PROTEIN-META L INTERACTIONS ADVANCES IN EXPERIMENTAL MEDICINE AND BIOLOGY Editorial Board: Nathan Back State University of New York at Buffalo N. R. Di Luzio Tulane University School of Medicine Bernard Halpern College de France and Institute of Immuno·Biology Ephraim Katchalski The Weizmann Institute of Science David Kritchevsky Wistar Institute Abel Lajtha New York State Research Institute for Neurochemistry and Drug Addiction Rodolfo Paoletti University of Milan Recent Volumes in this Series Volume 40 METAL IONS IN BIOLOGICAL SYSTEMS: Studies of Some Biochemical and Environmental Problems Edited by Sanat K. Dahr • 1973 Volume 41A PURINE METABOLISM IN MAN: Enzymes and Metabolic Pathways Edited by O. Sperling, A. De Vries, and J. B. Wyngaarden' 1974 Volume 41B PURINE METABOLISM IN MAN: Biochemistry and Pharmacology of Uric Acid Metabolism Edited by O. Sperling, A. De Vries, and J. B. Wyngaarden • 1974 Volume 42 IMMOBILIZED BIOCHEMICALS AND AFFINITY CHROMATOGRAPHY Edited by R. B. Dunlap' 1974 Volume 43 ARTERIAL MESENCHYME AND ARTERIOSCLEROSIS Edited-by William D. Wagner and Thomas B. Clarkson' 1974 Volume 44 CONTROL OF GENE EXPRESSION Edited by Alexander Kohn and Adam Shatkay • 1974 Volume 45 THE IMMUNOGLOBULIN A SYSTEM Edited by Jiri Mestecky and Alexander R. Lawton· 1974 Volume 46 PARENTERAL NUTRITION IN INFANCY AND CHILDHOOD Edited by Hans Henning Bode and Joseph B. Warshaw. 1974 Volume 47 CONTROLLED RELEASE OF BIOLOGICALLY ACTIVE AGENTS Edited by A. C. Tanquary and R. E. Lacey. 1974 Volume 48 PROTEIN-METAL INTERACTIONS Edited by Mendel Friedman • 1974 Volume 49 NUTRITION AND MALNUTRITION: Identification and Measurement Edited by Alexander F. Roche and Frank Falkner • 1974 Volume 50 ION·SELECTIVE MICROELECTRODES Edited by Herbert J. Berman and Normand C. Hebert • 1974 PROTEIN-METAL INTERACTIONS Edited by Mendel Friedman Western Regional Research Laboratory Agricultural Research Service U. S. Department of Agriculture Berkeley, California PLENUM PRESS • NEW YORK AND LONDON Library of Congress Cataloging in Publication Data American Chemical Society Symposium on Protein-Metal Interactions, Chicago, 1973. Protein-metal interactions. (Advances in experimental medicine and biology, v. 48) Includes bibliographies. 1. Metals in the body-Congresses. 2. Metals-Physiological effect-Congresses. 3. Proteins-Congresses. I. Friedman, Mendel, ed. II. American Chemical Society. III. Title. IV. Series. [DNLM: 1. Metals-Metabolism-Congresses. 2. Proteins Metabolism-Congresses. WIAD559 v. 48/ QU55 S9864p 1973] QP531.A42 1973 612'.0152 74·13406 ISBN 978-1-4684-0945-1 ISBN 978-1-4684-0943-7 (eBook) DOl 10.1007/978-1-4684-0943-7 Proceedings of the American Chemical Society Symposium on Protein-Metal Interactions held in Chicago, Illinois, August 27.29, 1973, with supplemental invited contributions. © 1974 Plenum Press, New York A Division of Plenum Publishing Corporation 227 West 17th Street, New York, N.Y. 10011 Softcover reprint of the hardcover 15t edition 1974 United Kingdom edition published by Plenum Press, London A Division of Plenum Publishing Company, Ltd. 4a Lower John Street, London WIR 3PD, England All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher Preface Metal ions and proteins are ubiquitous. Therefore, not surprisingly, new protein-metal interactions continue to be dis covered, and their importance is increasingly recognized in both physical and life sciences. Because the subject matter is so broad and affects so many disciplines, in organizing this Symposium, I sought participation of speakers with the broadest possible range of interests. Twenty-two accepted my invitation. To supplement the verbal presentations, the Proceedings include five closely re lated invited contributions. The ideas expressed are those of the various authors and are not necessarily approved or rejected by any agency of the United States Government. No official recommendation concerning the sub ject matter or products discussed is implied in this book. This book encompasses many aspects of this multifaceted field. Topics covered represent biochemical, immunochemical, bioorganic, biophysical, metabolic, nutritional, medical, physiological, toxi cological, environmental, textile, and analytical interests. The discoveries and developments in any of these areas inevitably illumine others. I feel that a main objective of this Symposium, bringing together scientists with widely varied experiences yet with common interests in protein-metal interactions, so that new understanding and new ideas would result has been realized. I hope that the reader enjoys and benefits from reading about the fascinat ing interactions of metal ions and proteins as much as I did. Although an adequate summary of the Symposium is not possible in a brief preface, I wish to express particular interest in the ideas reported by Professor Frieden: that the relative occurrence and participation of the various metals as essential elements in enzyme action and other life processes is an adaptive relationship to their relative abundance in the ocean. Undoubtedly, this adap tation is a continuing process. A more immediate practical concern voiced by D. K. Darrow and H. A. Schroeder that has received wide spread publicity and debate is that children are highly susceptible v vi PREFACE to lead poisoning and that their exposure to lead nowadays comes mainly from automobile exhaust. Of the invited contributions supplementing the Symposium, the paper by J. T. MacGregor and T. W. Clarkson deserves special mention. Dr. MacGregor collaborated with Dr. Clarkson, his former major pro fessor, in this thorough review while the latter was out of the country dealing directly with an episode of mercury poisoning de scribed in their paper. I believe their critical compilation of tissue distribution and toxicity of mercury compounds will greatly benefit the medical and other scientific communities in dealing with this useful but dangerous element. I am confident that the Proceedings of the Symposium on "Protein-Metal Interactions" will be a valuable contribution to the literature. I am particularly grateful to Dr. 1. A. Wolff, Chairman of the Protein Subdivision of the Division of Agricultural and Food Chemistry of the American Chemical Society, who invited me to organize this Symposium, to all contributors and participants for a well realized meeting of minds, and to R. N. Ubell, Editor in-Chief, Plenum Publishing Company, for arranging publication as a volume in the series, ADVANCES IN EXPERIMENTAL MEDICINE AND BIOLOGY. Mendel Friedman Moraga, California April 1974 Contents 1. THE EVOLUTION OF METALS AS ESSENTIAL ELEMENTS with special reference to iron and copper 1 Earl Frieden, Department of Chemistry, Florida State University, Tallahassee, Florida. 2. THE FUNCTIONAL ROLES OF METALS IN METALLOENZYMES. 33 J. F. Riordan and B. L. Vallee, Biophysics Research Laboratory, Department of Biological Chemistry, Harvard Medical School, Boston, Massachusetts. 3. STUDIES ON CARBOXYPEPTIDASE A • . 59 E. T. Kaiser, Tai-Wah Chan and Junghun Sub, Department of Chemistry, University of Chicago, Chicago, Illinois. 4. ZINC-WOOL KERATIN REACTIONS IN NONAQUEOUS SOLVENTS •• 81 N. H. Koenig and Mendel Friedman, Western Regional Research Laboratory, ARS, USDA, Berkeley, Calif. 5. HEME-PROTEIN-LIGAND INTERACTIONS. 97 J. B. Fox, Jr., M. Dymicky and A. E. Wasserman, Eastern Regional Research Center, ARS, USDA, Philadelphia, Pennsylvania. 6. 13C NMR STUDIES OF THE INTERACTION OF Hb AND CARBONIC ANHYDRASE WITH 13C02• • • • • • • • • • • • • • • • • 109 Frank R. N. Gurd, Jon S. Morrow, Philip Keirn, Ronald B. Visscher and Robert Marshall, Department of Chemistry, Indiana University, Bloomington, Indiana.. 7. THE ANION-BINDING FUNCTIONS OF TRANSFERRIN •..•. 125 P. Aisen, A. Leibman and R. A. Pinkowitz, Depart ments of Biophysics and Medicine, Albert Einstein College of Medicine, Bronx, New York. vii viii CONTENTS 8. LACTOFERRIN CONFORMATION AND METAL BINDING PROPERTIES 141 R. M. Parry, Jr. and E. M. Brown, Eastern Regional Research Center, ARS, USDA, Philadelphia, Penn. 9. PHYSICOCHEMICAL STUDIES OF Ca++ CONTROLLED ANTIGEN ANTIBODY SYSTEMS • • • • • . • • • • • • • • • • • 161 P. A. Liberti, H. J. Callahan and P. H. Maurer, Department of Biochemistry, Thomas Jefferson Uni- versity, Philadelphia, Pennsylvania. 10. CALCIUM BINDING TO ELASTIN • • • • •• 185 Robert B. Rucker, Department of Nutrition, Univer sity of California, Davis, California. 11. THE COORDINATION OF CALCIUM IONS BY CARP MUSCLE CALCIUM-BINDING PROTEINS A,B, AND C. 211 0 ••••• Carole J. Coffee, Department of Biochemistry, University of Pittsburgh, Pittsburgh, Pa., Ralph A. Bradshaw, Department of Biological Chemistry, Washington University School of Medicine, St. Louis, Mo., and Robert H. Kretsinger, Department of Biology, University of Virginia, Charlottesville, Va. 12. FERROXIDASES AND FERRlREDUCTASES: THEIR ROLE IN IRON METABOLISM. 235 E. Frieden and S. Osaki, Department of Chemistry, Florida State University, Tallahassee, Florida. 13. COPPER AND AMINE OXIDASES IN CONNECTIVE TISSUE METABOLISM • • • • • 267 0 • • 0 • 0 • • • • • 0 • E. D. Harris and Bo L. O'Dell, Department of Agricultural Chemistry, University of Missouri, Columbia, Mo. 14. COPPER- AND ZINC-BINDING COMPONENTS IN RAT INTESTINE 285 Gary Wo Evans, USDA, ARS Human Nutrition Labora- tory, Grand Forks, North Dakota, and Carole J. Hahn, Department of Biochemistry, University of North Dakota, Grand Forks, North Dakota. 15. METAL-ALBUMIN-AMINO ACID INTERACTIONS: CHEMICAL AND PHYSIOLOGICAL INTERRELATIONSHIPS • 299 0 • R. Io Henkin, Section of Neuroendocrinology, National Heart and Lung Institute, Bethesda, Maryland. CONTENTS ix 16. THE EFFECT OF ZINC DEPRIVATION ON THE BRAIN •..• 329 G. J. Fosmire, Y. Y. Al-Ubaidi, E. Halas and H. H. Sanstead, USDA, ARS Human Nutrition Labora tory, Grank Forks, North Dakota and Department of Psychology, University of North Dakota, Grand Forks, North Dakota. 17. BIOCHEMICAL AND ELECTRON MICROSCOPIC STUDIES OF RAT SKIN DURING ZINC DEFICIENCY • • . • . • . . • • • . 347 J. M. Hsu, K. M. Kim and W. L. Anthony, Veterans Administration Hospital, Department of Pathology, University of Maryland School of Medicine and Department of Biochemical Sciences, The Johns Hopkins University, Baltimore, Maryland. 18. NICKEL DEFICIENCY IN CHICKS AND RATS: EFFECTS ON LIVER MORPHOLOGY, FUNCTIONAL AND POLYSOMAL INTEGRITY. 389 F. H. Nielsen, D. A. Ollerich, G. J. Fosmire and H. H. Sanstead, USDA, ARS, Human Nutrition Labora- tory, Grand Forks, North Dakota and Department of Anatomy, University of North Dakota, Granq Forks, North Dakota. 19. SELENIUM CATALYSIS OF SWELLING OF RAT LIVER MITOCHONDRIA AND REDUCTION OF CYTOCHROME c BY SULFUR COMPOUNDS • • • • • • . • • • . . • • . • . • 405 o. A. Levander, V. C. Morris and D. J. Higgs, Agricultural Research Service, USDA, Beltsville, Maryland. 20. CHILDHOOD EXPOSURE TO ENVIRONMENTAL LEAD ..•• 425 D. K. Darrow and H. A. Schroeder, M.D., Trace Element Laboratory, Department of Physiology, Dartmouth Medical School, Hanover, New Hampshire. 21. CELLULAR EFFECTS OF LEAD. • 447 R. A. Goyer and J. F. Moore, Department of Pathology, University of North Carolina at Chapel Hill, N.C. 22. DISTRIBUTION, TISSUE BINDING AND TOXICITY OF MERCURIAL S • . • • . • . . • . . • • • • . • . 463 J. T. MacGregor, Western Regional Research Labora tory, ARS, USDA, Berkeley, California and T. W. Clarkson, The University of Rochester, School of Medicine and Dentistry, Rochester, New York. x CONTENTS 23. INTERACTIONS OF MERCURY COMPOUNDS WITH WOOL AND RELATED BIOPOLYMERS • • . • . . 505 Mendel Friedman and Merle Sid Hasri, Western Regional Research Laboratory, ARS, USDA, Berkeley, Ca lifornia. 24. INTERACTIONS OF KERATINS WITH METAL IONS: UPTAKE PROFILES, MODE OF BINDING, AND EFFECTS ON PROPERTIES OF WOOL . • . • . . . . . • . • . . . . 551 Merle Sid Masri and Mendel Friedman, Western Regional Research Laboratory, ARS, USDA, Berkeley, California. 25. X-RAY PHOTOELECTRON SPECTROSCOPIC STUDIES OF BIOLOGI CAL MATERIALS. METAL ION PROTEIN BINDING AND OTHER ANALYTICAL APPLICATIONS . . . • • • . . • . . • . . 589 M. H. Millard, Western Regional Research Labora- tory, ARS, USDA, Berkeley, California. 26. METAL ANALYSIS IN BIOLOGICAL HATERIAL BY ENERGY DISPERSIVE X-RAY FLUORESCENCE SPECTROSCOPY 621 F. William Reuter, Western Regional Research Laboratory, ARS, USDA, Berkeley, California and William L. Raynolds, Department of Nutritional Sciences, University of California, Berkeley, California. 27. THE APPLICATION OF PERTURBED DIRECTIONAL CORRELA TION OF GAHMA RAYS TO THE STUDY OF PROTEIN-METAL INTERACT IONS ••••• • • • • • • • • • • • 639 G. Graf, J. C. Glass, and L. L. Richer, Depart ments of Biochemistry and Physics, North Dakota State University, Fargo, North Dakota. . . . . . . . . . . . . . . . . . INDEX ••• 681