Chitin in Nature and Technology

561 Pages·1986·18.424 MB·English

by  K. D. Parker (auth.), Riccardo Muzzarelli, Charles Jeuniaux, Graham W. Gooday (eds.)

Chitin in Nature
and Technology
Chitin in Nature
and Technology
Edited by
Riccardo Muzzarelli
University of Ancona
Ancona, Italy
Charles Jeuniau((
University of Liege
Liege, Belgium
and
Graham W. Gooday
University of Aberdeen
Aberdeen, Scotland
PLENUM PRESS • NEW YORK AND LONDON
Library of Congress Cataloging in Publication Data
International Conference on Chitin and Chitosan (3rd: 1985: Ancona, Italy)
Chitin in nature and technology.
"Proceedings of the Third International Conference on Chitin and Chitosan, held
April 1-4, 1985, in Senigallia, Italy"-Verso of t.p.
Includes bibliographies and index.
1. Chitin-Congresses. 2. Chitosan-Congresses. I. Muzzarelli, Riccardo A. A.,
1937- . 2. Jeuniaux, Charles. III. Gooday, G. W., 1942- . IV. Title.
QP702.C5I58 1985 574.19'2482 85-28088
ISBN-13: 978-1-4612-9277-7 e-ISBN-13: 978-1-4613-2167-5
DOl: 10.1007/978-1-4613-2167-5
Proceedings of the Third International Conference on Chitin and
Chitosan, held April 1-4, 1985, in Senigallia, Italy
© 1986 Plenum Press, New York
Softcover reprint of the hardcover 1st edition 1986
A Division of Plenum Publishing Corporation
23i1 Spring Street, New York, N.Y. 10013
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
FOREWORD
Exegi monumentum ael'e perennius.
The monument I have built will last longer than bronze.
Horace
My previous book, "Chitin", (1977) was listed by the publisher, as a
"key research book", among the most requested books by libraries. It received
favorable comments from. each of the journals which reviewed it, Science,
198, 28 Oct. 1977, Physiological Entomology, 2(4), Dec. 1977, The Canadian
Institute of Food Science and Technology Journal, April 1978, The Quarterly
Review of Biology, 53:361, 1978, Oceanographic Abstracts, 15:182, 1979,
Annales de Zoologie-Ecologie Animale, 11:127, 1979, and Enzyme & Microbial
Technology, 2, 1980. The variety of these journals testifies to the interdisci
plinary character of chitin studies. "Chitin" has really been a landmark, to
use the definition given by Science, because it stimulated interest in the less
known polysaccharides and in modified chitins, besides chitin itself, to the
point that three International Conferences on Chitin / Chitosan were convened
(Boston, U.S.A. 1977, Sapporo, Japan 1982 and Senigallia, Italy 1985).
In convening the 3rd International Conference on Chitin / Chitosan (1-4
April 1985), one of the main objectives was the preparation of the present
book. While the proceedings of the previous two Conferences were very
valuable, they did not appear in any book catalogs and this severely Ii mi ted
their distribution. Therefore, in view of the need for a full-coverage book
accessible world-wide, and in consideration of the large attendance (238
participants from 16 Countries), Plenum Press agreed to publish the present
book which wants to be more than a mere proceeding. Its spirit is that of a
"Chitin" book for the eighties, of lasting interest for the expert, and of
passionate reading for the cultured man.
While offering the essential background, the present book is devoted
mostly to advanced aspects of pure and applied research. I think that "Chitin"
will remain a major reference for those who seek more basic information.
It is through the competence of the participants who supplied their
manuscripts without delay, the help offered by the coeditors, Prof. Charles
Jeuniaux and Prof. Graham W. Gooday, who also provided some of the "edi
tor's reports" on interesting material that would have otherwise been in
adequate for publication, and the understanding shown by the Government of
Regione Marche, Ancona, Italy, which offered a special grant, that the final
typescript has been produced, and it is a merit of Plenum Press that the
book has been published so shortly after the Conference.
v
I wish to express my heartful and sincere thanks to all participants in
the 3rd International Conference on Chitin / Chitosan, that I had the honor
to chair; its success is also a merit of Maria G. Weckx, general manager,
Irene MuzzareIli, secretary, Barbara B. Muzzarelli, social activities and Dome
nico MencareIli, social relations. I thank Frank Salvi and Catherine Lough
who assisted me in editing and producing the final typescript, as well as the
staff of Chito-Bios s. r.I. , Ancona, including among others Pamela La Marca
and Lorella Falcetelli. All of them join me in expressing best wishes to the
readers of this book, for fruitful studies and gratifying research activities.
Ancona, June 5th, 1985
Riccardo A. A. MuzzareIli
Professor of Chemistry and Biochemistry
Faculty of Medicine
University of Ancona
1-60100 Ancona, Italy
vi
CONTENTS
Progress toward solving the structures of polysaccharides 1
K. D. Parker
Section I
CHITIN IN SKELETAL STRUCTURES OF ANIMALS
Chitinoproteic complexes and mineralization in Mollusk skeletal structures 7
M. Poulicek, M.F. Voss-Foucart and Ch. jeuniaux
Characterization of the insect cuticle layers by laser Raman Spectrometry 13
M. Truchet and B. Mauchamp
Structural studies on the sci erotized insect cuticle 21
M. G. Peter, G. Kegel and R. Keller
Chitin-protein molecular organization in Arthropod cuticles 29
M. M. Giraud-GuiIIe and Y. Bouligand
Pore canals and organization of chitinoproteins in the cuticle of the crab
Carcinus maenas . 37
G. Goffinet and P. Compere
Lipid-linked intermediates in crustacean chitin synthesis 45
M. N. Horst
Section II
CHITIN IN SKELETAL STRUCTURES OF MICROBES
The role of chitin in fungal growth and morphogenesis 55
E. Lopez-Romero and j. Ruiz-Herrera
The role of chitin in hyphal morphogenesis 63
j. H. Sietsma, C.A. Vermeulen and j. G. H. Wessels
Chitin synthesis, dimorphism and virulence in the pathogenic fungus
Candida albicans 71
A. Cassone
Effect of Congo Red on yeast morphogenesis 79
G. L. Vannini, S. Pancaldi and F. PoIi
Roles of chitinases in fungal growth 83
G. W. Gooday, A. M. Humphreys and W. H. McIntosh
Chitin esti mation to measure fungal biomass 93
Editor's Report: G. W. Gooday
Studies of autolytic enzymes in fungi 99
Editor's Report: G. W. Gooday
vii
Comparison of chitin fibril structure and assembly in three unicellular
organisms 107
W. Herth, M. Mulish and P. Zugenmaier
Polygalactosamine produced by a microorganism 121
H. Takagi and K. Kadowaki
Section III
CHITIN SYNTHESIS. INHIBITION
Benzoylaryl ureas insecticides: compounds interfering with chitin synthesis 131
A. G. M. Willems, M. S. Brouwer and B. jongsma
Inhibition of chitin synthesis in insect systems 139
E. Cohen
Chitin biosynthesis in insects and its disruption as a means of pest control 147
A. Retnakaran
Comparative effects of benzoylaryl ureas on insects 165
Editor's Report: G. W. Gooday
Biosynthesis of chitin by insect epidermal cells: effect of benzoyl phenyl
ureas 171
B. Mauchamp and E. Caminade
Effect of diflubenzuron on the cuticle of crab larvae 175
M. E. Christiansen
Toxicity of diflubenzuron to non-target organisms 183
R. A. A. Muzzarelli
Chitin inhibitors in pest management in India 187
M. Balasubramanian
Mode of inhibition of chitin synthesis by diflubenzuron 193
T. Mitsui
New synthetic polyoxin analogs for chitin synthesis inhibition 197
H. A. Smith, P. Shenbagamurthy, F. Naider and G. M. Becker
Nikkomycin Z as inhibitor of Candida albicans growth 203
M. Gonneau, j. C. Yadan, P. Sarthou and F. Le Goffic
Section IV
MOLECULAR RECOGNITION AND BIODEGRADATION
Chitosan both activates genes in plants and inhibits RNA synthesis in fungi 209
L.A. Hadwiger, D. F. Kendra, B.W. Fristensky and W. Wagoner
Chitosan and other polyamines: antifungal activity and interaction with
biological membranes 215
j. L. Leuba and P. Stossel
Chitinase, a defense of higher plant against pathogens 223
T. Boller
Plant chitinases and lysozymes 231
Editor's Report: G. W. Gooday
The role of chitinases and chitin syntase inhibitors in controlling
plant pathogenic fungi
I. Chet, E. Cohen and I. Elster
Chitinase activities in ani mals, fungi and bacteria 241
Editor's Report: G. W. Gooday
Chitin deacetylases in invertebrates 263
Editor's Report: G. W. Gooday
viii
Recognition of human erythrocytes by a chitin-binding lectin of a
fungus, Conidiobolus lamprauges 269
K. Oishi and F. Ishikawa
Section V
CHEMISTRY OF CHITIN
Dry chitosan salts and complexes of aliphatic carboxyl acids 279
P. R. Austin and S. Sennett
Chemical modifications of chitin and chitosan 287
K. Kurita
Chemically modified chitosans 295
Editor's Report: R. A. A. Muzzarelli
The chelating ability of aminoacid glucans and sugar acid chitosans 321
R. A. A. Muzzarelli
Ionic interactions between chitosan and oxidised cellulose 331
J. G. Domszy and G. A. F. Roberts
Chitin and chitosan solutions 337
Editor's Report: R. A. A. MuzzarelIi
Synthesis of oligosaccharides representing the chitobiosyl
link in glycoproteins 353
E. KalIin, S. Svensson, G. Gronberg and O. Mansson
Stable isotopic studies on chitin, measurements on chitin / chitosan
isolates and D-glucosamine hydrochloride from chitin 357
A. Schimmelmann and M. J. De Niro
Characterization of chitin derivatives by pyrolysis-gas chromatography 365
D. H. Davies, E. R. Hayes and G. S. Lal
Synthesis and physico-chemical properties of the polyampholyte chitosan
6-sulfate 371
A. M. Naggi, G. Torri, T. Compagnoni and B. Casu
Small angle x-ray scattering study of chitosan 6-sulfate in water 379
S. S. Stivala, A. Patel and S. Patel
The determination of the degree of acetylation of chitosans by
spectrophotometry 385
R. A. A. Muzzarelli and R. Rocchetti
Filmogenic properties of chitin / chitosan 389
Editor's Report: R. A. A. Muzzarelli
Physical modifications of chitin and chitosan 403
M. Yalpani
Whole cells and enzymes immobilized on chitosan 407
Editor's Report: R. A. A. Muzzarelli
Section VI
MEDICAL USES OF CHITIN
Chitosan effect in vascular surgery, tissue culture and tissue regeneration 435
W. G. Malette, H. J. Quigley Jr. and E. D. Adickes
Evaluation of chitosan as a new hemostatic agent: in vitro and in vivo
experiments 443
G. Fradet, S. Brister, D. S. Mulder, J. Lough and B. L. Averbach
ix
Inhibitory action of sulfated chitin derivatives on the hydrolytic activity
of thrombin 453
W. Okiei, S. Nishimura, o. Somorin, N. Nishi and S. Tokura
Sulfated derivatives of chitosan and their characterization with respect
to biological activity 461
S. Hirano, j. Kinugawa and A. Nishioka
Sulfated N-carboxymethyl chitosans as blood anticoagulants 469
R. A. A. Muzzarelli, F. Tanfani, M. Emanuelli, E. Chiurazzi
and M. Piani
Immunological activity of chitin derivatives 477
K. Nishimura, S. Nishimura, N. Nishi, S. Tokura and I. Azuma
Immunopotentiating effect of N-acetyl-chito-oligosaccharides 485
S. Suzuki, K. Suzuki, A. Tokoro, Y. Okawa and M. Suzuki
Adhesion properties of mouse spleen lymphocytes on chitin
and its derivatives 493
S. Nishimura, N. Nishi, M. Kaneko and S. Tokura
Biomedical evaluation of acylated chitins as coating materials 497
T. Komai, S. Kaifu, M. Matsushita, I. Koshino and T. Kon
Chitosan in dentistry 507
P. L. Sapelli, V. Baldassarre, R. A. A. Muzzarelli and M. Emanuelli
Section VII
CHITIN ECOLOGY
Chitin production by animals and natural communities in marine
environment 515
Ch. jeuniaux, j. C. Bussers, M. F. Voss-Foucart and M. Poulicek
Chitin diagenesis in deep-water sediments 523
M. Poulicek, R. Machiroux and C. Toussaint
Anaerobic decomposition of chitin in fresh water sediments 531
H. Sturz and j. Robinson
Chitinolytic communities from an anaerobic estuarine environment 539
R. Pel and j. C. Gottschal
Chitin degradation in natural environment (Mollusk shells and crab
carapaces) 547
M. Poulicek, G. Goffinet, M. F. Voss-Foucart, j. C. Bussers,
M. F. jaspar-Versali and C. Toussaint
Chitosan as a tool for the purification of waters 551
Editor's Report: Ch. jeuniaux
Author Index 571
Organism Index
575
Subject Index
579
x
PROGRESS TOWARDS SOLVING THE
STRUCTURES OF POLYSACCHARIDES
K. D. PARKER
Astbury Department of Biophysics, The University of Leeds
Leeds, LS2 9jT, U.K.
STRUCTURE AT LOW RESOLUTION
The art of determining the structure of a regular fibrous molecule is
well illustrated by the example of a-chitin. In 1950 Darmon and Rudall
obtained good X-ray fibre diffraction patterns, good polarised infra-red
spectra and built analogue molecular models of the stick and ball kind.
Their conclusions are now considered to be wrong whilst Carlstrom in 1957
using almost the same data deduced a structure which is widely held to be
substantially correct. It appears to us now that both these attempts were
based on data which is insufficient to generate a uniquely correct solution.
Darmon and Rudall took account of some fine detail in the X-ray and I.R.
results and were led astray. Carlstrom, more selective, minimised or put
aside these details, used superior model building and gave an acceptable
solution. These discarded details still await a satisfactory explanation.
Many polysaccharide structures have been studied since then by similar
methods with similar certainty and uncertainty in the results. Progress in
protein and nucleic acid structures has tended to lead and inform parallel
work on polysaccharides, and whilst the practical techniques have improved
over 30 years the general approach has changed very little. Alginic acid
in our laboratory provides a good illustration. Astbury in 1945 was hope
lessly handicapped by lack of chemical information at that time. Sub
sequently in 1973 we were able to deduce crystal structures for the two
components of alginic acid, p-mannuronic acid and p-guluronic acid, studied
separately. The basic conformations of these molecular chains each in a
crystalline state is thus known with some confidence. We can also surmise
that the manner of packing of chains in the crystal is energetically
favourable. We were also able to make tentative suggestions about the dis
positions of some of the side groups, but it is at this level that hard
evidence weakens and personal judgement or guesswork enters.
In 1950 to study structure was an end in itself; now we do so with the
further aim of increasing our knowledge of the physical and chemical
potentialities of the substance examined. With nucleic acid the mere out
line structure has been sufficient to generate new ideas of molecular biology.
With alginic acid very limited structural information has stimulated specu
lation on the mechanism of gel formation which may be technologically
helpful. In both these examples the contribution of structure to the argu
ment is so general that its value is difficult to assess. Trying to be