There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

Controlled/living radical polymerization: Features, developments, and perspectives

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Degradable Controlled-Release Polymers and Polymeric Nanoparticles: Mechanisms of Controlling Drug Release

This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of reversible addition-fragmentation chain transfer (RAFT) that was published in June 2005 (Aust. J. Chem. 2005, 58, 379). The first update was published in November 2006 (Aust. J. Chem. 2006, 59, 669) and the second in December 2009 (Aust. J. Chem. 2009, 62, 1402). This review cites over 700 publications that appeared during the period mid 2009 to early 2012 covering various aspects of RAFT polymerization which include reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses, and a diverse range of applications. This period has witnessed further significant developments, particularly in the areas of novel RAFT agents, techniques for end-group transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

/pdf/living-radical-polymerization-by-the-raft-process-a-second-3rre2ur7xt.pdf

Living Radical Polymerization by the RAFT Process - A Second Update

2.1.6. Tacticity and Sequence: Advanced Control 4967 2.2. Transition Metal Catalysts 4967 2.2.1. Overviews of Catalysts 4967 2.2.2. Ruthenium 4967 2.2.3. Copper 4971 2.2.4. Iron 4971 2.2.5. Nickel 4975 2.2.6. Molybdenum 4975 2.2.7. Manganese 4976 2.2.8. Osmium 4976 2.2.9. Cobalt 4976 2.2.10. Other Metals 4976 2.3. Cocatalysts (Additives) 4977 2.3.1. Overview of Cocatalysts 4977 2.3.2. Reducing Agents 4977 2.3.3. Free Radical Initiators 4977 2.3.4. Metal Alkoxides 4977 2.3.5. Amines 4978 2.3.6. Halogen Source 4978 2.4. Initiators 4978 2.4.1. Overview of Initiators: Scope and Design 4978 2.4.2. Alkyl Halides 4978 2.4.3. Arenesulfonyl Halides 4979 2.4.4. N-Chloro Compounds 4979 2.4.5. Halogen-Free Initiators 4979 2.5. Solvents 4980 2.5.1. Overview of Solvents 4980 2.5.2. Catalyst Solubility and Coordination of Solvent 4981 2.5.3. Environmentally Friendly Solvents 4981 2.5.4. Water 4981 2.5.5. Catalytic Solvents: Catalyst Disproportionation 4981

Transition metal-catalyzed living radical polymerization : toward perfection in catalysis and precision polymer synthesis

Overview of cobalt-mediated radical polymerization: Roots, state of the art and future prospects

Highly efficient cobalt-mediated radical polymerization of vinyl acetate.

Over the past few years, cobalt-mediated radical polymerization (CMRP) has proved efficient in controlling the radical polymerization of very reactive monomers, such as vinyl acetate (VAc). However, the reason for this success and the intimate mechanism remained basically speculative. Herein, two mechanisms are shown to coexist: the reversible termination of the growing poly(vinyl acetate) chains by the Co(acac) 2 complex (acac: acetyl-acetonato), and a degenerative chain-transfer process. The importance of one contribution over the other strongly depends on the polymerization conditions, including complexation of cobalt by ligands, such as water and pyridine. This significant progress in the CMRP mechanism relies on the isolation and characterization of the very first cobalt adducts formed in the polymerization medium and their use as CMRP initiators. The structure proposed for these adducts was supported by DFT calculations. Beyond the control of the VAc polymerization, which is the best ever achieved by CMRP, extension to other monomers and substantial progress in macromolecular engineering are now realistic forecasts.

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Mechanistic insights into the cobalt-mediated radical polymerization (CMRP) of vinyl acetate with cobalt(III) adducts as initiators.

This review focuses on an emerging class of controlled radical polymerization named Organometallic-Mediated Radical Polymerization (OMRP). The latter is based on the temporary deactivation of the growing radical species by a transition metal complex and the reversible formation of a carbon-metal covalent bond. Initially developed with cobalt complexes, OMRP has extended to several metals today. As highlighted here, the choice of the metal, the structure of ligands, temperature, and additives deeply affect the course of the polymerization and its mechanism. Macromolecular engineering opportunities offered by OMRP are also described, as well as practical applications sustained by the resulting polymer materials.

Insight into Organometallic-Mediated Radical Polymerization

Poly(N-vinylcaprolactam) (PNVCL) is a thermoresponsive and biocompatible polymer that raises an increasing interest in the biomedical area, especially in drug delivery systems (DDS) that include micelles, hydrogels, and hybrid particles. The thermoresponsiveness of PNVCL, used alone or in combination with other stimuli- responsive polymers or particles (pH, magnetic field, or chemicals), is often key in the loading and/or release process in these DDS. The renewed focus on this polymer, which is known for decades, is to a large extent due to recent progress in synthetic strategies. Especially, the advent of efficient controlled radical polymerization (CRP) methods for NVCL monomer gives now access to unprecedented well-defined NVCL-based copolymers with unique properties. This Review article addresses up-to-date synthetic aspects, biological features, and biomedical applications of the latest NVCL-containing systems.

Antoine Debuigne

Papers

Overview of cobalt-mediated radical polymerization: Roots, state of the art and future prospects

Highly efficient cobalt-mediated radical polymerization of vinyl acetate.

Mechanistic insights into the cobalt-mediated radical polymerization (CMRP) of vinyl acetate with cobalt(III) adducts as initiators.

Insight into Organometallic-Mediated Radical Polymerization

Poly(N-vinylcaprolactam): a thermoresponsive macromolecule with promising future in biomedical field.