Editorial pubs.acs.org/CR
Introduction to Frontiers in Macromolecular and Supramolecular Science: Part 1
T
he word polymer was introduced by Berzelius in 1832.1,2 In spite of this, macromolecular chemistry is approaching only one century since organic chemists accepted polymer or macromolecular science as the newest subdiscipline of organic chemistry.3 Natural and synthetic polymers were already commercially available during the early days of the previous century. However, it was the demonstration of their chemical structure and the acceptance of their definition that delayed the development of this field. Staudinger defined macromolecules in 1920 via the following sentence. “For such colloid particles, in which the molecule is identical with the primary particle, and in which the individual atoms of this colloid molecule are linked together by covalent bonds, we propose for better definition the name macromolecule.”3 The existence of polymers and their definition were debated almost up to 1953, when Staudinger was awarded the first Nobel Prize for the field of macromolecular chemistry.3,4 The journal Chemical Reviews demonstrated to be in the frontiers of chemical sciences by accepting and publishing in 1931 the first comprehensive review on “Polymerization”.1 In the introductory part of this article, Wallace H. Carothers described the generally agreed by organic chemists definition of polymerization. “Polymerization is the chemical combination involving the operation of primary valence forces, and that the term polymer should not be used (as it f requently is by physical inorganic chemists) to name loose or vaguely defined molecular aggregates.” In the next sentence, Carothers states. “Beyond this def inition, however, there is not much agreement.” In the past 15 years the Editors of Chemical Reviews invited 3 thematic issues5−8 on the topics of “Frontiers in Polymer Chemistry”5 “Frontiers in Polymer Synthesis”,6 and “Frontiers in Macromolecular and Supramolecular Science (Part 1 and Part 2)”.7,8 From the first review published by Chemical Reviews in 19311 to the 3 thematic issues from the early 21st century,5−8 the definition of polymerization and polymers has changed to incorporate the molecular aggregates excluded from the earlier definition. “Dynamers, as Jean-Marie Lehn, the inventor of this field names them, may be defined as constitutional dynamic polymers of either supramolecular or molecular nature, i.e., polymeric entities whose monomeric components are linked through reversible connections, which can be either non-covalent interactions or reversible covalent bonds.9” Therefore, what the organic chemists used to state in 1931 that “should not be used”,1 in the past decade of the 20th century became accepted.9,10 Consequently, the title of the current thematic issue was expanded from Frontiers in Polymer Chemistry5 or Polymer Synthesis6 to Frontiers in Macromolecular and Supramolecular Science.7,8 This issue covers an entire range of topics outlined by its title. New methodologies for the radical polymerization of nonactivated olefins via reversible activation are reviewed by Merna, Vlček, Volkis, and Michl. The synthesis of side-chain modified polypeptides is discussed by Deming and constitutional dynamic polymers (dynamers) toward the natural selection of function by Zhang and Barboiu. Anastasaki, © 2016 American Chemical Society
Nikolaou, Nurumbetov, Wilson, Kempe, Quinn, Davis, Wittaker, and Haddleton review recent developments in SETLRP mediated by Cu(0), while Mavila, Eivgi, Berkovich, and Lemcoff discuss intramolecular cross-linking for the synthesis of polymer nanoparticles that are similar in function to proteins. Würthner, Saha-Mö ller, Fimmel, Ogi, Leowanawat, and Schmidt are reviewing the field of supramolecular assemblies derived from perylene bisimide dyes, while Gaitzsch, Huang, and Voit present the engineering of supramolecular polymer capsules as smart nanoreactors. Shen and Okamoto, the inventor of the field, teach us how organic chemists separate enantiomers on a daily basis with tools constructed from stereoregular chiral polymers, while Wöhrle, Wurzbach, Kirres, Kostidou, Kapernaum, Litterscheidt, Haenle, Staffeld, Baro, Giesselmann, and Laschat discuss the self-organization of discotic and their precursor molecules into columnar liquid crystals. Functional cis-stereoisomers of poly(phenylacetylene)s are used to construct unprecedented supramolecular assemblies, and that topic is reviewed by Freire, Quiñoá, and Riguera of the laboratory that pioneered this field. These tremendous advances in the frontiers of macromolecular and supramolecular science would not have been accessible without the new solid state NMR methodologies elaborated and discussed by the Hansen, Graf, and Spiess laboratory. Dendritic, oligomeric, and polymeric self-immolative molecular amplification is a concept elaborated by the Shabat laboratory and is reviewed together with Roth, Green, and Gnaim, while Ciferri discusses the transition of molecular order to the macroscopic level. Synthesis of boronic acid-containing polymers and their applications to materials and medicine is reviewed by Brooks and Sumerlin. All polyolefin composites and sustainable materials by multisite catalysis are discussed by Stürzel, Mihan, and Mülhaupt. Activated ester-containing polymers and their use in the synthesis of functional macromolecules are reviewed by Das and Theato, while Jungst, Smolan, Schacht, Schreibel, and Groll discuss strategies and molecular design criteria for 3D printable hydrogels. Renewable resources, ranging from lignocellulose, carbodydrates, furans, vegetable oils, and polysaccharides, for the replacement of oil and coal resources of synthetic monomers and polymers are reviewed by three research groups: Delidovich, Hausoul, Deng, Pfützeń ́ de Paz, and reuter, Rose, and Palkovits; Galbis, Garcia-Marti n, Galbis; and Gandini, Lacerda, Carvalho, and Trovatti. Finally, I would like to remind mostly the young practitioners of this field of a statement by a pioneer of the field of polymer science that I cited also in the previous two thematic issues.5,6 “I found out quickly that there is no substitute for reading every reference citedsecond-hand citations are incredibly unreliable.”2 However, I am convinced that these review articles will provide Special Issue: Frontiers in Macromolecular and Supramolecular Science Published: February 10, 2016 769
DOI: 10.1021/acs.chemrev.6b00058 Chem. Rev. 2016, 116, 769−770
Chemical Reviews
Editorial
an accelerated access to the primary references that facilitated the merger between macromolecular and supramolecular sciences.3,4,9 This thematic issue would not have been possible without the invitation from the Editors and Editorial Advisory Board of Chemical Reviews, the hard and dedicated work of all authors who have contributed to this thematic issue, and the reviewers who made their work publishable. I would like to thank all of them.
Romanian International Chapter C. Simionescu Award, and Medal for Excellence in Macromolecular Chemistry (2015).
REFERENCES (1) Carothers, W. H. Polymerization. Chem. Rev. 1931, 8, 353−426. (2) Morawetz, H. Polymers. The Origins and Growth of a Science; Wiley: New York, 1985. (3) Percec, V. Preface in Percec, V. Ed.; Hierarchical Macromolecular Structures: 60 Years after the Staudinger Nobel Prize I. Adv. Polym. Sci. 2013, 261, 1−421. (4) Percec, V. Ed.; Hierarchical Macromolecular Structures: 60 Years after the Staudinger Nobel Prize II. Adv. Polym. Sci. 2013, 262, 1−452. (5) Frontiers in Polymer Chemistry. Chem. Rev. 2001, 101 (12), http://pubs.acs.org/toc/chreay/101/12. (6) Frontiers in Polymer Synthesis. Chem. Rev. 2009, 109 (11), http://pubs.acs.org/toc/chreay/109/11. (7) Frontiers in Macromolecular and Supramolecular Science thematic issue, Part 1. Chem. Rev. 2016, 116 (3), http://pubs.acs.org/ toc/chreay/116/3. (8) Frontiers in Macromolecular and Supramolecular Science thematic issue, Part 2. Chem. Rev. 2016, 116 (4), http://pubs.acs.org/ toc/chreay/116/4 (to be published on February 24, 2016). (9) Lehn, J. M. Dynamers: From Supramolecular Polymers to Adaptive Dynamic Polymers. Adv. Polym. Sci. 2013, 261, 155−172. (10) Percec, V. From Synthetic Macromolecules to Biological-Like Complex Systems. Adv. Polym. Sci. 2013, 261, 173−198.
Virgil Percec
University of Pennsylvania
AUTHOR INFORMATION Notes
Views expressed in this editorial are those of the author and not necessarily the views of the ACS. Biography Virgil Percec was born and educated in Romania (Ph.D. in 1976). After postdoctorals at Hermann Staudinger Haus, University of Freiburg, Germany, and Institute of Polymer Science of University of Akron, United States, he joined the Department of Macromolecular Science of Case Western Reserve University in 1982, and became Full Professor in 1986 and Leonard Case Jr. Chair in 1993. In 1999 he joined the Department of Chemistry at the University of Pennsylvania as P. Roy Vagelos Chair and Professor of Chemistry. He is best known for his pioneering work on stereoisomers of polyarylacetylenes, the transplant of phase transfer catalysis from organic to polymer chemistry, intramolecular and intermolecular charge transfer complexes, the development of molecular, macromolecular, and supramolecular liquid crystals with complex architecture, the discovery and development of the field of nickel-catalyzed Suzuki cross-coupling, borylation, mixed-ligand and precatalyst concepts, the discovery of SET-LRP, and the discovery and development of supramolecular dendrimer chemistry and of complex functional systems by using Nature as a model and biological principles. He has contributed over 700 refereed publications, 80 patents, 18 books, and special issues and over 1140 endowed, plenary, and invited lectures. He has been editor of Journal of Polymer Science: Part A: Polymer Chemistry and of the Book Series Liquid Crystals and is editor of Advances in Polymer Science. Percec serves on the Editorial and Advisory Boards of 22 journals. His list of awards includes Honorary Foreign Member to the Romanian Academy (1993), Humboldt Award for Senior US Scientists (1997, 2011), NSF Award for Creativity in Research (1990, 1995, 2000, 2015), Fellow of IUPAC (2001), PTN Polymer Award from Netherlands (2002), Fellow of PMSE, ACS (2003), Fellow of AAAS (2004), ACS Award in Polymer Chemistry (2004), Staudinger Medal from ETH, Zurich (2005), Doctor Honoris Causa from Polytechnic University, Jassy (2007) and University of Athens, Greece (2007), International Award and Medal of the Society of Polymer Science, Japan (2007), H.F. Mark Medal and Award from the Austrian Institute for Science and Technology, Vienna, Austria (2008), Lecturer of the Swiss Chemical Society (2008), Honorary Member of the Israel Chemical Society (2009), Inaugural ACS Lecture Kavli Foundation Innovation in Chemistry (2011), Honorary Professor of the Australian Institute for Bioengineering & Nanoscience, University of Queensland, Brisbane, Australia (2012), Foreign Member of the Royal Swedish Academy of Engineering Sciences IVA (2013), Honorary Member and “Petru Poni” Medal of the Romanian Chemical Society (2014), “One of the World’s Most Influential Minds of Our Time” by Thomson Reuters (2014 and 2015), the ACS in Collaboration with the 770
DOI: 10.1021/acs.chemrev.6b00058 Chem. Rev. 2016, 116, 769−770
