Proceedings of the Fourth International Symposium on Cyclodextrins: Munich, West Germany, April 20–22, 1988

526 Pages·1988·21.612 MB·English

by  Friedrich Cramer (auth.), O. Huber, J. Szejtli (eds.)

PROCEEDINGS OF THE FOURTH INTERNATIONAL
SYMPOSIUM ON CYCLODEXTRINS
Advances in Inclusion Science
Proceedings of the
Fourth International Symposium
on Cyclodextrins
Munich, West Germany, April 20-22, 1988
Edited by
O.HUBER
Consortium/iir Elektrochemische Industrie GmbH.
Munich, F.R.G.
and
J. SZEJTLI
CHINOIN Pharmaceutical-Chemical Works, Budapest, Hungary
Dedicated to the 65th Birthday
of Professor F. Cramer
KLUWER ACADEMIC PUBLISHERS
DORDRECHT I BOSTON I LONDON
Library of Congress Cataloging in Publication Data
International SympOsium on Cyclodextrlns (4th: 1988 : Munich.
Germany>
Proceedings of the Fourth International Symposium on Cyclodextrln.
Munich. West Germany. April 20-22. 1988 edited by O. Huber. J.
SzeJtl1.
p. cm. -- (Advances In Inclusion science)
Bibliography: p.
1. Cyclodextrlns--Blotechnology--Congresses. 2. Cyclodextrlns In
pharmaceutical technology--Congresses. 3. Cyclodextrlns--Industrlal
appllcatlons--Congresses. I. Huber. O. II. SzeJtll. Jozsef.
III. Title. IV. Series.
TP248.64.C92I57 1988
547.7'815--dc19 88-26681
CIP
ISBN-13 :978-94-0 10 -7690-6 e-ISBN-13:978-94-009-2637-0
DOl: 10. 1007/978-94-009-2637-0
Published by Kluwer Academic Publishers,
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Softcover reprint of the hardcover lst edition 1988
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CONTENTS
Preface ix
Cramer, F. / Introductory Remarks
1. CHEMISTRY, ENZYMOLOGY AND PRODUCTION OF CYCLODEXTRINS
1.1. Horikoshi, K.
Enzymology and Molecular Genetics of CD-Forming Enzymes 7
1.2. Bender, H.
Studies on The Reaction Mechanism of Cyciodextrin Glyco-Syl- Transferases: Subsite
Analysis 19
1.3. Miikela, M. J., Paavilainen, S. K., Korpela T. K.
Cultural Characteristics of a Cyciomaltodextrin Glucano-Transferase-Producing
Alkalophilic Bacillus SP. 27
1.4. Annbruster, F. C.
Use of Cyciohexane in The Production of Pure Alpha-And Beta-Cyciodextrins 33
1.5. Bergsma, J., Bruinenberg, P. M., Hokse, H., Meiberg, J. B. M.
Cyciodextrins From Potato Starch. Recent Developments. 41
1.6. Crump, S. P., Rozzell, J. D.
Production of Cyciodextrins Using Immobilized Enzymes. 47
1.7. Sakano, Y., Shiraishi, T., Kusano, S., Kogure, Y., Norman, B. E., Yoshida, Y.
Immobilization of Pullulanase And Succesive Synthesis of Branched Cyciodextrins by
Immobilized Pullulanase. 55
1.8. SchOnberger, B. P., Jansen, A. C. A., Janssen, L. H. M.
The Acid Hydrolysis of Cyciodextrins and Linear Oligosaccharides: A Comparative
StUdy. 61
1.9. Mattsson, P., Miikelli, M., Korpela, T.
Isolation and Purification of Gamma-Cyciodextrin by Affinity Chromatography 65
1.10. Schmid, G., Englbrecht, A., Schmid, D.
Cloning and Nucieotide Sequence of a Cyciodextrin Glycosyltransferase Gene From The
Alkalophilic Bacillus 1-1. 71
1.11. Seydel, W., Binder, F., Schmid, G., Huber, 0., Bock, A.
Expression of The Gene For Cyciodextrin-Glycosyl-Transferase From Klebsiella In E.
Coli 77
1.12. Seres, G., Barcza, L.
Method Development For Economic Production of Cyciodextrins By Means Of Ternary
Complex Formation 81
1.13. Schmid, G., Huber, O. S., Eberle, H. J.
Selective Complexing Agents For The Production Of y-Cyciodextrin 87
2. CYCLODEXTRIN DERIVATIVES
2.1. Liptak:, A.
Preparation and NMR Study of Maitooligomers 95
2.2. Friedman, R. B.
A Chemically Modified Cyciodextrin 103
2.3. Fenichel, L., Bak6, P., T6ke, L., Szente, L., Szejtli, J.
Methylation of Cyclodextrins Via Phase-Transfer Catalysis 113
vi CONTENTS
2.4. Hadjoudis, E., Kondilis, P., Mavridis, 1., Tsoucaris, G.
Environmental Effects on Molecular Properties of Organic Compounds. III.
Cyclodextrins With a Schiff-Base Moiety. 119
2.5. O'Sullivan, T., Darcy, R., Mageswaran, S.
The Inclusion Properties of6-Linked ~-Cyclodextrin 1-Thio-~-D-Glycosides. 125
2.6. O'Sullivan, T., Darcy, R., Georganta, G.
Selective Multiple 6-Substitution in Cyclodextrin by Hydrophobic and Hydrophilic
Groups. 129
2.7. Wenz, G., von der Bey, E.
Inclusion Properties of Hydrophobic Derivatives of Cyclodextrins (CDs) 133
2.8. Otta, K., Zsadon, B., Farag6, J., Szejt1i, J., Tiid6s F.
Cyclodextrin-Cellulose Copolymers 139
2.9. Mischnick-Liibbecke, P., K5nig, W. A., Wenz, G.
Characterization of Cyclodextrin Derivatives by The Reductive-Cleavage Method 145
2.10. Coleman, A. W., Tsoucaris, G., Galons, H., Parrot, H., Miocque, M.
Modified Cyclodextrins; Substitution of 03 and Complexation of Metals 151
3. CHEMICAL AND PHYSICAL PROPERTIES OF CD-COMPLEXES
3.1. Saenger, W.
Chemical and Physical Studies On Cyclodextrin Inclusion Compounds 159
3.2. Ripmeester, J. A., Majid, A.
Preparation and 13C-NMR Identification of Solid Cyclodextrin Inclusion Compounds. 165
3.3. Barone, G., Castronuovo, G., Del Vecchio, P., Ella, V.
Inclusion Compounds in Water. Interaction of a-Cyclodextrin With Urea Derivatives at
25°C. 173
3.4. Yoshida, N., Seiyama, A., Fujimoto, M.
Dynamic Aspects of Molecular Inclusion Reactions by Cyclo-Dextrins 181
3.5. Casu, B., Grenni, A., Naggi, A., Torri, G.
Interaction ofCyclodextrins With Glycollpids. IH-NMR Studies 189
3.6. Stoddart, J., Zarzycki, R.
Chemically-Modified Cyclodextrins As Second Sphere Ligands for Transition Metal
Complexes 197
3.7. Norwig, J., Gelder, T., Kraus, Ch., Mehnert, W., Rehse, K., Fr5mming, K.-H.
Some Interesting Aspects in 1H -NMR Spectroscopy by Cyclodextrin Complexation 205
3.8. Taneya, A., Yoshida, N., Fujimoto, M.
Molecular Inclusion Reaction of Charged Cyclodextrins 209
3.9. Vecchi, C., Naggi, A., Torri, G.
Inclusion Complexes of Naphthols With Cyclodextrins in Aqueous Solution. A IH-NMR
Study 215
3.10. Ebel, S., Karger, A.
IR-Spectroscopic Measurement of the P-Nitrophenol ~-Cyclo-Dextrin Equilibrium in
Aqueous Solution 221
3.11. Fenyvesi, E., Decsei, L., UjMzy, A., Zsadon, B., Szejt1i, J.
Complexes of Insoluble Cyclodextrin Polymers 227
3.12. Bajor, T., Szente, L., Szejt1i, J.
Methods For Characterization of The Wettability of Cyclodextrin Complexes 237
3.13. Le Bas, G., Mason, S. A., Rysanek, N., Tsoucaris, G.
Detailed Structure of an a-Cyclodextrin-Cyclopentanone Clathrate by Neutron Diffrac-
tion 243
3.14. Taraszewska, J., Piasecki, A. K.
Influence of Ethanol on The Complexation of Isometric Chloronitrobenzenes By ~-
Cyclodextrin 247
3.15. RODs-Hoffet, A.
Characterisation of ~-Cyclodextrin Complexes 253
CONTENTS vii
4. CYCLODEXTRINS IN PHARMACEUTICALS
4.1. Duchene, D.
New Trends in Phannaceutical Applications of Cyclodextrin Inclusion Compounds 265
4.2. Fr()mming, K.-H., Norwig, J., Mehnert, W.
Menadione Inclusion Compounds With Mixtures of Natural Cyclodextrins 277
4.3. Doorne, H. V., Bosch, E. H., Lerk, C. F.
Interactions Between Cyclodextrins and Some Antimycotic Imidazole Derivatives:
Studies on Solubility and Antimicrobal Activity. 285
4.4. Kata, M., Aigner Z., Fahr, F.
Increasing The Solubility Characteristics of Iomegiamic Acid With ~-Cyclodextrin 293
4.5. Ueda, H., Nagai, T.
The Inclusion Complex of Tolbutamide With Maltosyl (G2) -~-Cyclo-Dextrin in
Aqueous Solution and in the Solid State 299
4.6. Vikmon, M., Gerl6czy, A., Szejtli, J.
Complexation of Polyene Antibiotics With y-Cyclodextrin 307
4.7. Bekers, 0., Beijnen, J. H., Underberg, W. J. M.
The Effect of Cyclodextrins on the Mitomycin Stability in Acidic Aqueous Media 313
4.8. Giordano, F., Pavan, M., La Manna A., Bettinetti, G. P., Pavesi, L., Bovis, G.
Assessment of the Stoichiometry of a Vinbumine and Gamma-Cyclodextrin Complex by
Microcalorimetry 319
4.9. Amdidouche, D., Darrouzet, H., Duchene, D.
Molecular Encapsulation Of Retinoic Acid by ~-Cyclodextrin, Characterization of the
Inclusion Compound 325
4.10. Weiszfeiler, V., Stadler-Sz6ke, A., Szejtii, J.
Solubility Enhancement of Ipriflavone by Cyclodextrin Complexation 329
4.11. Uvai, F., T6th, K., Szatmari, 1., Vargay, Z.,
The Effect of Beta-Cyclodextrin Complexation on Plasma Levels of Ipriflavone and Its
Main Metabolites 337
4.12. Uvai, F., Szatman, 1., Vergay, Z.
The Comparison of Absorption, Distribution and Elimination of Ipriflavone-14C and
Ipriflavone-14C-Beta-Cyclodextrin Inclusion Complex 343
4.13. Jansen, A. C. A., Hilbers, H. W., Poelma, F. G. J., Tukker, J. J.
The Influence of Inclusion by Cyclodextrins on Absorption Kinetics of Dantrolene in the
Rat 349
4.14. Thoss, M., Norwig, J., Mehnert, W., Fr()mming, K.-H.
Improvement on Photostability of Several Essential Oils and Menadione by Natural
Cyclodextrins 355
4.15. Weiszfeiler, V., Szejtli, J.
Bitterness Reduction With Beta-Cyclodextrin 359
5. CYCLODEXTRIN DERIVATIVES IN PHARMACEUTICALS
5.1. MUller, B. W., Brauns, U., Backensfeld, T.
Cyclodextrin Derivatives For Solubilisation, Stabilisation, and Absorption of Drugs 369
5.2. Pitha,J.
Biomedical Uses of Amorphous Water Soluble Derivatives of Cyclodextrins 383
5.3. Szeman, J., Szente, L., Szab6, T., Szejtii, J.
Highly Soluble ~-Cyclodextrin Derivatives, A Comparative Snidy 393
5.4. Brewster, M. E., Loftsson, T., Estes, K. S., Mullersman, G., Derendorf, H., Bodor, N.
Water Soluble Complexes of a Brain-Targeted Drug Delivery System 399
5.5. Szatman, 1., Vargay, Z.
Phannacokinetics of Dimethyl-Beta-Cyclodextrin in Rats 407
5.6. Ger16czy, A., Antal, S., Szejtli, J.
Percutaneous Absorption of Heptakis-(2,6-DI-O_14(;-Methyl)-~-Cyclodextrin in Rats 415
5.7. JodaI, 1., Nanasi, P., Szejtii J.
Investigation of the Hemolytic Effect of the Cyclo-Dextrin Derivatives 421
viii
CONTENTS
5.8. Szathmary S. CS.
Determination of Hydroxypropyl- ~-Cyclodextrin in Plasma and Urin by Size Exclusion
Chromatography With Post Column Complexation 427
6. CDs IN CATALYSIS AND ANALYTICAL CHEMISTRY
6.1. Armstrong, D. W.
Cyclodextrins in Analytical Chemistry 437
6.2. Smolkova-Keulemansova, E.
Cyclodextrins in Chromatography and Isotac-Hophoresis 451
6.3. Konig, W. A., Lutz, S., Wenz, G.
Enantioselective Capillary Gas Chromatography With Modified Cyclodextrins as Chiral
Stationary Phases 465
6.4. Simonyi, I., Kekesy, I.
HPLC of Chloramphenicol and Some of its Synthetic Intermediates on a Cyclodextrin-
Bonded Chiral Stationary Phase 473
6.5. Juvancz, Z., Racz, Zs., Alexander, G., Szejtli, J.
Gaschromatographic Capillary Columns With Cyclodextrins as Stationary Phases 479
6.6. Warner, I. M., Nelson, G.
Fluorescence Studies of Cyclodextrin Complexes 485
6.7. Ku~era, J.
Immobilized Cyclodextrins for Affinity Chromatography 493
6.8. UjMzi, A., Zsadon, B., Szejtli, J.
Gelchromatographic Separation of Proteins on Cyclodextrin Bead Polymers 497
6.9. Drabowicz, J., Dudzinski, B., TYzWa, P., Mikolajczyk, M.
~-Cyclodextrin in Optical Resolution of Chiral Sulphinyl Derivatives 503
6.10. Kojin, R., To, Y., Ikeda, H., Yoon, C., Iijima, M., Ikeda, T., Toda, F.
Catalytic Activity of Artificial Hydrolases Using Modified Cyclodextrins 509
6.11. Marzona, M., Giraudi, G.
Functionalized Cyclodextrins as Oxydo-Reductasic Enzyme Models 513
6.12. Bak6, P., Fenichel, L., T6ke, L., Szente, L., Szejtli, J.
Selective Reductions of CD Complexed Terpenes 519
6.13. Zhang, D., Huang, N., Chen, G., Wu, Y., Duan, D., Yuan, S.
Reactions in the Presence of Cyclodextrins 525
7. CYCLODEXTRINS IN FOODS AND AGRICULTURE
7.1. Hashimoto, H.
Application of Cyclodextrins to Foods, Toiletries and Other Products in Japan 533
7.2. Szente, L., Harangi, J., Szejtli, J.
Long Term Storage Stability Studies on Flavour-~-Cyclo-Dextrin Complexes 545
7.3. Juhasz, A., Salg6, A., Seb6k, A.
Application of ~-Cyclodextrin in Meat Industry 551
7.4. Linssen, J. P. H., Wilsum, J. V.
Effect of Cyclodextrin and Glycerolmonostearate on Starch Gelatinization 557
7.5. Szejtli, J.
Fungicidal Activity of Benomyl in Presence of ~-Cyclo-Dextrin 561
Index 569
PREFACE
The rapidly growing number of papers and patents on Cyclodextrins and
their potential or actual industrial uses raised the idea to organize a
Symposium on Cyclodextrins. This Symposium - held in September 1981 in
Budapest, with more than 200 participants from 17 countries - proved to
be very succesfull in every respect, therefore it has been accepted
unanimously to organize the lInd CD-Symposium in 1984, in Tokyo. (The
Budapest-Symposium got posteriorly the "First" adjective). The IInd
Symposium was held together with the III. Int. Symposium on Chlatrate
Compounds and Molecular Inclusion Phenomena. The IIIrd CD-Symposium also
was held as a Joint Symposium, with the IVth. Chlatrate Symposium in
Lancaster, U.K.,1986. The limited time however showed, that such a broad
field - from calixarenes to zeolites - can not be managed efficiently.
Therefore the International Organizing Committee voted for separation of
the two Symposia in the future. The IVth Int. CD-Symposium was held in
Munich, in April 1988, and the Vth Chlatrate Symposium (called already
Vth Int. Symposium on Inclusion Phenomena and Molecular Recognition) was
held in Alabama, Sept. 1988.
In Munich 220 participants from 21 countries attended 32 verbal lectures
and 54 posters. This volume contains the submitted 71 manuscripts of the
IVth Cyclodextrin Symposium.
Because in the case of such Symposium-Proceedings the most important
factor of the success is the possible shortest time between the
symposium and the publication of the book, the Editors have to apologize
for the strongly objectionable style and language of the majority of the
contributions. A linguistic checking, with concomittant rewriting and
correspondence with the authors would delay the publication by at least
half a year - without notable improvement of the material - at least
concerning the scientific value.
Nowadays every day more than one new paper or patent is published on the
CDs, therefore the possible quickest publication of this book seemed to
be the desirable. While in the preface of the Proceeding of the 1st CO
Symposium the following words were written:
" ... during the last 30 months 239 papers and patents were published on
CDs". In 1988 six months produces a similar number.
The Munich-Symposium was held under the auspices of the "Gesellschaft
Deutscher Chemiker", with the generous financial and personnel support
of the Chemie GmbH, Munich.
\~acker
The Editors,
Budapest and Munich, June 1988.
ix
WELCOME ADDRESS TO THE PARTICIPANTS OF THE
IVTH INTERNATIONAL SYMPOSIUM ON CYCLODEXTRINS
O. S. Huber
Consortium fUr elektrochemische Industrie GmbH
Zielstattstr. 20, D-8000 MUnchen 70, F.R.G.
Good morning Ladies and Gentlemen,
On behalf of the organizers I would like to welcome you here
in Munich to the IVth International Symposium on Cyclodextrins.
It has been a great pleasure for me to organize this Symposium
and to see how many people from allover the world are interested in
these cyclic sugar-molecules. I hope this Symposium will push forward
Cyclodextrins and their derivatives to a broader understanding in
academic work as well as in their industrial applications.
I wish you a very fruitful Symposium and want to apologize in
advance for any inconvenience which might arise in the course of our
meeting.
Before we start with the Scientific Program, please let me thank
all people who have contributed to the Symposium, either with an oral
presentation or a poster and who in any way helped in the organization.
And last not least, I want to thank you here in the audience for
coming to Munich from more than 20 different countries to this pure
Cyclodextrin-Symposium.
Now my special welcome goes to Professor Cramer and
Professor Szejtli. I think without the work of these two scientists
this pure Cyclodextrin-Symposium would not have been possible and it is
a great pleasure for me and I am most grateful to them that they both
have agreed to give a contribution at this meeting.
And in my last sentence, please let me express in advance my best
wishes to Prof. Cramer who will celebrate his 65th birthday later this
year. Congratulations!