Abstract The first well‐controlled aqueous atom‐transfer radical polymerization (ATRP) conducted in the open air is reported. This air‐tolerant ATRP was enabled by the continuous conversion of oxygen to carbon dioxide catalyzed by glucose oxidase (GOx), in the presence of glucose and sodium pyruvate as sequential sacrificial substrates. Controlled polymerization using initiators for continuous activator regeneration (ICAR) ATRP of oligo(ethylene oxide) methyl ether methacrylate (OEOMA,Mn=500) yielded polymers with low dispersity (1.09≤Đ≤1.29) and molecular weights (MWs) close to theoretical values in the presence of pyruvate. Without added pyruvates, lower MWs were observed due to generation of new chains by H2O2formed by reaction of O2with GOx. Successful chain extension of POEOMA500macroinitiator with OEOMA300(Đ≤1.3) and Bovine Serum Albumin bioconjugates (Đ≤1.22) confirmed a well‐controlled polymerization. The reactions in the open air in larger scale (25 mL) were also successful. 
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                            Fully oxygen-tolerant atom transfer radical polymerization triggered by sodium pyruvate
                        
                    
    
            ATRP (atom transfer radical polymerization) is one of the most robust reversible deactivation radical polymerization (RDRP) systems. However, the limited oxygen tolerance of conventional ATRP impedes its practical use in an ambient atmosphere. In this work, we developed a fully oxygen-tolerant PICAR (photoinduced initiators for continuous activator regeneration) ATRP process occurring in both water and organic solvents in an open reaction vessel. Continuous regeneration of the oxidized form of the copper catalyst with sodium pyruvate through UV excitation allowed the chemical removal of oxygen from the reaction mixture while maintaining a well-controlled polymerization of N -isopropylacrylamide (NIPAM) or methyl acrylate (MA) monomers. The polymerizations of NIPAM were conducted with 250 ppm (with respect to the monomer) or lower concentrations of CuBr 2 and a tris[2-(dimethylamino)ethyl]amine ligand. The polymers were synthesized to nearly quantitative monomer conversions (>99%), high molecular weights ( M n > 270 000), and low dispersities (1.16 < Đ < 1.44) in less than 30 min under biologically relevant conditions. The reported method provided a well-controlled ATRP ( Đ = 1.16) of MA in dimethyl sulfoxide despite oxygen diffusion from the atmosphere into the reaction system. 
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                            - Award ID(s):
- 2000391
- PAR ID:
- 10249186
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 11
- Issue:
- 33
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 8809 to 8816
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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