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Mechanistic Bioinorganic Chemistry
Thorp and Pecoraro; Mechanistic Bioinorganic Chemistry Advances in Chemistry; American Chemical Society: Washington, DC, 1996.
Thorp and Pecoraro; Mechanistic Bioinorganic Chemistry Advances in Chemistry; American Chemical Society: Washington, DC, 1996.
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ADVANCES IN CHEMISTRY SERIES 246
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Mechanistic Bioinorganic Chemistry H . Holden Thorp, EDITOR University of North Carolina at Chapel Hill
Vincent L. Pecoraro, EDITOR University of Michigan
Developed from a symposium sponsored by the Division of Inorganic Chemistry, Inc., at the 205th National Meeting of the American Chemical Society, Denver, Colorado, March 28-April 2, 1993
American Chemical Society, Washington, DC 1995
Thorp and Pecoraro; Mechanistic Bioinorganic Chemistry Advances in Chemistry; American Chemical Society: Washington, DC, 1996.
QP 531
.M4
1995 Copy 1
Mechanistic bioinorganic chemistry
Library of Congress Cataloging-in-Publication Data American Chemical Society. Meeting. (205th: 1993: Denver, Colo.)
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Mechanistic bioinorganic chemistry / [editors] H . Holden Thorp, Vincent L . Pecoraro; developed from a symposium sponsored by the Division of Inorganic Chemistry, Inc., at the 205th National Meeting of the American Chemical Society, Denver, Colorado, March 28-April 2, 1993. p. 246)
cm.—(Advances in chemistry series, ISSN 0065-2393;
Includes bibliographical references and indexes. ISBN 0-8412-3062-5 (clothbound) 1. Bioinorganic chemistry—Congresses. I. Thorp, H . Holden, 1964. II. Pecoraro, Vincent L . III. American Chemical Society. Division of Inorganic Chemistry. IV. Title. V. Series. QP531.A395 1993 574.19'214—dc20
95-15128 CIP
This book is printed on acid-free paper.
Copyright © 1995 American Chemical Society All Rights Reserved. The appearance of the code at the bottom of the first page of each chapter in this volume indicates the copyright owner's consent that reprographic copies of the chapter may be made for personal or internal use or for the personal or internal use of specific clients. This consent is given on the condition, however, that the copier pay the stated per-copy fee through the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, M A 01923, for copying beyond that permitted by Sections 107 or 108 of the U.S. Copyright Law. This consent does not extend to copying or transmission by any means—graphic or electronic—for any other purpose, such as for general distribution, for advertising or promotional purposes, for creating a new collective work, for resale, or for information storage and retrieval systems. The copying fee for each chapter is indicated in the code at the bottom of the first page of the chapter. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by A C S of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of any right or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto. Registered names, trademarks, etc., used in this publication, even without specific indication thereof, are not to be considered unprotected by law. PRINTED IN
THE
UNITED
STATES
OF
AMERICA
Thorp and Pecoraro; Mechanistic Bioinorganic Chemistry Advances in Chemistry; American Chemical Society: Washington, DC, 1996.
1995
Advisory
Board
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Advances in Chemistry Series
Cynthia A. Maryanoff Robert J. Alaimo R. W. Johnson Pharmaceutical Procter & Gamble Pharmaceuticals Research Institute Mark Arnold Roger A. Minear University of Iowa University of Illinois at Urbana-Champaign David Baker University of Tennessee Omkaram Nalamasu AT&T Bell Laboratories Arindam Bose Pfizer Central Research Vincent Pecoraro University of Michigan Robert F. Brady, Jr. Naval Research Laboratory George W. Roberts Mary E. Castellion North Carolina State University ChemEdit Company John R. Shapley University of Illinois MargaretA.Cavanaugh at Urbana-Champaign National Science Foundation Douglas A. Smith Arthur B. Ellis Concurrent Technologies University of Wisconsin at Madison Corporation Gunda I. Georg L. Somasundaram University of Kansas DuPont Madeleine M. Joullie University of Pennsylvania
Michael D. Taylor Parke-Davis Pharmaceutical Research
Lawrence P. Klemann Nabisco Foods Group
William C. Walker DuPont
Peter Willett Douglas R. Lloyd University of Sheffield (England) The University of Texas at Austin
Thorp and Pecoraro; Mechanistic Bioinorganic Chemistry Advances in Chemistry; American Chemical Society: Washington, DC, 1996.
FOREWORD The
A D V A N C E S IN C H E M I S T R Y SERIES was
founded in 1949
by
the
Amer-
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i c a n C h e m i c a l S o c i e t y as a n o u t l e t f o r s y m p o s i a a n d c o l l e c t i o n s o f d a t a i n s p e c i a l areas o f t o p i c a l i n t e r e s t t h a t c o u l d n o t b e a c c o m m o d a t e d i n t h e S o c i e t y ' s j o u r n a l s . It p r o v i d e s a m e d i u m f o r s y m p o s i a t h a t w o u l d otherwise be fragmented because their papers w o u l d be distributed a m o n g s e v e r a l j o u r n a l s o r n o t p u b l i s h e d at a l l . P a p e r s are r e v i e w e d c r i t i c a l l y a c c o r d i n g to A C S e d i t o r i a l standards and receive the careful attention and processing characteristic of A C S p u b l i c a t i o n s . V o l u m e s i n the A D V A N C E S IN C H E M I S T R Y SERIES
maintain
t h e i n t e g r i t y o f t h e s y m p o s i a o n w h i c h t h e y are b a s e d ; h o w e v e r , v e r b a t i m r e p r o d u c t i o n s of p r e v i o u s l y p u b l i s h e d papers are not a c c e p t e d . P a p e r s m a y i n c l u d e r e p o r t s o f r e s e a r c h as w e l l as r e v i e w s , b e c a u s e s y m p o s i a may embrace b o t h types of presentation.
Thorp and Pecoraro; Mechanistic Bioinorganic Chemistry Advances in Chemistry; American Chemical Society: Washington, DC, 1996.
A B O U T THE E D I T O R S
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H.
HOLDEN
T H O R P s t a r t e d h i s c a r e e r as a n
u n d e r g r a d u a t e w i t h T h o m a s J . M e y e r at t h e U n i v e r s i t y o f N o r t h C a r o l i n a at C h a p e l H i l l , w h e r e he studied the electrocatalytic r e d u c t i o n of carbon dioxide. H e c o m p l e t e d his P h . D . on the photochemistry of dioxorhen i u m ( V ) w i t h H a r r y B . G r a y at t h e C a l i f o r n i a Institute of Technology. H i s postdoctoral w o r k at Y a l e U n i v e r s i t y w i t h G a r y W . B r u d vig centered on the redox chemistry of oxomanganese clusters i n aqueous solution. H e is c u r r e n t l y assistant p r o f e s s o r o f c h e m i s t r y at t h e U n i v e r s i t y o f N o r t h C a r o l i n a at C h a p e l H i l l . H i s r e s e a r c h is d i r e c t e d t o w a r d u n d e r standing the fundamental redox pathways i n D N A oxidation, d e v e l o p i n g e l e c t r o c h e m i c a l sensors f o r D N A h y b r i d i z a t i o n , e l u c i d a t i n g t h e m e c h anisms o f excited-state p r o t o n transfer to m u l t i p l y b o n d e d ligands, a n d a c t i v a t i n g s m a l l m o l e c u l e s o f b i o l o g i c a l s i g n i f i c a n c e . H e has r e c e i v e d the C a m i l l e Dreyfus T e a c h e r - S c h o l a r A w a r d , a Presidential Y o u n g I n vestigator A w a r d from the N a t i o n a l Science F o u n d a t i o n , a n d a fellowship in science and engineering from the D a v i d and L u c i l e P a c k a r d F o u n d a t i o n . T h o r p has a p p e a r e d t h r o u g h o u t t h e S o u t h e a s t as t h e bassist f o r N i c k D e m o s a n d the G r e e k Islanders, a n d he a n d his w i f e Patti e n j o y watching college basketball and their n e w son, John.
V I N C E N T L . P E C O R A R O r e c e i v e d his B . S .
de-
gree i n biochemistry from the University of C a l i f o r n i a — L o s A n g e l e s a n d was g r a n t e d the P h . D . i n chemistry, w o r k i n g on m i c r o bial and mammalian iron metabolism under t h e m e n t o r s h i p o f K e n n e t h N . R a y m o n d at the University of C a l i f o r n i a — B e r k e l e y . H e r e v e r t e d to b i o c h e m i s t r y again w h e n he j o i n e d the laboratory of W . W . C l e l a n d i n t h e b i o c h e m i s t r y d e p a r t m e n t at t h e U n i v e r sity of W i s c o n s i n — M a d i s o n . I n M a d i s o n , he was an N I H postdoctoral f e l l o w , using c h i r a l m e t a l l o n u c l e o t i d e s to p r o b e the m e c h a n i s m of p h o s p h o r y l g r o u p transfer i n kinases a n d vii
Thorp and Pecoraro; Mechanistic Bioinorganic Chemistry Advances in Chemistry; American Chemical Society: Washington, DC, 1996.
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A T P s y n t h a s e s . H e j o i n e d t h e f a c u l t y i n t h e c h e m i s t r y d e p a r t m e n t at t h e U n i v e r s i t y o f M i c h i g a n — A n n A r b o r as a n assistant p r o f e s s o r a n d w a s p r o m o t e d t o p r o f e s s o r . H e s p e n t a t e r m at t h e U n i v e r s i t y o f N o r t h C a r o l i n a at C h a p e l H i l l as v i s i t i n g a s s o c i a t e p r o f e s s o r o f c h e m i s t r y . H e is a m e m b e r o f t h e m e t a l l o b i o c h e m i s t r y s t u d y s e c t i o n f o r t h e N a t i o n a l I n s t i t u t e s o f H e a l t h a n d w a s a p p o i n t e d a n a s s o c i a t e e d i t o r o f Inorganic Chemistry. H i s a w a r d s i n c l u d e t h e G . D . S e a r l e B i o m e d i c a l R e s e a r c h Scholarship and an A l f r e d P. Sloan F e l l o w s h i p . H i s research interests span a w i d e range of disciplines that i n c l u d e the b i o l o g i c a l c h e m i s t r y of manganese and v a n a d i u m , the development and exploitation of m e t a l l a c r o w n s for n e w m a t e r i a l s , a n d t h e d e n o v o s y n t h e s i s o f m e t a l l o p e p t i d e s . H e has b e e n i n v o l v e d i n u n d e r g r a d u a t e c u r r i c u l a r r e f o r m a n d w a s a recipient of the University of M i c h i g a n L i t e r a t u r e , Sciences, and the A r t s A w a r d for E x c e l l e n c e i n U n d e r g r a d u a t e I n s t r u c t i o n a n d the U n i versity of M i c h i g a n F a c u l t y R e c o g n i t i o n A w a r d for his c o n t r i b u t i o n s i n science, education, a n d professional service. V i n c e a n d his wife P e g g y Carver enjoy traveling, cooking, and especially eating.
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