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1. Atom transfer radical polymerization

   https://doi.org/10.1038/s43586-024-00370-y  

   Harrisson, Simon; Whitfield, Richard; Anastasaki, Athina; Matyjaszewski, Krzysztof (December 2025, Nature Reviews Methods Primers)
2. Redox-switchable atom transfer radical polymerization

   https://doi.org/10.1039/c8cc09209e  

   Dadashi-Silab, Sajjad; Lorandi, Francesca; Fantin, Marco; Matyjaszewski, Krzysztof (January 2019, Chemical Communications)

   Temporal control in atom transfer radical polymerization (ATRP) relies on modulating the oxidation state of a copper catalyst, as polymer chains are activated by L/Cu I and deactivated by L/Cu II . (Re)generation of L/Cu I activator has been achieved by applying a multitude of external stimuli. However, switching the Cu catalyst off by oxidizing to L/Cu II through external chemical stimuli has not yet been investigated. A redox switchable ATRP was developed in which an oxidizing agent was used to oxidize L/Cu I activator to L/Cu II , thus halting the polymerization. A ferrocenium salt or oxygen were used to switch off the Cu catalyst, whereas ascorbic acid was used to switch the catalyst on by (re)generating L/Cu I . The redox switches efficiently modulated the oxidation state of the catalyst without sacrificing control over polymerization. 

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3. Aerobic mechanochemical reversible-deactivation radical polymerization

   https://doi.org/10.1038/s41467-024-50562-z  

   Feng, Haoyang; Chen, Zhe; Li, Lei; Shao, Xiaoyang; Fan, Wenru; Wang, Chen; Song, Lin; Matyjaszewski, Krzysztof; Pan, Xiangcheng; Wang, Zhenhua (December 2024, Nature Communications)

   Abstract Polymer materials suffer mechano-oxidative deterioration or degradation in the presence of molecular oxygen and mechanical forces. In contrast, aerobic biological activities combined with mechanical stimulus promote tissue regeneration and repair in various organs. A synthetic approach in which molecular oxygen and mechanical energy synergistically initiate polymerization will afford similar robustness in polymeric materials. Herein, aerobic mechanochemical reversible-deactivation radical polymerization was developed by the design of an organic mechano-labile initiator which converts oxygen into activators in response to ball milling, enabling the reaction to proceed in the air with low-energy input, operative simplicity, and the avoidance of potentially harmful organic solvents. In addition, this approach not only complements the existing methods to access well-defined polymers but also has been successfully employed for the controlled polymerization of (meth)acrylates, styrenic monomers and solid acrylamides as well as the synthesis of polymer/perovskite hybrids without solvent at room temperature which are inaccessible by other means. 

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4. Externally controlled atom transfer radical polymerization

   https://doi.org/10.1039/c8cs00259b  

   Pan, Xiangcheng; Fantin, Marco; Yuan, Fang; Matyjaszewski, Krzysztof (January 2018, Chemical Society Reviews)

   Spatial and temporal regulations of ATRP by external stimuli are presented. Various ATRP techniques, e ATRP, photoATRP, and mechanoATRP, are controlled by electrical current, light, and mechanical forces, respectively. Conversely, ARGET and SARA ATRP are controlled by chemical reducing agents. ICAR ATRP is a thermally regulated process through decomposition of a radical initiator. The aim of this review is to highlight the use of external regulations in ATRP and to summarize the state-of-the-art and future perspectives, focusing on mechanistic aspects, synthetic procedures, preparation of polymers with complex architectures and functional materials, and their applications. 

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5. Photoinduced Miniemulsion Atom Transfer Radical Polymerization

   https://doi.org/10.1021/acsmacrolett.8b00371  

   Wang, Yi; Dadashi-Silab, Sajjad; Matyjaszewski, Krzysztof (June 2018, ACS Macro Letters)