CALCIFIED TISSUE TOPICS IN MOLECULAR AND STRUCTURAL BIOLOGY Series Editors Stephen Neidle Watson Fuller Institute of Cancer Research Department of Physics Sutton, Surrey, UK University of Keele, UK Volume 1 Topics in Nucleic Acid Structure, Part 1 Edited by Stephen Neidle (1981) Volume 2 Topics in Nucleic Acid Structure, Part 2 Edited by Stephen Neidle (1982) Volume 3 Molecular Aspects of Anti-Cancer Drug Action Edited by Stephen Neidle and Michael Waring (1983) Volume 4 Biomembrane Structure and Function Edited by Dennis Chapman (1984) Volume 5 Connective Tissue Matrix Edited by David Hukins (1984) Volume 6 Metalloproteins, Part 1: Metal Proteins with Reclox Roles Edited by Pauline Harrison (1985) Volume 7 Metalloproteins, Part 2: Metal Proteins with Non-Redox Roles Edited by Pauline Harrison (1985) Volume 8 Polysaccharides Edited by E.D.T. Atkins (1985) Volume 9 Topics in Nucleic Acid Structure, Part 3 Edited by Stephen Neidle (1987) Volume 10 Protein-Nucleic Acid Interaction Edited by Wolfram Saenger and Udo Heinemann (1989) Volume 11 Calcified Tissue Edited by David Hukins (1989) CALCIFIED TISSUE Edited by DAVID W. L. HUKINS Department of Medical Biophysics University of Manchester, UK M MACMILLAN PRESS Scientific & Medical © The contributors 1989 Softcover reprint ofthe hard cover 1st edition 1989 All rights reserved. No reproduction, copy or transmission of this publication may be made without written permission. No paragraph of this publication may be reproduced, copied or transmitted save with written permission or in accordance with the provisions of the Copyright Act 1956 (as amended), or under the terms of any licence permitting limited copying issued by the Copyright Licensing Agency, 33--4 Alfred Place, London WClE 7DP. Any person who does any unauthorised act in relation to this publication may be liable to criminal prosecution and civil claims for damages. First published 1989 Published by THE MACMILLAN PRESS LTD Houndmills, Basingstoke, Hampshire RG212XS and London Companies and representatives throughout the world Typeset by Wearside Tradespools Fulwell, Sunderland Printed in Great Britain by The Camelot Press Ltd, Southampton British Library Cataloguing in Publication Data Calcified tissue 1. Organisms. Tissues. Calcification I. Hukins, David W.L. II. Series 574.8'21 ISSN 0265-4377 ISBN 978-1-349-09870-5 ISBN 978-1-349-09868-2 (eBook) DOI 10.1007/978-1-349-09868-2 Contents Preface IX The contributors xi 1 Mineral deposits in tissues D. W. L. H ukins 1 Introduction 1 Importance of mineral deposits 2 Characterisation 3 Calcium phosphates 12 Remaining problems 14 2 Histology of mineralised tissues A. J. Freemont 21 Introduction 21 Bone 21 Cartilage 31 Pathological mineralisation 33 3 Scanning X-ray microradiography and microtomography of calcified tissues J. C. Elliot, P. Anderson, R. Boakes and S.D. Dover 41 Introduction 41 Absorption of X-rays by calcified tissues 42 Photographic contact and point projection microradiography 48 Scanning X-ray microradiography and X-ray microtomography 50 Future developments and applications for scanning microradiography and microtomography 61 4 X-ray absorption spectroscopy of mineral deposits D. W. L. Hukins, S. S. Hasnain andJ. E. Harries 65 Introduction 65 Experimental techniques 67 Principles 67 vi Contents Model compounds 75 Biological deposits 82 Conclusions 87 5 Fourier transform infrared spectroscopy and characterisation of biological calcium phosphates R. T. Bailey and C. Holt 93 Introduction 93 Theory 94 Accessories 98 Vibrational spectra of crystalline phosphates 103 Amorphons calcium phosphates 111 Mixed calcium phosphate phases 115 Complex mineralised deposits 118 Concluding remarks 119 6 Sonic velocity and the ultrastructure of mineralised tissues S. Lees 121 Introduction 121 Sonic wave propagation 123 Anisotropy in bone 128 Bone shrinkage 132 Some parameters influencing the sonic plesio-velocity 134 Equatorial diffraction spacing of the collagen in hard tissues 137 A generalised packing model 141 The composition of hard tissues 146 Conclusions 149 7 Some characteristics of mineralised collagen S. Lees 153 Introduction 153 Osteolathyrism and cross-linking density 154 Thermodynamic considerations 160 Water content of mineralised tissue 161 Mobility of the collagen molecule within the fibril 162 Phosphorylated collagen in the bone matrix 164 Influence of the calcium-rich environment 166 Physiocochemical considerations 168 Recapitulation 169 8 The interaction of phosphoproteins with calcium phosphate C. Holt and M. J. J. M. van Kemenade 175 Introduction 175 The caseins 176 Salivary phosphoproteins 190 Dentine phosphophoryns 195 Contents vii Phosvitins 197 Bone phosphoproteins 200 Osteonectin 201 Summary, speculations and conclusions 204 9 Phospholipids and calcification A. L. Boskey 215 Introduction 215 Definitions and properties 215 Distribution of phospholipids in calcified and calcifying tissues 219 Phospholipids in disease states where calcification is altered 225 Phospholipid metabolism 227 In vitro studies 230 Discussion 236 Index 245 Preface The most obvious property of calcified tissues is their rigidity, which enables them to perform such mechanical functions as grinding food, in the case ofteeth, and supporting the body, in the case of bones. However, they also contain macromolecules which are essential for their function and are implicated in the calcification process. Thus bone, for example, has a complex structure at both the histological and the macromolecular levels. An understanding of the relationship between structure and function is essential for understanding the pathology of calcified tissues, and so is of practical as well as academic interest. For example, bone may be inapprop­ riately formed, in rickets, or destroyed during ageing, in osteoporosis. These pathological processes involve cells, as well as the extracellular matrix, and emphasise that bone is a living tissue. Pathological calcification can also occur at sites which are not normally calcified. Deposition of minerals in joints is often associated with rheumatic diseases. Furthermore, hard 'stones' can be formed in many parts of the body- especially in the urinary tract. Minerals can also be deposited on foreign materials which are introduced into the body and so can interfere with the action of, for example, prosthetic heart valves. Therefore, the emphasis in this book is on aspects of calcification that are important in humans- although much of the research described here involves tissue from other mammals, and sometimes other vertebrates. The aim of this book is not to present a comprehensive account of calcified tissues. In common with the rest of the series, it is intended to select some aspects of contemporary research - especially those in which attempts are being made to relate biological function to the structures and interactions of macromolecules. A consequence of this selection is that many of the chapters stress the importance of the extracellular matrix and the interactions of its macromolecules with mineral. Thus this book may be regarded as a sequel to Volume 5 of the series, Connective Tissue Matrix. Since much current research in calcified tissues is aimed at understanding events at the cellular level, the emphasis here on physical, rather than X Preface more obviously biological, techniques is unusual. I have attempted to redress the balance, to some extent, by the inclusion of Chapter 2, which provides a more conventionally biological introduction to the remaining chapters. Nevertheless, there are important reasons for not neglecting the struc­ ture and physical properties of the calcified matrix. Interactions of macromolecules with minerals are an essential feature of the deposition and dissolution of calcified tissues. Furthermore, the most obvious func­ tions of the tissues arise from their physical properties. I hope, therefore, that the selection of material presented here will provide an informative view of the more physical and physico-chemical aspects of contemporary calcified tissue research. Manchester, 1989 D.W.L.H. The contributors P. Anderson A. J. Freemont Department of Biochemistry Departments of Rheumatology and The London Hospital Medical College Pathology Turner Street University of Manchester LondonE12AD, UK Stopford Building Manchester M13 9PT, UK R. T. Bailey Department of Chemistry J. E. Harries University of Strathclyde SERC Dares bury Laboratory Glasgow G11XL, UK Warrington WA4 4AD, UK Adele L. Boskey S. S. Hasnain Department of Ultrastructural SERC Daresbury Laboratory Biochemistry Warrington WA4 4AD, UK The Hospital for Special Surgery 535 East 70th Street C. Holt New York Hannah Research Institute NY 10021, USA Ayr KA6 5HL, UK R. Boakes D. W. L. Hukins Department of Biochemistry Department of Medical Biophysics The London Hospital Medical College University of Manchester Turner Street Stopford Building London E1 2AD, UK Manchester M13 9PT, UK S.D. Dover M. J. J. M. van Kemenade Department of Biophysics Van 't Hoff Laboratory King's College Transitorium 3, Padualaan 8 26-29 Drury Lane 3548 CH Utrecht, The Netherlands London WC2B 5RL, UK Sidney Lees J. C. Elliot Bioengineering Department Department of Biochemistry Forsyth Dental Center The London Hospital Medical College 140Fenway Turner Street Boston London E1 2AD, UK MA02115, USA .