Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA, 15213, USA.
Department of Chemical Engineering, Carnegie Mellon University, 5000 Forbes Avenue, Pittsburgh, PA, 15213, USA.
Angew Chem Int Ed Engl. 2018 Jan 22;57(4):933-936. doi: 10.1002/anie.201711105. Epub 2018 Jan 2.
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, M =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 H O formed by reaction of O with GOx. Successful chain extension of POEOMA macroinitiator with OEOMA (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.
首次在开放体系中进行了可控的水相原子转移自由基聚合（ATRP）。该空气稳定的 ATRP 是通过葡萄糖氧化酶（GOx）催化氧气连续转化为二氧化碳来实现的，在该体系中，葡萄糖和丙酮酸钠作为连续牺牲性底物存在。使用引发剂连续激活剂再生（ICAR）ATRP 引发低聚（氧化乙烯）甲醚甲基丙烯酸酯（OEOMA，M=500）的可控聚合，在存在丙酮酸的情况下，可得到低分散度（1.09≤Đ≤1.29）和接近理论值的分子量（MWs）的聚合物。如果不添加丙酮酸，由于 O 与 GOx 反应生成的 H2O 会产生新的链，因此观察到 MWs 较低。POEOMA 大分子引发剂与 OEOMA（Đ≤1.3）和牛血清白蛋白生物缀合物（Đ≤1.22）的成功链延伸证实了聚合反应得到了很好的控制。在更大规模（25 mL）下在开放体系中进行的反应也是成功的。
