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.

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Living Radical Polymerization by the RAFT Process - A Second Update

Advanced energy conversion and storage (ECS) devices (including fuel cells, photoelectrochemical water splitting cells, solar cells, Li-ion batteries and supercapacitors) are expected to play a major role in the development of sustainable technologies that alleviate the energy and environmental challenges we are currently facing. The successful utilization of ECS devices depends critically on synthesizing new nanomaterials with merits of low cost, high efficiency, and outstanding properties. Recent progress has demonstrated that nanostructured metal chalcogenides (MCs) are very promising candidates for efficient ECS systems based on their unique physical and chemical properties, such as conductivity, mechanical and thermal stability and cyclability. In this review, we aim to provide a summary on the liquid-phase synthesis, modifications, and energy-related applications of nanostructured metal chalcogenide (MC) materials. The liquid-phase syntheses of various MC nanomaterials are primarily categorized with the preparation method (mainly 15 kinds of methods). To obtain optimized, enhanced or even new properties, the nanostructured MC materials can be modified by other functional nanomaterials such as carbon-based materials, noble metals, metal oxides, or MCs themselves. Thus, this review will then be focused on the recent strategies used to realize the modifications of MC nanomaterials. After that, the ECS applications of the MC/modified-MC nanomaterials have been systematically summarized based on a great number of successful cases. Moreover, remarks on the challenges and perspectives for future MC research are proposed (403 references).

Nanostructured metal chalcogenides: synthesis, modification, and applications in energy conversion and storage devices

Radical addition-fragmentation chemistry in polymer synthesis

The attachment strategy based on catecholic chemistry has been arousing renewed interest since the work on polymerized catecholic amine (polydopamine) (Messersmith et al., Science, 2007, 318, 426) was published. Catechols and their derived compounds can self-assemble on various inorganic and organic materials, including noble metals, metals, metal oxides, mica, silica, ceramics and even polymers. It opens a new route to the modification of various substrates and the preparation of functional composite materials by simple chemistry. However, there is still not a full review so far about the attachment chemistry despite the dramatically increasing number of publications. This critical review describes the state-of-the-art research in the area: the design and synthesis of catecholic molecules, their adsorption mechanisms and the stability of assemblies in solution, and their applications etc. Some perspectives on future development are raised (195 references).

Bioinspired catecholic chemistry for surface modification.

A living radical polymerization (LRP) is a free radical polymerization that aims at displaying living character, (i.e., does not terminate or transfer and is able to continue polymerization once the initial feed is exhausted by addition of more monomer). However, termination reactions are inherent to a radical process, and modern LRP techniques seek to minimize such reactions, therefore providing control over the molecular weight and the molecular weight distribution of a polymeric material. In addition, the better LRP techniques incorporate many of the desirable features of traditional free radical polymerization, such as compatibility with a wide range of monomers, tolerance of many functionalities, and facile reaction conditions. The control of molecular weight and molecular weight distribution has enabled access to complex architectures and site specific functionality that were previously impossible to achieve via traditional free radical polymerizations. These LRPs are classified in three different subgroups: (1) stable free-radical polymerization such as nitroxide mediated polymerization (NMP),1,2 (2) degenerative transfer polymerization, such as iodine transfer polymerization (ITP and RITP),3,4 single electron transfer-degenerative transfer living radical polymerization(SET-DTLRP),5,6reversibleaddition-fragmentation chain transfer (RAFT),7,8 and macromolecular design via the interchange of xanthates (MADIX)9,10 polymerization, and (3) metal mediated catalyzed polymerization, such as atom transfer radical polymerization (ATRP),11-14 single electron transfer-living radical polymerization (SET-LRP),15 and organotellurium mediated living radical polymrization16-19 Among the existing LRP techniques, RAFT and MADIX are probably the most versatile processes, as they are tolerant * E-mail: T.P.D., T.Davis@UNSW.edu.au; S.P., S.Perrier@ chem.usyd.edu.au. † Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences & Engineering, UNSW. ‡ Centre for Advanced Macromolecular Design (CAMD), School of Biotechnology & Biomolecular Sciences, UNSW. § The University of Sydney. Chem. Rev. 2009, 109, 5402–5436 5402

Bioapplications of RAFT polymerization.

Synthesis of pentafluorophenyl(meth)acrylate polymers: New precursor polymers for the synthesis of multifunctional materials

Reversible addition fragmentation chain transfer (RAFT) polymerization of pentafluorophenyl methacrylate (PFMA) was carried out in the presence of cumyldithiobenzoate and 4-cyano-4-((thiobenzoyl)sulfanyl)pentanoic acid, respectively. These chain transfer agents with 2,2'-azoisobutyronitrile (AIBN) as initiator yielded the active ester polymer poly(PFMA) with M n up to 17000 g . mol -1 and low polydispersity index (M w /M n <1.2). Kinetic analysis using 19 F NMR spectroscopy and gel permeation chromatography (GPC) measurements showed controlled polymerization behavior for both chain transfer agents. Successful preparation of linear diblock copolymers consisting of an active ester block and methyl methacrylate, N-acryloylmorpholine, or N,N-diethylacrylamide, respectively, could be demonstrated. These polymers could easily react with amines in a polymer analogous reaction to form multifunctional polymers.

RAFT Polymerization of Pentafluorophenyl Methacrylate: Preparation of Reactive Linear Diblock Copolymers

Reactive polymers: a versatile toolbox for the immobilization of functional molecules on TiO2 nanoparticles.

Overcoming the Insolubility of Molybdenum Disulfide Nanoparticles through a High Degree of Sidewall Functionalization Using Polymeric Chelating Ligands

From Single Molecules to Nanoscopically Structured Functional Materials: Au Nanocrystal Growth on TiO2 Nanowires Controlled by Surface‐Bound Silicatein

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