Self-Production of Supramolecular Structures NATO ASI Series Advanced Science Institutes Series A Series presenting the results of activities sponsored by the NATO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities. The Series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division A Life Sciences Plenum Publishing Corporation B Physics London and New York C Mathematical Kluwer Academic Publishers and Physical Sciences Dordrecht, Boston and London D Behavioural and Social Sciences E Applied Sciences F Computer and Systems Sciences Springer-Verlag G Ecological Sciences Berlin, Heidelberg, New York, London, H Cell Biology Paris and Tokyo I Global Environmental Change NATO-PCO-DATA BASE The electronic index to the NATO ASI Series provides full bibliographical references (with keywords and/or abstracts) to more than 30000 contributions from international scientists published in all sections of the NATO ASI Series. Access to the NATO-PCO-DATA BASE is possible in two ways: - via online FILE 128 (NATO-PCO-DATA BASE) hosted by ESRIN, Via Galileo Galilei, I-00044 Frascati, Italy. - via CD-ROM "NATO-PCO-DATA BASE" with user-friendly retrieval software in English, French and German (© WTV GmbH and DATAWARE Technologies Inc. 1989). The CD-ROM can be ordered through any member of the Board of Publishers or through NATO-PCO, Overijse, Belgium. Series C: Mathematical and Physical Sciences - Vol. 446 Self-Production of Supramolecular Structures From Synthetic Structures to Models of Minimal Living Systems edited by Gail R. Fleischaker Center for the Philosophy & History of Science, Boston University, Boston, Massachusetts, U.S.A. Stefano Colonna Departimento di Chimica, Universitä degli Studi di Milano, Milano, Italy and Pier Luigi Luisi Institut für Polymere, ETH-Zürich, Switzerland Springer-Science+Business Media, B.V. Proceedings of the NATO Advanced Research Workshop on Self-Production of Supramolecular Structures From Synthetic Structures to Models of Minimal Living Systems Acquafredda di Maratea, Italy September 12-16, 1993 A C.I.P. Catalogue record for this book is available from the Library of Congress. ISBN 978-94-010-4324-3 ISBN 978-94-011-0754-9 (eBook) DOI 10.1007/978-94-011-0754-9 Printed on acid-free paper All Rights Reserved © 1994 Springer Science+Business Media Dordrecht Originally published by Kluwer Academic Publishers in 1994 Softcover reprint of the hardcover 1st edition 1994 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photo copying, recording or by any information storage and retrieval system, without written permission from the copyright owner. This book contains the proceedings of a NATO Advanced Research Workshop held within the programme of activities of the NATO Special Programme on Supramolecular Chemistry as part of the activities of the NATO Science Committee. Other books previously published as a result of the activities of the Special Programme are: WlPFF, G. (Ed.), Computational Approaches in Supramolecular Chemistry. (ASIC.426) 1994. ISBN 0-7923-2767-5 TABLE OF CONTENTS Introduction (Pier Luigi Luisi) IX Acknowledgments (The Organizing Committee) xiii Workshop Speakers xv HISTORICAL AND PHILOSOPHICAL PERSPECTIVES S Hoffmann Historical overview to the quest of self-reproduction and artificial life 3 FJ Varela On defining life 23 GR Fleischaker A few precautionary words concerning terminology 33 TEMPLATE CHEMISTRY D Sievers, T Achilles, J Burmeister, S Jordan, A Terfort & G von Kiedrowski Molecular replication: From minimal to complex systems 45 ESzathmary Self-replication and reproduction: From molecules to protocells 65 J Rebek,Jr. Extrabiotic replication and self-assembly 75 JP Ferris The prebiotic synthesis and replication of RNA oligomers: The transition from prebiotic molecules to the RNA world 89 JT Goodwin, P Luo, JC Leitzel & DG Lynn Template-directed synthesis of oligomers: Kinetic vs. thermodynamic control 99 CHIRALITY AND REPLICATION A W Schwartz & MJ Van Vliet Chirality and the first self-replicating molecules 107 A Brack Are peptides possible support for self-amplification of sequence information? 115 viii THE RNA WORLD RR Breaker & GF Joyce Minimonsters: Evolutionary by-products of in vitro RNA amplification 127 L Giver, S Lato & A Ellington Models for the autocatalytic replication of RNA 137 CK Biebricher RNA species that multiply indefinitely with RNA polymerase 147 PV Coveney Chemical oscillations and non-linear chemical kinetics 157 THE CELL VIEW AND CELL MODELS PL Luisi The chemical implementation of autopoiesis 179 JS Nowick, JS Chen, T Cao & G Noronha Molecular recognition in micelles 199 PWalde Self-reproducing vesicles 209 DWDeamer Sources and syntheses of prebiotic amphiphiles 217 V Garci'a-Meza, A Gonzalez-Rodriguez & A Lazcano Ancient paralogous duplications and the search for Archean cells 231 POSTERS C Bohler, W Bannwarth & PL Luisi Self-replication of oligonucleotides in reverse micelles 249 S Bonaccio, C Cescato, P Walde & PL Luisi Liposomes from lipidonucleotides and from lipidopeptides 255 S Campagna, G Denti, S Serroni, A Juris, M Venturi & V Balzani Dendritic luminescent and redox-active supermolecules made of transition metal complexes 261 G Decher, J-D Hong, K Lowack, Y Lvov & J Schmitt Layer-by-Iayer adsorption: The solidlliquid-interface as a template for the controlled growth of well-defined nanostructures of polyelectrolytes, proteins, DNA and polynucleotides 267 P Burgstaller, D Faulhammer & M Famulok Molecular recognition of amino acids by RNA 273 ix DL Gerloff Towards nature's structural guidelines: Conclusions on the unsolved structures of RNA-dependent RNA polymerases 279 M Fresta, M Maestro & F Mavelli A self-catalyzed (autopoietic) synthesis of an anionic surfactant: Experimental evidence and theoretical modeling 285 V Rotello, Q Feng, J-I Hong & J Rebek, Jr Competition, reciprocity, and mutation at the molecular level: Irradiation of a synthetic replicator generates a superior species 291 R Wick, P Walde & PL Luisi Giant vesicles 295 Index 303 INTRODUCTION The term "self-replication" has a strong representational power: it calls to mind the capability of a natural or synthetic system to make copies of itself as well as the fact that the copying must be an autocatalytic process. The qualifying "selt"--so often misused in current biologicalliterature--has here a very precise meaning: it is the original system that is the primary cause of its own replication. It was timely to call a conference on the subject, and this for two good reasons. First, the field of self-replication has undergone a considerable development in the past three to four years with on-going discussion of new concepts and new semantics. Second, this development derives from different schools of thought--from different fields and different philosophies--and is therefore anything but homogeneous. It was important at this time to compare notes, possibly confronting differences, not only on the subject of self-replication but on more general themes such as the definition of 'life' or 'minimal life.' Of these different schools, I recognize three as most influential, both in the general field and at the Maratea meeting. First, is the molecular biological approach, which presents self-replication within the framework of the "RNA world," an approach represented here by the work of Gerald Joyce at the Scripps Research Institute and Jack Szostak at Massachusetts General Hospital. For these authors, self-replication is intrinsically linked to molecular darwinian evolution. Accordingly, the main hero is the RNA molecule which provides at one and the same time the capability both of replication and mutation. Extrapolated to the limits, this view traces the emergence of life to the point at which a family of RNA molecules were able to catalyze their own formation and mutate in the process. One can say that this school of thought has its matrix in the classic work of Sol Spiegelman and Eigen's group in G6ttingen, although in the literature at large this fact is not always recognized. At the Maratea meeting, the G6ttingen group was represented by Christof Biebricher and by John McCaskill (now in Jena, Germany). The second school is that of small chemical replica tors, epitomized by the work of Julius Rebek at the Massachusetts Institute of Technology and Gunter von Kiedrowski, originally at G6ttingen and now in Freiburg i.B. Germany. Here the main ingredient is an oligonucleotide template or other parent structure which binds two smaller components via recognition (most usually, base-pairing). These two components are generally the two halves of the template, and the tight binding to the template facilitates their chemical coupling, transforming them into a copy (usually palindromic) of the template. Both template-recognition and base-pairing are expressed on synthetic structures obtained with the classic tools and handouts of organic chemistry. The philosophy underlying this work is much like that underlying the RNA xi xii World in that the basis for self-replication and for life processes is the chemistry of nucleic acids. Both for small chemical replicators and RNA-world scenarios, there is a single molecule or family of parent chemical structures which "does it all." By contrast, the third school emphasizes the fact that basic life processes are not the attribute of any single kind of molecule but the result of an organized complex system of molecular interactions that occur within and also produce the system's physical boundary structure. The philosophical matrix of this school lies in the concept of 'autopoiesis,' a term introduced in the early 1970's by the biologists Humberto Maturana and Francisco Varela. Autopoiesis emphasizes the organiza tional pattern of life processes, including the notion of dynamic compartmentation- that is, that an inside space is made distinct from an outside space by virtue of a closed, spherical cell-like boundary that is itself a product of those life processes. This is exemplified most clearly in the simplest contemporary bacterial cell. It is in these simple cell systems that one may discover the basic mechanisms of life, and from which one may model a minimal living system. Based on this concept of autopoiesis, the experimental work of Luisi's group at the ETH-Ziirich centers on self-replication within spherically-bounded structures such as micelles and vesicles, arriving at definitional patterns of minimal living systems without invoking the particular structures and properties of nucleic acids. This school has an historical scientific matrix in Oparin's work of the 1920's and 1930's with its emphasis on metabolism and, more recently, in David Deamer's work on bio-membranes and liposomes. These three schools, albeit so different, are part of the general field of supramolecular chemistry. In work concerning the RNA world or small replicators, intermolecular interactions between template and subtrates play a major role; in work concerning autopoiesis, supramolecular assemblies (micelles, vesicles), held together by intermoleular interactions, have the major role. It is for this reason that the Maratea workshop was held within the Supramolecular Chemistry Programme of the NATO Research Institute. Despite the importance of recognition chemistry and assembly within this field at large, we decided in advance not to solicit contributions on these subjects so that we could focus the workshop on self-replication. Likewise, we did not include talks explicitly on the origins of life, although this subject is also closely related to self replication. We felt, however, that because these two themes would be intense even in the background, they could and would make their presence known. Mixing people together with such differences in approach is an act of some courage. And what could one expect from such a mix? If one were to take a very optimistic stand, one may expect that it would be possible to find a common philosophical ground, a unified nomenclature, and hope that joint research programs between and across the three schools might spontaneously arise. A more down-to Earth view would suggest instead that the first two expectations (to find a common philosophy, to carve out a common nomenclature) are illusions: molecular biologists may not even take notice of the autopoietic approach which does not pay respect to the holy RNA molecules; synthetic chemists probably will show their traditionally