Metal Ions in Biological Systems Volume 40 The Lanthanides

and Their Interrelations with Biosystems 1st Edition

Visit the link below to download the full version of this book:

https://medipdf.com/product/metal-ions-in-biological-systems-volume-40-the-lanth
anides-and-their-interrelations-with-biosystems-1st-edition/

Click Download Now

 METAL IONS IN
B K H M A L SYSTEMS
Edited by
Astrid Sigel
and Helmut Sigel
Department of Chemistry
Inorganic Chemistry
University of Basel
CH-4056 Basel, Switzerland

VOLUME 40

The Lanthanides and

Their Interrelations with Biosystems

Boca Raton London New York

CRC Press is an imprint of the

Taylor & Francis Group, an informa business
 First published 2003 by a joint publication ofFontisMedia S.A. and Marcel Dekker, Inc.

Published 2018 by CRC Press

Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742

© 2003 by Taylor & Francis Group, LLC

CRC Press is an imprint of Taylor & Francis Group, an Informa business

No claim to original U.S. Government works

ISBN 13: 978-0-8247-4245-4 (hbk)

This book contains information obtained from authentic and highly regarded sources.
Reasonable efforts have been made to publish reliable data and information, but the author and
publisher cannot assume responsibility for the validity of all materials or the consequences of
their use. The authors and publishers have attempted to trace the copyright holders of all
material reproduced in this publication and apologize to copyright holders if permission to
publish in this form has not been obtained. If any copyright material has not been acknowledged
please write and let us know so we may rectify in any future reprint.

Except as permitted under U.S. Copyright Law, no part of this book may be reprinted,
reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means,
now known or hereafter invented, including photocopying, microfilming, and recording, or in
any information storage or retrieval system, without written permission from the publishers.

For permission to photocopy or use material electronically from this work, please access www.
copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc.
(CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit
organization that provides licenses and registration for a variety of users. For organizations that
have been granted a photocopy license by the CCC, a separate system of payment has been
arranged.

Trademark Notice: Product or corporate names may be trademarks or registered trademarks,

and are used only for identification and explanation without intent to infringe.

Visit the Taylor & Francis Web site at

http://www.taylorandfrancis.com

and the CRC Press Web site at

http://www.crcpress.com

The figure on the dustcover is Figure 5a of Chapter 9

by C. Turro, P. K.-L. Fu, and P. M. Bradley.

This book is a joint publication ofFontisMedia S.A.

FontisMedia S.A.
Avenue Vinet 19
CH-1004 Lausanne, Switzerland
tel: 41-21-648-3971; fax: 41-21-648 39 75
WWW: http://www.fontismedia.com
 Preface to the Series

Recently, the importance of metal ions to the vital functions of living

organisms, hence their health and well-being, has become increasingly
apparent. As a result, the long-neglected field of “bioinorganic chemistry”
is now developing at a rapid pace. The research centers on the synthesis,
stability, formation, structure, and reactivity of biological metal ion-
containing compounds of low and high molecular weight. The metabolism
and transport of metal ions and their complexes is being studied, and new
models for complicated natural structures and processes are being devised
and tested. The focal point of our attention is the connection between the
chemistry of metal ions and their role for life.
No doubt, we are only at the brink of this process. Thus, it is with
the intention of linking coordination chemistry and biochemistry in their
widest sense that the Metal Ions in Biological Systems series reflects the
growing field of “bioinorganic chemistry”. We hope, also, that this series
will help to break down the barriers between the historically separate
spheres of chemistry, biochemistry, biology, medicine, and physics, with
the expectation that a good deal of future outstanding discoveries will be
made in the interdisciplinary areas of science.
Should this series prove a stimulus for new activities in this fascinating
“field”, it would serve its purpose and would be a satisfactory result for the
efforts spent by the authors.

Fall 1973 Helmut Sigel

Department o f Chemistry
Inorganic Chemistry
University o f Basel
CH-4056 Basel, Switzerland
iii
 Preface to Volume 40

The term 'lanthanides' usually encompasses lanthanum plus the following

14 elements from cerium (element 58) to lutetium (element 71). Together
with yttrium, element 39 (and partly even scandium, element 21), they are
sometimes collectively termed 'rare earth elements'. However, this name
is misleading since the lanthanides are not rare: Thulium, the scarcest of
them, is approximately twice as abundant as iodine in the Earth's crust and
its occurrence is about equal to that of bismuth. These and other aspects
are dealt with in the first two chapters, where also some of the chemical
properties of the lanthanides such as oxidation states and ionic radii are
summarized as well as their mobilization through microorganisms like
bacteria and fungi.
Properties of lanthanide complexes with amino acids, nucleotides,
and other bioligands in solution are presented in the third chapter whereas
Chapter 4 summarizes the coordination chemistry of these elements as
it follows from X-ray structural studies. Indeed, as discussed in the next
three chapters, certain properties of the lanthanides resemble those of
biologically relevant metal ions, e.g., Ca2+, and this allows to use the
lanthanides as substitutes and to probe metal ion-dependent enzymes.
The well known property of certain lanthanide chelates to emit a strong
characteristic fluorescence when excited with ultraviolet light, enables
their utilization as diagnostic labels. The use of fluorescent sensors and
the involvement of lanthanides is now common place in biological, physi­
ological, and clinical applications.
Chapter 8 discusses lanthanides as probes for electron transfer in
proteins. The feature that single-stranded oligonucleotides enhance the
emission of Eu(III) and Tb(III) in solution is utilized in the detection of
v
VI PREFACE TO VOLUME 40

distorted DNA regions, and also in probing the interactions of DNA and
RNA with enzymes, proteins, and drugs (Chapter 9). Artificial peptidases,
nucleases, and hydrolases based on lanthanide ions and their complexes
are dealt with in Chapters 10-12. The search for such catalysts is a chal­
lenging topic for chemists, especially regarding the hydrolysis of phos­
phate ester bonds because these belong to the kinetically most stable
binding units in nature. In Chapter 13 lanthanide ions are examined as
probes for biological metal ions in the structure and catalytic mechanism
of ribozymes, and this is followed by an account about lanthanides as
shift and relaxation agents in determining the structure of proteins and
nucleic acids.
Magnetic resonance imaging (MRI) has evolved over the last 10
years into one of the most powerful techniques in medical diagnostics.
In 2001 around 40 million MRI examinations were conducted worldwide
and Gd(III)-based contrast agents play here significant roles (Chapter
15). The interaction of such agents with proteins, e.g., human serum
albumin, is described in Chapter 16. The metabolism and toxicity of
lanthanides as outlined in the following Chapter 17 is clearly an important
topic considering the medical application of their complexes. Finally,
in the terminating chapter cell responses to lanthanides and potential
pharmacological actions of these elements are considered.

Astrid Sigel
Helmut Sigel
 Contents

PREFACE TO THE SERIES iii

PREFACE TO VOLUME 40 v
CONTRIBUTORS xvii
CONTENTS OF PREVIOUS VOLUMES xxi
HANDBOOK ON TOXICITY OF INORGANIC COMPOUNDS lvii
HANDBOOK ON METALS IN CLINICAL
AND ANALYTICAL CHEMISTRY lvii
HANDBOOK ON METALLOPROTEINS lvii

Chapter 1
DISTRIBUTION OF THE LANTHANIDES IN THE
EARTH'S CRUST 1
Stuart Ross Taylor and Scott M. McLennan
1. Geochemical Behavior of the Lanthanides 2
2. Lanthanide Mineralogy 10
3. Samarium-Neodymium and Hafnium-Lutetium Isotope
Geochemistry 11
4. The Oceanic Crust of the Earth 12
5. The Continental Crust 14
6. Lanthanides in the Continental Crust 21
7. Europium as a Geochemical Tracer 32
Abbreviations and Definitions 33
References 35

VII
viii CONTENTS

Chapter 2
MOBILIZATION OF LANTHANIDES THROUGH THE
TERRESTRIAL BIOSPHERE 39
Robert A. Bulman
1. Basic Lanthanide Chemistry 40
2. Sources of Lanthanides for Environmental Processes 42
3. Weathering of Rocks: Formation of Soil and Abundance
of Lanthanides 44
4. Microbial Interactions with Lanthanides 51
5. Uptake of Lanthanides into Plants 55
6. General Conclusions 61
Acknowledgments 61
Abbreviations and Definitions 62
References 62

Chapter 3
COMPLEXES OF LANTHANIDE IONS WITH AMINO ACIDS,
NUCLEOTIDES, AND OTHER LIGANDS OF BIOLOGICAL
INTEREST IN SOLUTION 69
Herbert B. Silber and Sarah J. Paquette
1. Introduction 70
2. Results from Complexes with Model Ligands 75
3. Complexes of Amino Acids with LanthanideIons 79
4. Lanthanide Phospholipid Complexes 84
5. Interactions of Nucleotides and Lanthanide Ions 86
6. Complexes of Lanthanides with Sugar-TypeLigands 89
7. Conclusions and Perspectives 93
Acknowledgments 94
Abbreviations and Definitions 94
References 95

Chapter 4
BIOLOGICALLY RELEVANT STRUCTURAL
COORDINATION CHEMISTRY OF SIMPLE
LANTHANIDE ION COMPLEXES 105
Jack M. Harrowfield
CONTENTS IX

1. Introduction 106
2. X-Ray Structural Studies of Simple Lanthanide Ion Complexes 107
3. Summary and Overview 136
Acknowledgments 145
Abbreviations 145
References 146

Chapter 5
LANTHANIDE IONS AS PROBES IN STUDIES OF METAL
ION-DEPENDENT ENZYMES 161
Etsuro Yoshimura and Tokuko Watanabe
1. Introduction 162
2. Modulation of Enzyme Activity by Lanthanide Ions and
Suitability as Probes 163
3. Conclusions 181
4. Appendix: Methodologies 183
Abbreviations 188
References 188

Chapter 6
LANTHANIDE CHELATES AS FLUORESCENCE LABELS
FOR DIAGNOSTICS AND BIOTECHNOLOGY 191
Kazuko Matsumoto andJingli Yuan
1. Introduction 192
2. Lanthanide Fluorescent Complexes and Labels 194
3. Application to Time-Resolved Fluoroimmunoassay 210
4. Application to DNA Hybridization Assay and Cell
Activity Assay 216
5. Application to Chromatography 219
6. Application to Time-Resolved FluorescenceImaging 221
7. Conclusions 223
Abbreviations 224
References 226
X CONTENTS

Chapter 7
RESPONSIVE LUMINESCENT LANTHANIDE COMPLEXES 233
David Parker and J. A. Gareth Williams
1. Introduction 234
2. Mechanistic Basis for Mode of Action 243
3. pH Dependent Luminescence 251
4. Anion Dependent Luminescence 262
5. Oxygen Dependent Luminescence 269
6. Modulation by Metal Ions and Selected Molecules 271
7. Concluding Remarks 274
Abbreviations 275
References 276

Chapter 8
LANTHANIDE IONS AS PROBES OF ELECTRON
TRANSFER IN PROTEINS 281
Ronald M. Supkowski and William DeW. Horrocks, Jr.
1. Introduction 282
2. The Parvalbumin/Lanthanide Model System 285
3. Proof of Electron Transfer in the Model System 290
4. Application of Markus Theory of Electron Transfer to
the Model System 295
5. Conclusions 316
Acknowledgments 317
Abbreviations and Definitions 318
References 318

Chapter 9
LANTHANIDE IONS AS LUMINESCENT PROBES
OF PROTEINS AND NUCLEIC ACIDS 323
Claudia Turro, Patty K.-L. Fu, and Patricia M. Bradley
1. Introduction 324
2. Photophysical Properties of Lanthanides 325
3. Nucleic Acids 333
CONTENTS Xi

4. Proteins and Enzymes 340

5. Conclusions 345
Acknowledgments 345
Abbreviations 345
References 347

Chapter 10
LANTHANIDE-PROMOTED PEPTIDE BOND HYDROLYSIS 355
Makoto Komiyama and Tohru Takarada
1. Introduction 356
2. Peptide Hydrolysis by Ce(IV) 357
3. Activities of Other Lanthanide and Non-LanthanideIons 359
4. Mechanism of Peptide Hydrolysis 360
5. Homogeneous Hydrolysis of Peptides by
Lanthanide-Cyclodextrin Complexes 363
6. Origin of the Remarkable Activity of Ce(IV) 364
7. Conclusion 365
Acknowledgments 366
Abbreviations 366
References 366

Chapter 11
LANTHANIDE-CATALYZED HYDROLYSIS OF PHOSPHATE
ESTERS AND NUCLEIC ACIDS 369
Hans-Jorg Schneider and Anatoly K. Yatsimirsky
1. Introduction and Scope 370
2. Mechanisms of Phosphate Ester Hydrolysis 374
3. Formation of Lanthanide Complexes in Water and
Their Catalytic Use 394
4. Kinetics of Catalytic Phosphate Ester Hydrolysis 400
5. Lanthanide Alkoxide and Hydroperoxide Complexes 421
6. Catalysis with Di- and Polynuclear Complexes 425
7. Analogs of Functional Amino Acids in Catalytic Centers 431
8. Other Lanthanide-Based Systems 438
9. A Final Performance Comparison of Lanthanides
with Other Metal Ions 440
XII CONTENTS

10. Conclusions and Outlook 443

Acknowledgments 444
Abbreviations 444
References 446

Chapter 12
SEQUENCE-SELECTIVE SCISSION OF DNA AND RNA
BY LANTHANIDE IONS AND THEIR COMPLEXES 463
Makoto Komiyama
1. Significance of Site-Selective Scission of DNA and RNA 464
2. Molecular Design for a Sequence-Selective Scission 465
3. Sequence-Selective DNA Cutters (Artificial
Restriction Enzymes) 466
4. Sequence-Selective RNA Cutters (Ribozyme Mimics) 468
5. Conclusion 472
Acknowledgments 473
Abbreviations 473
References 473

Chapter 13
LANTHANIDE IONS AS PROBES FOR METAL IONS IN
THE STRUCTURE AND CATALYTIC MECHANISM
OF RIBOZYMES 477
Roland K. O. Sigel and Anna Marie Pyle
1. Introduction 478
2. Using Lanthanides to Study the Catalytic Mechanism
of Ribozymes 481
3. Defining Metal Ion Binding Sites by Lanthanide-Induced
Cleavage of the Phosphodiester Backbone 492
4. X-Ray Crystal Structures of Ribozymes and Lanthanides 503
5. Conclusions and Possible Future Applications of
Lanthanides in Ribozyme Chemistry 504
Acknowledgments 504
Abbreviations and Definitions 504
References 505
CONTENTS xiii

Chapter 14
LANTHANIDES AS SHIFT AND RELAXATION AGENTS IN
ELUCIDATING THE STRUCTURE OF PROTEINS
AND NUCLEIC ACIDS 513
Carlos F. G. C. Geraldes and Claudio Luchinat
1. Introduction 514
2. Lanthanides as Structural Probes 516
3. Theory of Paramagnetic NMR Effectsof Lanthanide Ions 518
4. Stable Lanthanide-Macromolecule Complexes 531
5. Structural Studies of Proteins in Solution 542
6. Probing Protein Surfaces and Protein Interactions with
Lanthanide Chelates 562
7. Ln3+ as Probes of Nucleic Acids 568
8. Conclusions and Perspectives 572
Acknowledgments 575
Abbreviations 575
References 577

Chapter 15
LANTHANIDE IONS AS MAGNETIC RESONANCE IMAGING
AGENTS. NUCLEAR AND ELECTRONIC RELAXATION
PROPERTIES. APPLICATIONS 589
Lothar Helm, Eva Toth, and André E. Merbach
1. Introduction 590
2. Physical Principles of Medical Imaging by Nuclear
Magnetic Resonance 593
3. Relaxation Enhancement Induced by Gd(III) Complexes 594
4. Application: Design of High Relaxivity Agents 617
5. Conclusions 626
Acknowledgments 627
Abbreviations 627
Structural Formulas of Ligands 628
References 635
XIV CONTENTS

Chapter 16
INTERACTIONS OF LANTHANIDES AND THEIR
COMPLEXES WITH PROTEINS. CONCLUSIONS
REGARDING MAGNETIC RESONANCE IMAGING 643
Silvio Aime, Alessandro Barge, Mauro Botta, andEnzo Terreno
1. Generalities on Magnetic Resonance Imaging and Gd(III)-Based
Contrast Agents 644
2. Interactions of Lanthanide(III) Ions with Proteins 651
3. Interactions of Gadolinium(III)Complexes with Proteins 653
4. Responsive Systems Based on Protein Binding 667
5. Concluding Remarks 677
Acknowledgments 677
Abbreviations 678
References 679

Chapter 17
METABOLISM AND TOXICITY OF THE LANTHANIDES 683
Robert A. Bulman
1. Introduction 684
2. Chemistry 684
3. Sites of Deposition in Animals 687
4. Routes of Uptake by Man 689
5. Aspects of Biochemical Behavior and Toxicity 697
6. General Conclusions 700
Acknowledgments 701
Abbreviations 701
References 701

Chapter 18
CELL RESPONSES TO LANTHANIDES AND POTENTIAL
PHARMACOLOGICAL ACTIONS OF LANTHANIDES 707
Kiii Wang, Yi Cheng, Xiaoda Yang, and Rongchang Li
1. Introduction 709
2. Biological Effects of Potential Medical Significance 712