Catalyst transfer polymerization (CTP) is widely applied to the synthesis of well-defined π-conjugated polymers. Unlike other polymerization reactions that can be performed in water (e.g., controlled radical polymerizations and ring-opening polymerizations), CTP has yet to be adapted for the modification of biopolymers. Here, we report the use of protein–palladium oxidative addition complexes (OACs) that enable catalyst transfer polymerization to furnish protein–polyarene conjugates. These polymerizations occur with electron-deficient monomers in aqueous buffers open to air at mild (≤37 °C) temperatures with full conversion of the protein OAC and an average polymer length of nine repeating units. Proteins with polyarene chains terminated with palladium OACs can be readily isolated. Direct evidence of protein–polyarene OAC formation was obtained using mass spectrometry, and all protein–polyarene chain ends were uniformly functionalized via C–S arylation to terminate the polymerization with a small molecule thiol or a cysteine-containing protein.

中文翻译：

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钯介导的蛋白质-聚芳烃偶联物的合成

催化剂转移聚合 (CTP) 广泛应用于合成定义明确的 π-共轭聚合物。与可在水中进行的其他聚合反应（例如，受控自由基聚合和开环聚合）不同，CTP 尚未适用于生物聚合物的改性。在这里，我们报告了使用蛋白质-钯氧化加成络合物 (OAC) 使催化剂转移聚合能够提供蛋白质-聚芳烃共轭物。这些聚合发生在水性缓冲液中的缺电子单体在温和 (≤37 °C) 温度下对空气开放，蛋白质 OAC 完全转化，平均聚合物长度为九个重复单元。具有以钯 OAC 终止的聚芳烃链的蛋白质可以很容易地分离。