www.advmat.de www.MaterialsViews.com REVIEW Progressive Macromolecular Self-Assembly: From Biomimetic Chemistry to Bio-Inspired Materials Yu Zhao , Fuji Sakai , Lu Su , Yijiang Liu , Kongchang Wei , Guosong Chen ,* and Ming Jiang * Dedicated to the 20th Anniversary of the Department of Macromolecular Science of Fudan University was highlighted, with the purpose of Macromolecular self-assembly (MSA) has been an active and fruitful research expanding the scope of chemistry.[ 1b ] At fi eld since the 1980s, especially in this new century, which is promoted by its early stage, biomimetic chemistry was the remarkable developments in controlled radical polymerization in polymer regarded as a branch of organic chemistry and the work concentrated on the level chemistry, etc. and driven by the demands in bio-related investigations and of molecules, formation and cleavage of applications. In this review, we try to summarize the trends and recent pro- covalent bonds following the way learning gress in MSA in relation to biomimetic chemistry and bio-inspired materials. from the living body. Artifi cial enzymes Our paper covers representative achievements in the fabrication of artifi cial aiming at fast and high selectivity have building blocks for life, cell-inspired biomimetic materials, and macro- been the key research subject in biomi- metic chemistry with emphasis on the molecular assemblies mimicking the functions of natural materials and their idea of molecular recognition, which is applications. It is true that the current status of the deliberately designed and also the center of supramolecular chem- obtained nano-objects based on MSA including a variety of micelles, multi- istry. Later, the principle and methodology compartment vesicles, and some hybrid and complex nano-objects is at their of biomimetic chemistry have gradually very fi rst stage to mimic nature, but signifi cant and encouraging progress expanded and penetrated to other sub-dis- has been made in achieving a certain similarity in morphologies or properties ciplines with great successes. In polymer science, the achievements in precise poly- to that of natural ones. Such achievements also demonstrate that MSA has merization that were developed in the last played an important and irreplaceable role in the grand and long-standing two decades provide a good example. Now, research of biomimetic and bio-inspired materials, the future success of the preparation of a remarkably diverse which depends on mutual and persistent efforts in polymer science, material and growing range of precise polymers science, supramolecular chemistry, and biology. with mimic complex and hierarchical architectures from the natural prototypes become realistic. [ 2 ] Looking back the tremendous pro- 1. Introduction gresses of polymer science achieved in the past 30 years, we do admire and appreciate the unusual foresight of Helmut Humans have admired, learned from, and been inspired by Ringsdorf as shown in his article in Angewandte Chemie in Nature from the beginning of civilization. The dream of mim- 1988. [ 3 ] In the paper, which has been cited more than one icking nature is becoming more realistic step by step due to the thousand times so far, Ringsdorf put forward the questions: developments in modern science. In the long march to achieve “where is the future, where are the adventures” of polymer sci- such mimicry, the birth of biomimetic chemistry in the 1970s ence as it became a classical discipline and a mature science. marked a turning point where mimicking research in chem- He clearly presented the answer, “Polymer science fi nds itself [1] istry was really launched. As defi ned by Ronald Breslow, bio- not only on the borderland between chemistry and physics, but mimetic chemistry is the fi eld in which chemists invent new also between materials science and life science” and “On the substances and reactions that imitate biological chemistry. In border between the different disciplines of science, adventures this defi nition, the intellectual fl ow from biology into chemistry are waiting”. It meant that polymer science could no longer restrict itself to common plastics and should expand to neigh- Y. Zhao, F. Sakai, L. Su, Y. Liu, K. Wei, boring science, particularly biology. Along this line, Helmut is Prof. G. Chen, Prof. M. Jiang a pioneer in practice as well since he designed the fi rst artifi cial State Key Laboratory of Molecular Engineering polymeric liposomes, and pointed out possible contributions of Polymers and Department from polymers to the simulation of cellular processes, such of Macromolecular Science as the stabilization of biomembranes and specifi c surface rec- Fudan University, Shanghai, China ognition. [ 3 ] He also pointed out that the functions of biomac- E-mail: [email protected]; [email protected] romolecules, including polysaccharides and nucleic acids, are DOI: 10.1002/adma.201302215 in all cases based on the combination of molecular mobility Adv. Mater. 2013, 25, 5215–5256 © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com 5215 www.advmat.de www.MaterialsViews.com and high order. Led and encouraged by such pioneering work, the mimetic research of macromolecular science have gradu- Yu Zhao was born in Harbin, ally moved to materials level, i.e., constructing artifi cial living northeast China in 1988. elements mimicking the morphology fi rst and then functions He received his BS in REVIEW turned to the main stream in this area. Among the various 2011 in the Department of research areas of polymers, macromolecular self-assembly Macromolecular Science, (MSA), which emerged in 1970s, no doubt contributes most Fudan University. Currently he to the biomimetic chemistry and bio-inspired materials. It is a graduate student in Prof. is understandable as the central mission of MSA is to con- Jiang’s group. His research structing well-defi ned assemblies varying in architectures, size focuses on the synthesis and scales and complexities, etc . from macromolecules as main self-assembly of dendritic building blocks. MSA experienced an amazing progress and glycopolymers. steadily began to contribute to biomimetic and bio-inspired study by its own way. This is the thesis of this review. This review paper pays special attention to the integration Dr. Guosong Chen got her BS of MSA with supramolecular chemistry and material science in 2001 and her PhD in 2006 under the light of biomimetics. [ 4 ] We have to mention that in in the Chemistry Department, the past ten years, quite a few valuable review articles picked the Nankai University, China. topics related to biomimetics focusing on the progresses made Her PhD work was on in the fi eld of inorganic materials, nanotechnology and nano- cyclodextrin-based supra- engineering, which will not be covered in this article.[ 5 ] Regard molecular chemistry. Then to applications of assembled objects of macromolecules, no she did her postdoc work on doubt, those towards medicine such as drug and gene delivery, carbohydrate chemistry in medical imaging, etc. have been the hottest subject currently as the Chemistry Department, thousands papers including timely reviews published per year. Iowa State University, So this article will not cover this area. We make this article with USA. In 2009, she joined a ’beads-on-a-string’ structure where MSA is the string which Prof. Ming Jiang’s group as a lecturer in Department of wraps and connects all of the important recent fruits including: Macromolecular Science at Fudan University. She was pro- (a) a brief introduction of some representative developments moted to Associate Professor in Oct. 2011. Currently, she of MSA which have been used or have potential usage in the is working on interdisciplinary studies of macromolecular mimic research; (b) artifi cial basic building blocks of life built self-assembly, supramolecular chemistry and glycoscience. by MSA; (c) cell-inspired bio-mimetic materials, mainly vesi- cles; (d) assembled materials with property of self-healing and self-sorting and a few applications, e.g., template synthesis, Ming Jiang graduated from nanoreactors etc . We hope that by our elaborate reorganization the Chemistry Department of the intelligent relevant research papers in literature, the sig- at Fudan University, China nifi cant role and bright future of MSA as an alternative avenue in 1960. Since then he in achieving biomimetic or bio-inspired materials is clearly and has served within the concisely presented. Chemistry, Materials, and Macromolecular Science Department at Fudan 2. Aspects of MSA Developments University as assistant, lec- turer, and then as associate The studies on self-assembly of synthetic macromolecules professor. He was promoted started in 1960s when block copolymers with well-defi ned to professor in 1988. He was structures in terms of composition, molecular weight and its also visiting scientist at the University of Liverpool, UK distribution, and the chain architectures, etc. were attained in from 1979 to 1981. Professor Jiang was elected Member laboratory and part of them was commercialized as thermo- of the Chinese Academy of Sciences in 2005 and Fellow plastic elastomer. Various different regular morphologies of of Royal Society of Chemistry in 2009. His research is the block copolymers formed by ’microphase separation’ in mainly in physical chemistry of polymers and supramo- solution or bulk aroused great interest of polymer community lecular chemistry with emphasis on macromolecular as such regular mesophase structures had not been