His Ph.D. was in collaboration with Solvay-Solexis and devoted to the synthesis of new graft copolymers using grafting "to". In 2005, he undertook a postdoctorate position with Dupont Performance and Elastomers (Willmington, United States) and Dr. B. Ameduri dealing with the synthesis of original fluorinated elastomers using controlled radical polymerization (e.g., iodine transfer polymerization). Since October 2006, he has been a senior research fellow under the direction of Prof. Thomas Davis in the Centre of Advanced Macromolecular Design (CAMD), University of New South Wales. His research interests mainly cover the preparation of well-defined polymers, protein-polymer conjugates, and hybrid organic-inorganic nanoparticles using controlled radical polymerization. He has coauthored over 40 peer-reviewed research papers, including 2 book chapters, and 2 patents. Volga Bulmus received her B.E. and M.Sc. in Chemical Engineering and her Ph.D. in bioengineering (Hacettepe University, Turkey), in 2000. She worked as a postdoctoral research fellow in the Bioengineering Department at the University of Washington between 2001 and 2003. In 2004, she was granted a highly competitive The University of New South Wales (UNSW) Vice Chancellor's Research Fellowship (Australia). In 2008, she was appointed as a Senior Lecturer at the School of Biotechnology and Biomolecular Sciences (UNSW). She is also an adjunct member of The Centre for Advanced Macromolecular Design (CAMD) at UNSW. Dr. Bulmus leads a group of 5-10 researchers working on the development of advanced polymers for biotechnology and biomedical applications. She has published over 45 peer reviewed research papers. Her research interests include design, synthesis, and evaluation of well-defined polymeric systems for nanobiotechnology and drug delivery applications ranging from antitumor chemotherapy and gene silencing to bioseparations and biosensors. Tom Davis has been an academic at UNSW for 17 years following a stint in industry as a research manager at ICI in the U.K. He has coauthored 315+ reviewed papers, patents, and book chapters. He is the Director of the Centre for Advanced Macromolecular Design (CAMD) at UNSWsa Centre with expertise in bio/organic polymer synthesis and polymerization kinetics. He is also a visiting Professor at the Institute for Materials Research & Engineering (IMRE) in Singapore. In 2005 he was awarded a Federation Fellowship by the Australian Research Council. He serves (or has served) on the editorial advisory boards of Macromolecules,

Recent advances in controlled/living polymerization techniques and highly efficient coupling chemistries have enabled the facile synthesis of complex polymer architectures with controlled dimensions and functionality. As an example, star polymers consist of many linear polymers fused at a central point with a large number of chain end functionalities. Owing to this exclusive structure, star polymers exhibit some remarkable characteristics and properties unattainable by simple linear polymers. Hence, they constitute a unique class of technologically important nanomaterials that have been utilized or are currently under audition for many applications in life sciences and nanotechnologies. This article first provides a comprehensive summary of synthetic strategies towards star polymers, then reviews the latest developments in the synthesis and characterization methods of star macromolecules, and lastly outlines emerging applications and current commercial use of star-shaped polymers. The aim of this work is to promote star polymer research, generate new avenues of scientific investigation, and provide contemporary perspectives on chemical innovation that may expedite the commercialization of new star nanomaterials. We envision in the not-too-distant future star polymers will play an increasingly important role in materials science and nanotechnology in both academic and industrial settings.

A previously published simulation and data fitting procedure for the reversible addition fragmentation chain transfer (RAFT) process using the PREDICI simulation program has been extended to cumyl phenyldithioacetate mediated styrene and methyl methacrylate (MMA) bulk homopolymerizations. The experimentally obtained molecular weight distributions (MWDs) for the styrene system are narrow and unimodal and shift linearly with monomer conversion to higher molecular weights. The MMA system displays a hybrid of conventional chain transfer and living behavior, leading to bimodal MWDs. The styrene system has been subjected to a combined experimental and modeling study at 60 °C, yielding a rate coefficient for the addition reaction of free macroradicals to polymeric RAFT agent, k β, of approximately 5.6 × 105 L mol-1 s-1 and a decomposition rate coefficient for macroradical RAFT species, k - β, of about 2.7 × 10-1 s-1. The transfer rate coefficient to cumyl phenyldithioacetate is found to be close to 2.2 × 105 L mol-1 s-1. The MMA system has been studied over the temperature range 25−60 °C. The hybrid behavior observed in the MMA polymerizations has been exploited (at low monomer conversions) to perform a Mayo analysis allowing the determination of the temperature dependence of the transfer to cumyl phenyldithioacetate reaction. The activation energy of this process is close to 26 kJ mol-1. In contrast to the styrene system, the PREDICI simulation procedure cannot be successfully applied to cumyl phenyldithioacetate mediated MMA polymerizations for the deduction of k β and k - β. This inability is due to the hybrid nature of the cumyl phenyldithioacetate−MMA system, leading to a significantly reduced sensitivity toward k β and k - β.

A full kinetic scheme for the free‐radical reversible addition–fragmentation chain transfer (RAFT) process is presented and implemented into the program package PREDICI®. With the cumyl dithiobenzoate‐mediated bulk polymerization of styrene at 60 °C as an example, the rate coefficients associated with the addition–fragmentation equilibrium are deduced by the careful modeling of the time‐dependent evolution of experimental molecular weight distributions. The rate coefficient for the addition reaction of a free macroradical to a polymeric RAFT species (kβ) is approximately 5 · 105 L mol−1 s−1, whereas the fragmentation rate coefficient of the formed macroradical RAFT species is close to 3 · 10−2 s−1. These values give an equilibrium constant of K = kβ/k−β = 1.6 · 107 L mol−1. Conclusive evidence is given that the equilibrium lies well on the side of the macroradical RAFT species. The high value of kβ is comparable in size to the propagation rate coefficients reported for acrylates. The transfer rate coefficient to cumyl dithiobenzoate is close to 3.5 · 105 L mol−1 s−1. A careful sensitivity analysis was performed, which indicated that the reported rate coefficients are accurate to a factor of 2. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1353–1365, 2001

In this Perspective, we reflect on a decade of research on the protein corona and contemplate its broad implications for future science and engineering at the bio-nano interface. Specifically, we focus on the physical origins and time evolution of the protein corona, differences in the nanoparticle-protein entity in in vitro and in vivo environments, the role of stealth polymers to minimize the formation of the protein corona, relevant computational and theoretical developments, and the "biocorona", a concept extrapolated from the field of nanomedicine. We conclude the Perspective by outlining future directions and opportunities concerning the protein corona in the coming decade.

The reversible addition fragmentation chain transfer (RAFT) bulk polymerization of a fast propagating monomer (methyl acrylate, MA) has been studied using 1-phenylethyl dithiobenzoate (1-PEDB) and 2-(2-cyanopropyl) dithiobenzoate (CPDB) as RAFT agents at 60 °C. Rate retardation with increasing initial RAFT agent concentrations is common to both 1-PEDB-and CPDB-mediated MA polymerizations and occurs in comparable magnitude. A pronounced inhibition period is observed in 1-PEDB-mediated MA polymerizations, whereas the corresponding CPDB-mediated polymerizations show considerably less inhibition. The cause for this inhibition may either be associated with the leaving group of the initial RAFT agent or with the slow fragmentation of the initial intermediate macroRAFT radical. The present experimental data suggest that slow fragmentation is the probable cause for inhibition. We conclude that the radical intermediate formed by addition of radicals to the initial RAFT agent is different in stability than the macroRAFT radical formed analogously from macroRAFT agent. The inhibition period is effectively reduced by the use of CPDB as the initial RAFT agent in methyl acrylate polymerizations.

Biotechnology, biomedicine, and nanotechnology applications would benefit from methods generating well-defined, monodisperse protein-polymer conjugates, avoiding time-consuming and difficult purification steps. Herein, we report the in situ synthesis of protein-polymer conjugates via reversible addition-fragmentation chain transfer polymerization (RAFT) as an efficient method to generate well-defined, homogeneous protein-polymer conjugates in one step, eliminating major postpolymerization purification steps. A water soluble RAFT agent was conjugated to a model protein, bovine serum albumin (BSA), via its free thiol group at Cys-34 residue. The conjugation of the RAFT agent to BSA was confirmed by UV-visible spectroscopy, matrix-assisted laser desorption ionization--time of flight (MALDI-TOF), and 1H NMR. BSA-macroRAFT agent was then used to control the polymerization of two different water soluble monomers, N-isopropylacrylamide (NIPAAm) and hydroxyethyl acrylate (HEA), in aqueous medium at 25 degrees C. The growth of the polymer chains from BSA-macroRAFT agent was characterized by size exclusion chromatography (SEC), 1H NMR, MALDI-TOF, and polyacrylamide gel electrophoresis (PAGE) analyses. The controlled character of the RAFT polymerizations was confirmed by the linear evolution of molecular weight with monomer conversion. The SEC analyses showed no detectable free, nonconjugated polymer formation during the in situ polymerization. The efficiency of BSA-macroRAFT agent to generate BSA-polymer conjugates was found to be ca. 1 by deconvolution of the SEC traces of the polymerization mixtures. The structural integrity and the conformation-related esterase activity of BSA were found to be unaffected by the polymerization conditions and the conjugation of the polymer chain. BSA-poly(NIPAAm) conjugates showed hybrid temperature-dependent phase separation and aggregation behavior. The lower critical solution temperature values of the conjugates were found to increase with the decrease in molecular weight of poly(NIPAAm) block conjugated to BSA.

This highlight describes recent developments in reversible addition-fragmentation transfer (RAFT) polymerization. Succinct coverage of the RAFT mechanism is supplemented by details of synthetic methodologies for making a wide range of architectures ranging from stars to combs, microgels, and blocks. In addition, RAFT reactions in different media such as emulsion and ionic liquids receive attention. Finally, a specific example of a novel material design is briefly introduced, whereas polymers prepared via RAFT are adopted for microporous/honeycomb membrane design.