biotechnolgoy
University of Tubingen
Tubingen, Germany
First published 1991 by CRC Press
Taylor & Francis Group
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Reissued 2018 by CRC Press
© 1991 by Taylor & Francis
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PREFACE
The present handbook seeks to bring into one book theoretical and practical information
on the various aspects of microbial iron chelates which are now collectively called sider-
ophores. While an earlier comprehensive treatise on Iron Transport in Microbes, Plants and
Animals, edited by Gunther Winkelmann, Dick van der Helm, and Joe B. Neilands in 1987
emphasized the different biological systems, the present handbook focuses on the various
iron chelating compounds. Thus, the reader will find important physicochemical and bio­
logical data of the presently known natural siderophores and of many synthetic analogues
which have been synthesized in recent years. Few branches of natural science have been so
rapidly altered by recent advances as has microbiology. Since the field of microbial iron
chelates in particular has increased tremendously during the past five years, an updated
compilation of the available data in the form of a handbook seemed to be necessary.
It was the intention of the editor to create a reference book for both the chemists involved
in analysis and synthesis of natural compounds, as well as for the biologists interested in
aspects of biosynthesis, function, and genetic regulation of microbial iron transport com­
pounds. The first part of the handbook deals with the isolation procedures, the various
siderophores, their producing organisms as well as with physiological and genetic aspects
of siderophore transport in microorganisms. The second part focuses on the physicochemical
data, such as formation constants, electrochemistry, and other spectroscopic properties of
natural and synthetic iron chelates. Moreover, some chapters describe in detail the methods
of characterization and structure elucidation. The last part of the book is concerned with
synthetic aspects of siderophores which may open the possibility to tailor particular sider­
ophores for scientific and commercial purposes. Last but not least, the potential of several
natural and synthetic compounds for clinical use is discussed, which will encourage estab­
lishment of closer links between those working on basic biological aspects and those involved
in aspects of therapeutical treatments of iron disorders in human health. This brief introduction
touches on only a few of the topics covered in this handbook. I believe that it is good
practice to compile the data for those entering the field and also for those who want to see
what is happening in other fields. I hope that those entering the study of microbial iron
chelates will find it as fascinating and rewarding as I do.
I would like to thank all my colleagues who have contributed to this handbook. The
friendly cooperation that exists between the “iron people” made it easy and pleasant to edit
this comprehensive handbook on microbial iron chelates.
Günther Winkelmann
September 1990
THE EDITOR
Günther Winkelmann, Dr. rer. nat. is Professor of Microbiology at the Department
of Microbiology & Biotechnology, University of Tübingen, Germany.
Dr. Winkelmann obtained his diploma and doctoral degree at the University of Hamburg
in Biology and Biochemistry in 1967 and 1969, respectively. After his habilitation in 1976
he was appointed as a Professor of Microbiology in 1980 at the University of Tübingen.
Dr. Winkelmann is a member of the German Society for Microbiology (VAAM), the
American Society for Microbiology (ASM), and the International Society for Human and
Animal Mycology (ISHAM).
He has been the recipient of research grants from the Deutsche Forschungsgemeinschaft
(DFG). Most of his papers and books focus on microbial iron transport compounds and
antimicrobial agents. He is the Editor-in-Chief of the journal Biology of Metals. His current
major research interests are in isolation and characterization of microbial products, aspects
of molecular recognition, and microbial degradation of natural products.
CONTRIBUTORS
Mohamed A. Abdallah, D.Sc., D.I.C. Hans-Beat Jenny, Ph.D.
Department of Chemistry Head of Analytical Laboratories
University of Strasbourg 1 Pharmaceuticals Research
Strasbourg, France Biotechnology Subdivision
CIBA-GEIGY Limited
Raymond J. Bergeron, Ph.D. Basel, Switzerland
Professor of Medicinal Chemistry
Departments of Medicinal Chemistry, Jacqueline Libman, Ph.D.
Medicine and Chemistry Senior Staff Scientist
University of Florida Department of Organic Chemistry
Gainesville, Florida Weizmann Institute of Science
Rehovot, Israel
Volkmar Braun, Ph.D.
Professor of Microbiology Joey D. Marugg, Ph.D.
Department of Microbiology Research Manager
University of Tubingen Gene Technology and Fermentation
Tubingen, Germany Unilever Research Laboratory
Vlaardingen, The Netherlands
Alvin L. Crumbliss, Ph.D.
Professor Berthold F. Matzanke, Ph.D.
Department of Chemistry Associate Professor
Duke University Department of Biology
Durham, North Carolina University of Tubingen
Tubingen, Germany
John B. Dionis, Ph.D.
Assistant Professor James S. McManis, Ph.D.
Department of Pediatrics Research Associate
New England Medical Center Department of Medicinal Chemistry
Tufts University School of Medicine University of Florida
Boston, Massachusetts Gainesville, Florida
Klaus Hantke, Ph.D. Kayoko Nakamura, Ph.D.
Professor Associate Professor
Department of Microbiology Department of Radiology
University of Tubingen Keio University
Tubingen, Germany Tokyo,Japan
Dick van der Helm, Ph.D. J. B. Neilands, Ph.D.
Research Professor Professor
Department of Chemistry and Department of Biochemistry
Biochemistry University of California
University of Oklahoma Berkeley, California
Norman, Oklahoma
Heinrich H. Peter, Ph.D.
Mahbubul A. F. Jalal, Ph.D. Head of Microbial Chemistry Section
Scientist Pharmaceuticals Research
Metabolism and Development Studies Biotechnology Subdivision
The Plant Cell Research Institute CIBA-GEIGY Limited
Dublin, California Basel, Switzerland
Abraham Shanzer, Ph.D. Gunther Winkelmann, Ph.D.
Associate Professor Professor
Department of Organic Chemistry Department of Microbiology and
Weizman Institute of Science Biotechnology
Rehovot, Israel University of Tubingen
Tubingen, Germany
Peter. J. Weisbeek, Ph.D.
Professor
Department of Molecular Cell Biology
University of Utrecht
Utrecht, The Netherlands
TABLE OF CONTENTS
Detection, Determination, Isolation, Characterization and Regulation of Microbial Iron
Chelates.................................................................................................................................. 1
Joe B. Neilands and Kayoko Nakamura
Structures, Coordination Chemistry and Functions of
Microbial Iron
Chelates................................................................................................................................15
Berthold F. Matzanke
Specificity of Iron Transport in Bacteria and Fungi..........................................................65
Gunther Winkelmann
Genetics of Bacterial Iron Transport..................................................................................107
Volkmar Braun and Klaus Hantke
Pyoverdins and Pseudobactins...........................................................................................139
Mohamed A. Abdallah
Molecular Genetics of Siderophore Biosynthesis in Fluorescent
Pseudomonads.....................................................................................................................155
Joey D. Marugg and Peter J. Weisbeek
Aqueous Solution Equilibrium and Kinetic Studies of Iron Siderophore
and Model Siderophore Complexes....................................................................................177
Alvin L. Crumbliss
Isolation and Spectroscopic Identification of Fungal Siderophores..................................235
Mahbubal A. F. Jalal and Dick van der Helm
Synthesis of Catecholamide and Hydroxamate Siderophores..........................................271
Raymond J. Bergeron and James S. McManis
Biomimetic Siderophores....................................................................................................309
Abraham Shanzer and Jacqueline Libman
Therapeutically Useful Iron Chelators...............................................................................339
John B. Dionis, Hans B. Jenny, and Heinrich H. Peter
Index....................................................................................................................................357

1
DETECTION, DETERMINATION, ISOLATION,
CHARACTERIZATION AND REGULATION OF MICROBIAL
IRON CHELATES
J. B. Neilands and Kayoko Nakamura
HISTORICAL
It is not a simple matter to identify the first microbial iron chelates to appear in the
research literature. This distinction is usually accorded to the ferrichromes since these were
the compounds first prepared by low iron growth of the microorganisms and attention was
focused initially on their capacity to bind iron as a biological activity. When applied to
selected species of both bacteria and fungi, growth under low iron stress disclosed the
synthesis of ferric chloride positive material to be a response fairly general for microorganisms
growing under such cultural conditions. Propagation of the smut fungus, Ustilago sphaer-
ogena, at low iron gave high yields of the ligands of ferrichrome and, especially, ferrichrome
A. Addition of excess iron salt then afforded the ferric complexes in amounts of the better
part of a gram per liter. In the course of chemical characterization of the ferrichromes, it
was discovered that the ferric ion is held in a trihydroxamate center. A search of the literature
revealed that a microbial product, aspergillic acid, had been characterized from Aspergillus
flavus in 1947. Other hydroxamic acid or ferric hydroxamate compounds which have to be
regarded as contemporaries of the ferrichromes include coprogen, mycobactin, grisein-
albomycin, nocardamin, mycelianamide, and the ferrioxamines.
Meanwhile the purple ferric chloride positive product of iron-stressed Bacillus subtilis
was identified as the 2,3-dihydroxybenzoate conjugate of glycine. These two chelating
groups, the hydroxamic acid and the catechol, are still the most commonly found among
the microbial iron chelates although, as expected, the structural diversity of these compounds,
which have assumed importance in fields as diverse as clinical medicine and agriculture,
continues to expand.
The apparent general ability, with some notable exceptions, of microorganisms to syn­
thesize ferric chelating agents required the invention of a new generic name. The earlier
designations, siderochromes, sideramines, and sideromycins, were replaced by the single
term siderophores. This was suggested by Lankford1 who, prophetically, reasoned that not
all of these ferric chelates might be colored and that the inclusion of “chrome” in the name
hence could both be inappropriate and misleading.
Siderophores are technically defined as virtually ferric ion specific binding compounds
produced by bacteria and fungi growing under low iron stress.
To date probably a hundred different siderophores have now been described at some
level of detail ranging from an initial detection of a biological activity through a full, three-
dimensional X-ray structure to a molecular mechanism of regulation of synthesis by iron.
However, many more siderophores remain to be characterized, new bio-chelation centers
for Fe(III) will be discovered and the present, primitive level of understanding of the
regulatory mechanism will be refined, This, then, is the rationale and justification for the
present survey of these aspects of the field of microbial iron chelates.
DETECTION AND DETERMINATION
LOW IRON MEDIA
Because of a tight control by iron on their biosynthesis, production of excess siderophore
cannot be expected until the culture is actually stressed for the metal ion. Thus regardless