Cobalt-mediated radical polymerizations (CMRPs) have been initiated by the radical decarboxylation of tetrachlorophthalimide activated esters. This allows for the controlled radical polymerization of activated monomers across a broad temperature range with a single cobalt species, with the incorporation of polymer end groups derived from simple carboxylic acid derivatives and termination with an organozinc reagent. This method has been applied to the synthesis of a polymer/graphene conjugate and a water-soluble protein/polymer conjugate, demonstrating the first examples of CMRP in graphene and protein conjugation.
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http://dx.doi.org/10.1021/jacsau.1c00453 | DOI Listing |
Methods Mol Biol
November 2023
Department of Chemical Engineering and Chemistry & Institute for Complex Molecular Systems, Eindhoven University of Technology, Eindhoven, the Netherlands.
Cobalt-mediated radical polymerization (CMRP) enables the preparation of both short and long polymers from acrylic and vinyl ester monomers with low dispersity. Here we describe the synthesis, purification, and characterization of polymeric mimics of ice-binding proteins based on the water-soluble polymer poly(vinyl alcohol) by CMRP. Block copolymers of poly(vinyl alcohol) and poly(acrylic acid) were prepared from the precursor copolymers poly(vinyl acetate)-b-poly(acrylonitrile) upon hydrolysis.
View Article and Find Full Text PDFJ Am Chem Soc
September 2023
Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States.
Installing ketones into a polymer backbone is a known method for introducing photodegradability into polymers; however, most current methods are limited to ethylene-carbon monoxide copolymerization. Here we use isocyanides in place of carbon monoxide in a copolymerization strategy to access degradable nonalternating poly(ketones) that either maintain or enhance the thermal properties. A cobalt-mediated radical polymerization of acrylates and isocyanides synthesizes nonalternating poly(acrylate--isocyanide) copolymers with tunable incorporation using monomer feed ratios.
View Article and Find Full Text PDFJ Am Chem Soc
September 2023
Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States.
Advances in controlled radical polymerizations by cobalt complexes have primarily taken advantage of the reactivity of cobalt as a persistent radical to reversibly deactivate propagating chains by forming a carbon-cobalt bond. However, cobalt-mediated radical polymerizations require stoichiometric ratios of a cobalt complex, deterring its utility in synthesizing well-defined polymers. Here, we developed a strategy to use cobalt as a catalyst to control radical polymerizations via halogen atom transfer with alkyl halide initiators.
View Article and Find Full Text PDFPolymers (Basel)
July 2023
Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, V.le Teresa Michel, 5, 15121 Alessandria, Italy.
Poly(methylmethacrylate--methacrylic acid) (PMMA--MAA) polymers were prepared via cobalt-mediated free radical copolymerization and were characterized after synthesis. The synthesis led to a 98.5% conversion and a final ratio between the two units, MMA/MAA, was equal to 63:37 mol%.
View Article and Find Full Text PDFAnal Chem
July 2023
School of Biomedical Engineering, Shenzhen University Health Science Center, Shenzhen, Guangdong 518060, P.R. China.
Cobalt-mediated radical polymerization is noted for its great level of control over the polymerization of acrylic and vinyl esters monomers, even at high molar mass. Vitamin B, a natural bionic enzyme cobalt complex, involves the conversion of organic halides to olefins through chain-growth polymerization. In this work, the notion of R-Co(III) free radical persistent free radical effect and vitamin B circulation were first reported for the perception of ultralow abundance of microRNA-21, a lung cancer biomarker.
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