Mikiharu Kamachi· Akira Nakamura (Eds.) New Macromolecular Architecture and Functions Mikiharu Kamachi· Akira Nakamura {Eds.} New Macromolecular Architecture and Functions Proceedings of the OUMS '95 Toyonaka, Osaka, Japan, 2-5 June, 1995 With 136 Figures and 28 Tables , Springer Professor Mikiharu Kamachi Professor Akira Nakamura Osaka University Dept. of Macromolecular Science Toyonaka 560 Osaka Japan Library of Congress Cataloging-in-Publication Data OUMS '95 (1995: Osaka, Japan)New macromolecular architecture and functions: proceedings of the OUMS '95Toyonaka, Osaka, Japan, 2-5 June 1995/ Mikiharu Kamachi,Akira Nakamura(eds.). Includes bibliographical references. ISBN-13:978-3-642-80291-1 e-ISBN-13:978-3-642-80289-8 DOl: 10.1007/978-3-642-80289-8 I. Macromolecules--Congresses. 2. Polymerization--Congresses. 3. Polymers--Congresses. I. Kamachi, Mikiharu. II. Nakamura, Akira. III. Title. QD380.094 1995 547.7--dc20 96-43179 ISBN-13: 978-3 -642-80291-1 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfIlm or in other ways, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer-Verlag. Violations are liable for prosecution act under German Copyright Law. © Springer-Verlag Berlin Heidelberg 1996 Softcover repint of the hardcover 1st edition 1996 The use of general descriptive names, registered names, trademarks, etc. i~ this publication does not imply, even in the absence ofa specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Production: PRODUserv Springer Produktions-Gesellschaft, Berlin Cover-Layout: de'blik, Berlin Typesetting: Camera-ready copies from authors SPIN: 10503791 2/3020 -5 4 3 21 0 -Printed of acid-free paper Springer Berlin Heidelberg New York Barcelona Budapest Hong Kong London Milan Paris Santa Clara Singapore Tokyo Preface This volume summarizes the papers presented at the second Osaka University Macromolecular Symposium OUMS '95 on "New Macromolecular Architecture and Functions" which was held at Senri Life Science Center, Osaka, Japan, on June 2 through June 5, 1995. The symposium covered the three topics, (1) Controlled Polymerizations, (2) Macromolecular Organized Systems and (3) Biomimetic Polymers, and invited leading scientists in these fields. At present, any of these topics is a hot issue in itself and frequently taken up separately on many occasions. It is noted, however, that all these topics are correlated with each other with the keyword "molecular design of new types of polymers" and their combination provides a unique feature of the present symposium in reflecting the interactions among investigators working in these important fields with the common ground expressed by the keyword "molecular design of new types of polymers". Twenty five invited lectures and twenty nine posters were presented at the Symposium, and twenty of the lectures contribute to this volume. In the first topic, preparations of sequentially of stereoregularly controlled polymers were discussed from the view points of precise design of polymer preparation on the molecular level; attention was paid to a possibility of living radical polymerization, preparations of new types of living polymers, recent advances in preparation of stereospecific living polymers, sequential control in block copolymers, and molecular design of initiators and/or catalysts for the controlled polymerizations. The second topic was mainly concerned with preparation of supramolecular polymers and macromolecular organized systems, and their function. Preparations, structures, and functions of supramolecular polymers and macromolecular organized systems were discussed from the points of views of molecular recognition and assembly formation, and, in addition, molecular design of new types of materials. In the final topic, recent advances in preparations and fuctionalities of biomimetic polymers was shown, and characteristics of the polymers were discussed in relation to biological behavior and the preparation of new materials. Since the three topics are deeply correlated each other, the program of the symposium was arranged so that the three topics were properly mixed. The papers contributed to this volume should also reflect the outcome from such interaction at this meeting. Thus, we believe this volume will be useful for specialists working in these related fields on one hand, and serve as a refernce book for those who wish to get familiar with these fields on the other hand. March 1996 Mikiharu Kamachi Akira Nakamura Table of Contents Atom Transfer Radical Polymerization Including Degenerative Transfer: Novel and General Pathways Towards "Living"/Controlled Radical Polymerization S.G. Gaynor, D. Greszta, J-S. Wang, and K. Metyjaszewski .......... 1 Living Radical Polymerization via Reversible Homolytic Activation of Carbon-Halogen Bonds with Metal Complexes M. Sawamoto and M. Kamigaito ...................................................... 11 Molecular Information and Its Expression by Oligomeric Carbon Chain Compounds; What Steroidal Molecules Tell Us Miyata ................................................................................................ 21 Stereospecific Living Polymerization of Methacrylate with Binary Initiator Systems T. Kitayama and K. Hatada ............................................................. 31 Single Site Polymerizations of Ethylene and l-Olefins Catalyzed by Rare Earth Metal Complexes E.Ihara and H. Yasuda ..................................................................... 41 Non-Conjugated and Conjugated Dienes in Acyclic Diene Metathesis (ADMET) Chemistry K.B. Wagener and T.A. Davidson ..................................................... 51 Design and Synthesis of New Substituted Polyacetylenes T. Masuda and Y. Misumi ................................................................. 59 Precursor Method for Polymeric LB Films M. Kakimoto, A. Wu, and Y. Imai .................................................... 69 Polyethyleneimine Derivatives as Nucleic Acid Model and Interaction with DNA Y. Inaki and T. Wada ........................................................................ 79 Helical Polymers: Synthesis, Conformation, and Function Y. Okamoto, T. Nakano, and S. Habaue .......................................... 89 The Dendritic Box; Synthesis, Properties, and Applications J.F.G.A. Jansen, E.M.M. de Brabander-van den Berg, and E.W. Meijer ................................................................................. 99 New Macromolecular Architectures and Functions Through Macromolecular Recognition by Cyclodextrins Harada and M. Kamachi ................................................................... 107 Novel Unimolecular Micelles of Hydrophobically Modified Polyelectrolytes: Synthesis, Characterization, and Functions Y. Morishima and M.Kamachi .......................................................... 117 Optical Characterization of Ultrathin Polymer Films Prepared by the Langmuir-Blodgett Technique S. Ito and M. Yamamoto ............................................................................ 127 Excited State Electron Transfer from Polyelectrolyte-Bound Chromophores S.E. Webber ................................................................................................ 137 Chemical Functions ofNH---S Hydrogen Bonds in Model Complexes of Iron-Sulfur Metalloproteins N. Ueyama, T. Okamura, and A. Nakamura ............................................ 147 Genetically Expressed Monodisperse Helical Polypeptides (l J.S. Bartlett, RJ. Samulski, Y. Li, and E.T. Samulski ............................ 159 Enzymatic Synthesis of Polysaccharides: A New Concept in Polymerization Chemistry S. Kobayashi and S. Shoda ........................................................................ 171 Self Assembling Organic N anotubes J.D. Hartgerink and M.R. Ghadiri ............................................................ 181 Development of a Rapid and Facile Method for Protein Synthesis Using Partially Protected Peptide Thioesters as Building Blocks S. Aimoto and H. Hojo................................................................................. 189 Molecular Weight Dependent Antimicrobial Activity by Chitosan S. Tokura, K. Ueno, S. Miyazawa, and N. Nishi ...................................... 199 Atom Transfer Radical Polymerization Including Degenerative Transfer: Novel and General Pathways Towards "Living" I Controlled Radical Polymerization Scott G. Gaynor, Dorota Greszta, Jin-Shan Wang, KrzysztofMatyjaszewski* Department of Chemistry, Carnegie Mellon University 4400 Fifth Avenue, Pittsburgh, PA 15213 ABSTRACT. A novel and general "living" radical polymerization, namely, Atom Transfer Radical Polymerization, ATRP, affords various pathways towards the synthesis of tailor -made (co)polymers with predetermined molecular weights up to Mn '" 105 and molecular weight distributions as narrow as 1.05. This paper describes four different approaches to "living" ATRP, i.e., iodide-based degenerative transfer, alkyl halide / transition metal species promoted halogen atom transfer, R-X / Mtn / Lx; radical initiator / transition metal species promoted halogen atom transfer, 1-1/ Mtn+1 / Lx; and alkyl halide / radical initiator / transition metal species promoted halogen atom transfer, R-X / I-I / Mtn+1 / Lx. Introduction. Atom transfer radical addition, ATRA, is an important method for carbon -carbon bond fonnation in organic synthesis.1 Two types of atom transfer methods have been developed. One of them is based on a univalent atom (e.g., hydrogen and halogen) or a group (e.g., SePh) transfer from a neutral molecule to a radical to fonn a new a-bond and a new radical, Scheme 1.2 R- X + R' + A-X Scheme 1 A univalent atom or a group transfer radical reaction Another atom transfer method is promoted by a transition metal species, in which the catalytic amount of the transition metal compound acts as a carrier of the halogen atom in a redox process, Scheme 2.3 In analogy with A TRA, atom transfer radical polymerization, AT RP, can also be catalyzed by radicals or transition metal complexes.4,5 For successful atom transfer radical reactions, A TRA and A TRP both require the presence of a low concentration of free radicals in order to minimize the extent of tennination reactions between radicals. However, there appears to be two principal differences between ATRP and ATRA. M. Kamachi . A. Nakamura (Eds) New Macromolecular Architecture and Functions Proceedings of the OUMS '95 Toyonaka, Osaka, Japan, 2-5 June, 1995 © Springer-Verlag Berlin Heidelberg 1996 2 R-X Scheme 2 Transition metal catalyzed atom transfer radical addition First, an efficient ATRA process should avoid any kind of consecutive atom transfer processes, i.e., oligomerization or polymerization. This is the reason why, in ATRA, a very active atom transfer precursor and an inactive terminal alkene are often chosen by organic chemists. By contrast, ATRP involves a number of consecutive ATRA processes. Second, in ATRA most transfer reactions are irreversible under normal conditions, i.e., leading to degradative transfer, whereas the presence of fast and reversible atom transfer is necessary for obtaining well-defined polymers with predetermined molecular weights and low polydispersities. In addition, it is well known that telomers can be synthesized by radical polymerization using either a transition metal species I alkyl halide combined initiating system or a radical initiator in the presence of a large amount of organic halide.6 As discussed previously, in telomerization, s the polymeric halides behave as dead chains. They cannot be further activated, i.e., the transfer process is degradative (irreversible). Contrary to telomerization, ATRP represents a reversible transfer, in which the resulting polymeric halides are dormant species and can be repeatedly activated. Consequently, the molecular weight of the obtained polymer does not increase with monomer conversion in telomerization, whereas the molecular weight increases linearly with increasing monomer conversion in A TRP. Degenerative Transfer. The detailed mechanism of a univalent atom X transfer based ATRP is outlined in Scheme 3. The radical, R·, is generated by the atom X transfer from R -X to an initiator radical, In·, which is generated by decomposition of a conventional initiator, e. g., AlliN or BPO. The radical R·, can then react with an alkene to form the radical species, R -M·. This species can subsequently abstract the X from R -X, to form a dormant species, R -M -X, and R·. The transfer process then occurs again. Because this process is a chain reaction, only small quantities of the initiator, relative to the transfer agent, are required to drive the reaction to completion. Assuming the reactivities of R -X and R - M - X are similar, competitive atom transfer may occur leading to the formation of polymers. Since the propagation in such a type of ATRP accompanies a thermodynamically neutral (reversible) exchange process, we called such a process degenerative transfer. A similar process probably also occurs in silyl ketene acetal mediated group transfer polymerization in the presence of nucleophilic catalysts.7