The development of advanced materials based on well-defined polymeric architectures is proving to be a highly prosperous research direction across both industry and academia. Controlled radical polymerization techniques are receiving unprecedented attention, with reversible-deactivation chain growth procedures now routinely leveraged to prepare exquisitely precise polymer products. Reversible addition-fragmentation chain transfer (RAFT) polymerization is a powerful protocol within this domain, where the unique chemistry of thiocarbonylthio (TCT) compounds can be harnessed to control radical chain growth of vinyl polymers. With the intense recent focus on RAFT, new strategies for initiation and external control have emerged that are paving the way for preparing well-defined polymers for demanding applications. In this work, the cutting-edge innovations in RAFT that are opening up this technique to a broader suite of materials researchers are explored. Emerging strategies for activating TCTs are surveyed, which are providing access into traditionally challenging environments for reversible-deactivation radical polymerization. The latest advances and future perspectives in applying RAFT-derived polymers are also shared, with the goal to convey the rich potential of RAFT for an ever-expanding range of high-performance applications.

The metal-free semiconductor, graphitic carbon nitride (g-C3N4), was introduced into RAFT polymerization for the first time. The production of linear polyacrylate and polyacrylamide has been achieved via PET-RAFT polymerization using g-C3N4 as a photoactive organocatalyst without prior deoxygenation. The resulting polymers display controlled molecular weights, narrow polymer dispersities, and high end-group fidelity as exemplified by 1 H NMR analysis, MALDI-TOF-MS measurement and chain extension experiment. Temporal control is illustrated by intermittent light and dark cycles, with polymer growth arrested in the absence of irradiation. The effects of changing RAFT agents (i.e. trithiocarbonates), solvents, catalyst concentrations and degrees of polymerization in this system have been investigated. The successful polymerization of non-purified monomer (i.e. still containing radical inhibitors) demonstrates the robust nature of the presented PET-RAFT system. 28 via ET processes to generate reactive species. Although various semiconductors have been employed in copper-catalysed CRPs of methacrylates, 26 there are few studies reporting the controlled RDRP of acrylates based on semiconductor

Fine control over the architecture and/or microstructure of synthetic polymers is fast becoming a reality owing to the development of efficient and versatile polymerization techniques and conjugation reactions. However, the transition of these syntheses to automated, programmable, and high-throughput operating systems is a challenging step needed to translate the vast potential of precision polymers into machine-programmable polymers for biological and functional applications. Chain-growth polymerizations are particularly appealing for their ability to form structurally and chemically well-defined macromolecules through living/controlled polymerization techniques. Even using the latest polymerization technologies, the macromolecular engineering of complex functional materials often requires multi-step syntheses and purification of intermediates, and results in sub-optimal yields. To develop a proof-of-concept of a framework polymerization technique that is readily amenable to automation requires several key characteristics. In this study, a new approach is described that is believed to meet these requirements, thus opening avenues toward automated polymer synthesis.

Selective cancer treatment using combined Fenton and starvation therapies through hemoglobin and glucose oxidase encapsulated in pH-sensitive ZIF-8.

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