Biochemistry of the Amino Acids

617 Pages·1965·8.29 MB·English

by  Alton Meister (Auth.)

BIOCHEMISTRY
OF
THE AMINO ACIDS
Second Edition
ALTON MEISTER
Department of Biochemistry
Tufts University School of Medicine
Boston, Massachusetts
Volume II
1965
ACADEMIC PRESS
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Preface
to the Second Edition
The author has attempted, as in the first edition, to present a compre-
hensive picture of the current status of amino acid biochemistry. It is
apparent to those who have followed the biochemical literature of the last
eight years that we are now in the midst of an extraordinarily productive
period, and that much of the important progress made has concerned the
amino acids. Thus, about a hundred new amino acids have been dis-
covered and more than this number of amino acid analogs have been
synthesized and studied. The incorporation of certain amino acid analogs
into proteins has been amply substantiated. Earlier work on the trans-
aminases and other vitamin B enzymes has been extensively elaborated
6
with highly purified enzymes. The study of protein synthesis has exploded
from a stage in which a handful of biochemists was interested in the
problem to one in which hundreds are now working. Recent studies
provide explanations for the translation of genetic information into the
amino acid sequences of proteins as well as for the mechanisms of the
individual steps involved in peptide bond formation. These investigations
and others that have elucidated most of the enzymatic steps involved in
the biosynthesis and transformations of the protein amino acids now make
it possible to approach such problems as the control of enzyme synthesis,
the mechanism of action of hormones, and the chemical defects associated
with certain human diseases.
In the second edition it has been necessary to revise and expand
virtually every section of the first edition; most of the original text has
been completely rewritten. It was inevitable that there would be a con-
siderable increase in the number of pages, and indeed the second edition
is more than double the size of the first and contains more than twice as
many references to the literature. It has therefore seemed desirable to
VI Preface to the Second Edition
publish the present edition in two volumes, each of which contains the
complete subject index. Chapter I was enlarged to include recently
discovered amino acids and peptides. Chapters II and III of the second
edition cover the area presented in Chapter II of the first edition. The
study of amino acid antagonists has proceeded far beyond the nutritional
stage, and a separate chapter (Chapter III) has therefore been written.
Chapter IV covers amino acid transport and many of the * 'general
reactions'' of amino acids including oxidative deamination, nonoxidative
deamination, the action of amino acid oxygenases, and the multitude of
reactions catalyzed by vitamin B enzymes. Protein synthesis and the
6
synthesis of smaller molecules containing peptide bonds are now covered
in a separate chapter (Chapter V). (About nine pages of the original edition
were devoted to protein synthesis in comparison to 83 pages in the present
edition.) Volume II (Chapters VI and VII) is concerned with the inter-
mediary metabolism of the amino acids. Although the outlines of the
pathways of biosynthesis and metabolism of most of the protein amino
acids were known at the time the first edition of this book was written, a
considerable increase in knowledge of this area has been achieved, and
about three times as much space is devoted to this field as in the first
edition. The final chapter of Volume II deals with disorders of amino
acid metabolism in man; several new diseases associated with defects of
amino acid metabolism have been discovered in the last few years, and it
seems probable that the number of such conditions is much larger than
hitherto suspected.
The most dramatic developments of the last eight years have been in
the area of protein synthesis; the data that have been obtained about the
nucleic acid-amino acid code, the mechanism of protein synthesis, and
the elaboration of these findings in terms of genetics and in the control
of enzymatic activity (and therefore of metabolism) seem to represent only
a starting point for more exciting future investigations. Although the
individual steps in the intermediary metabolism of the protein amino
acids are largely understood, there are still some hazy areas, and more
information about the relative quantitative importance of various path-
ways is needed. In addition, the mechanisms of most of these enzymatic
reactions are not yet known nor is the manner in which these enzymes are
controlled fully understood. The presence in nature of more than a hun-
dred nonprotein amino acids raises additional questions about biosynthe-
sis, metabolism, and function; these phenomena have not yet been
extensively investigated nor have the effects of these potential amino acid
Preface to the Second Edition vii
antagonists on animal organisms been fully evaluated. Another important
problem that remains for future investigation is the mechanism of trans-
port of amino acids. Thus, it is evident that although the present edition
of this work represents an expansion and largely rewritten version of the
original text, it must also be accepted as a statement and summary of
presently available data upon which future developments will be built.
A number of attempts have been made in recent years to improve and
standardize biochemical nomenclature. Although such efforts have been
of some value, potentially confusing situations have sometimes developed
because of the continued use in the literature of more than one term for a
given compound. In this treatise nomenclature has been used that will be
understandable in terms of current usage in the literature rather than any
specific set of rules. It is probable that the final nomenclature of this field
will be achieved only when progress has stopped. Well-known abbrevi-
ations such as ATP, DPN, DNA, and RNA, and others which are defined
in the text have been used sparingly. The text was completed toward the
end of 1963 and the beginning of 1964. An attempt was made to add in
proof, insofar as possible, pertinent material that appeared later than this
(to approximately the middle of 1964).
ALTON MEISTER
January, 1965
Acknowledgments
The author is pleased to acknowledge the help of individuals who called
his attention to errors and omissions in the first edition, provided him
with manuscripts and figures prior to publication, and offered advice. He
is appreciative of the permission granted by several authors and publishers
to reproduce various tables and figures, whose sources are cited in the text.
He is particularly grateful to his students for their stimulation, assistance
in reading proofs, and patience during the time that the second edition
was being written. He is also indebted to Dean Joseph M. Hayman, Jr.,
for his skill in maintaining at Tufts University School of Medicine an
environment so free of administrative problems that even a chairman of a
department may work in the laboratory and write a book. The author
wishes to thank John J. Corrigan, Ezra Khedouri, P. R. Krishnaswamy,
James M. Manning, Kivie Moldave, Elizabeth Dodd Mooz, Jonathan S.
Nishimura, Gerhard Schmidt, Saul Slapikoff, Daniel Wellner, and Edith
Wilson of the Department of Biochemistry of Tufts University School of
Medicine, and Alexander E. Braunstein, Morris E. Friedkin, Van L.
Johnson, Roy L. Kisliuk, Owen J. Koeppe, Herbert Tabor, Sidney
Udenfriend, and Hubert B. Vickery for various and valued assistance in
offering advice and constructive criticisms, and in proofreading. It is a
pleasure to thank Miss Selma Frank and her associates, especially Mrs.
Patience Barry and Miss Susan Doughty, for their careful and skillful
efforts in drawing structures, typing, and checking references. Finally,
the author wishes to acknowledge the patience, encouragement, and
valuable assistance of his wife, Leonora Garten Meister, who read the
entire galley proof and assisted in preparing the subject index, and also
his sons Jonathan and Kenneth Meister for help in organizing the refer-
ences for publication.
ix
Contents
of Volume I
Chapter I. The Natural Amino Acids . . .. 1
A. General Considerations 1
B. The Common Amino Acids of Proteins 3
C. General Properties of the Amino Acids 27
D. Other Natural Amino Acids 57
E. Natural D-Amino Acids 113
F. Peptides and Related Compounds 118
G. Stereochemical Considerations 139
H. Preparation of the Optical Isomers of Amino Acids . . . 155
I. The a-Keto Acid Analogs of Amino Acids 161
References 167
Chapter II. The Role of Amino Acids in Nutrition 201
A. General Considerations 201
B. Amino Acid Requirements of Higher Animals . . .. 202
C. Growth Studies on Animals with Amino Acid Mixtures . . 209
D. Effects of Amino Acid Deficiencies in Mammals . . . 214
E. Amino Acid Requirements of Cells Grown in Tissue Culture . 216
F. Amino Acid Requirements of Lower Animal Forms . . . 218
G. Amino Acid Requirements of Microorganisms . . . . 219
H. Utilization of D-Amino Acids and a-Keto Acids . . . 220
References 225
Chapter III. Amino Acid Antagonists .231
A. General Considerations 231
B. Antagonism between Naturally Occurring Amino Acids . . 239
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xviii Contents of Volume I
C. Methionine Antagonists 241
D. Glutamic Acid and Glutamine Antagonists 244
E. Aspartic Acid Antagonists 247
F. Phenylalanine and Tyrosine Antagonists 248
G. Tryptophan Antagonists 251
H. Arginine Antagonists 252
I. Lysine Antagonists 253
J. Histidine Antagonists 254
K. Proline Antagonists 255
L. Leucine, Isoleucine, and Valine Antagonists . . .. 256
M. Antagonism Involving D-Amino Acids 258
N. Peptides as Reversing Agents for Amino Acid Antagonists . 259
0. Concluding Remarks 260
References 261
Chapter IV. General Biochemical and
Physiological Considerations . . .. 269
A. Transport of Amino Acids into Cells 269
B. Metabolism of the Amino Group 283
C. Metabolism of the Carbon Chain 293
D. Oxidative Deamination 294
E. Nonoxidative Deamination 319
F. Amino Acid Oxygenases 323
G. Decarboxylation 325
H. Transamination 338
1. Racemization and Epimerization 369
J. The Function of Vitamin B in Amino Acid Metabolism . . 375
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References 413
Chapter V. Formation of Peptide Bonds and
Protein Synthesis 439
A. General Considerations 439
B. Acylation of Amino Acids 441
C. Glutamine Synthesis 446
D. Glutathione and Related Peptides 452
Contents of Volume I xix
E. Carnosine and Related Peptides 454
F. Pantothenic Acid 456
G. Asparagine 457
H. Peptide Antibiotics 460
I. Bacterial Cell Wall Peptides 468
J. Reactions Catalyzed by Hydrolytic Enzymes . . .. 473
K. Protein Synthesis 482
References 564
Author Index Volume I 1
Subject Index for Volumes I and II . . . . . .. 59
Tables and Figures
Volumes I and II
Discovery of the Natural Amino Acids 2
Amino Acid Composition of Several Proteins . . .. 20
Amino Acid Sequence of Insulin from Cattle . . . . 21
Species Differences in the Amino Acid Sequences of Insulin . 22
Amino Acid Sequence of Beef Ribonuclease 23
Amino Acid Sequence of the Protein Subunit of Tobacco Mosaic
Virus 24
Amino Acid Sequence of the ß-Chain of Human Hemoglobin . 25
Amino Acid Sequence of Horse Heart Cytochrome c . 26
Some Properties of the Common Amino Acids of Proteins . . 28
Dissociation Curve of Glycine 30
Separation of an Amino Acid Mixture on a Dowex 50 Column . 48
Quantitative Determination of Amino Acids by the Automatic
Procedure of Spackman et al 49
Ion Exchange Chromatography of Amino Acids and Related Com-
pounds by a Procedure Similar to That of Spackman et al. . 50
Diagram of a 2-Dimensional Paper Chromatogram . . . 53
Gas Chromatogram of the Protein Amino Acids . . . . 56
The Free Amino Acids of Several Materials of Mammalian Origin 110
Free Amino Acids in Hemolymph of the Phylum Arthropoda . 112
Natural D-Amino Acids 115
Amino Acid Sequences of the Corticotropins and Melanocyte-
Expanding Hormones 126
Specific Optical Rotations of the Amino Acids Commonly Found
in Protein Hydrolyzates 141
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