Editorial pubs.acs.org/CR
Introduction to Frontiers in Macromolecular and Supramolecular Science: Part 2 discussed the field of carbohydrates in supramolecular chemistry. Gangloff, Ulbricht, Lorson, Schlaad, and Luxenhofer reviewed the revitalized area of peptoids and polypeptoids at the frontier of supra- and macromolecular engineering. By contrast to conventional amino acids forming peptides and proteins, this active area of research is generated from Nsubstituted amino acids. Boyer, Corrigan, Jung, Nguyen, Nguyen, Adnan, Oliver, Shanmugam, and Yeow have discussed the area of copper-mediated living radical polymerization (atom transfer radical polymerization and copper(0)-mediated polymerization): from fundamentals to bioapplications. One of the most important developments in polymer synthesis involves the transformation of step-growth polymerization, pioneered by Carothers and reviewed for the first time in 1931 in Chemical Reviews,1 into living chain-growth polymerization. This topic was reviewed by Yokozawa and Ohta from the laboratory that contributed most to the development of this active area of research. Teator, Lastovickova, and Bielawski discussed the field of switchable polymerization catalysts, while Soller, Salzinger, and Rieger present the development of rare earth metalmediated precision polymerization of vinylphosphonates and conjugated nitrogen-containing vinyl monomers that was discovered and developed mostly in their laboratory. Mimicking the cell: bioinspired functions of supramolecular assemblies was reviewed by Tu, Peng, Adawy, Men, Abdelmohsen, and Wilson, and demonstrated the power of supramolecular chemistry in the elucidation of cell biology with the aid of nonbiological building blocks. The expanding field of supramolecular architectures of dendritic amphiphiles in water was discussed by Thota, Urner, and Haag while Hammer and Müllen, of the laboratory that demonstrated the evolution of polyphenylenesexpanding in all directionshave updated the most recent developments, in their review. Reactions and polymerizations at the liquid−liquid interface were reviewed by Piradashvili, Alexandrino, Wurm, and Landfester. Herzberger, Niederer, Pohlit, Seiwert, Worm, Wurm, and Frey have discussed the most recent developments in the polymerization of ethylene oxide, propylene oxide, and other alkylene oxides: synthesis, novel polymer architectures, and bioconjugation, while Asandei reviewed the photomediated controlled radical polymerization and block copolymerization of vinylidene fluoride, a field developed by his laboratory. Continuing the series of three reviews from Part 1 of this thematic issue on renewable resources for the synthesis of polymers, Upton and Kasko have discussed strategies for the conversion of lignin to high-value polymeric materials: review and perspective, in a review that is complementary to those from the previous issue. Enzymes as green catalysts for precision macromolecular synthesis were reviewed by Shoda, Uyama, Kadokawa, Kimura,
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 Part 2 issue covers an entire range of topics outlined by its title and is a continuation of the Part 1 issue that was published as the previous issue of Chemical Reviews. Miura, Hoshino, and Seto have reviewed the field of glycopolymer nanotechnology and contributed the front cover for this issue. Delbianco, Bharate, Varela-Aramburu, and Seeberger, from the premier laboratory involved in carbohydrates chemistry, have © 2016 American Chemical Society
Special Issue: Frontiers in Macromolecular and Supramolecular Science Published: February 24, 2016 1671
DOI: 10.1021/acs.chemrev.6b00069 Chem. Rev. 2016, 116, 1671−1672
Chemical Reviews
Editorial
and Kobayashi from the laboratory that discovered and developed this field. Krieg, Bastings, Besenius, and Rybtchinski, from the laboratory that pioneered and developed the field, have discussed in their review the impressive developments on supramolecular polymers in aqueous media, a forefront from the prohibited part of the definition of polymers from the early days of polymers.1,9 Cavallo, Metrangolo, Milani, Pilati, Priimagi, Resnati, and Terraneo, from the laboratory that discovered and developed the field of the halogen bond, have reviewed the halogen bond and also forecast its future. The laboratory of Kamaly, Yameen, Wu, and Farokhzad presented in their review degradable controlled-release polymers and polymeric nanoparticles: mechanisms of controlling drug release, while Ricapito, Ghobril, Zhang, Grinstaff, and Putnam have reviewed synthetic biomaterials from metabolically derived synthons. Last but not least, Tomalia and Khanna have discussed in a landmark review article a systematic framework and nanoperiodic concept for unifying nanoscience: hard/soft nanoelements, superatoms, meta-atoms, new engineering properties, periodic property patterns, and predictive Mendeleev-like nanoperiodic tables, an idea and concept elaborated in the same laboratory. 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 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.
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 Romanian International Chapter C. Simionescu Award, and Medal for Excellence in Macromolecular Chemistry (2015).
ACKNOWLEDGMENTS Financial support from the National Science Foundation (grants DMR-1066116, DMR-1120901, and OISE-1243313), the P. Roy Vagelos Chair at the University of Pennsylvania, and the Humboldt Foundation is gratefully acknowledged, for the editorial work of both Part 1 and Part 2 of this thematic issue.
Virgil Percec
REFERENCES
University of Pennsylvania
(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. (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.
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 1672
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