A S-Sn Lewis Pair-Mediated Ring-Opening Polymerization of α-Amino Acid N-Carboxyanhydrides: Fast Kinetics, High Molecular Weight, and Facile Bioconjugation,ACS Macro Letters

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A S-Sn Lewis Pair-Mediated Ring-Opening Polymerization of α-Amino Acid N-Carboxyanhydrides: Fast Kinetics, High Molecular Weight, and Facile Bioconjugation
ACS Macro Letters ( IF 5.1 ) Pub Date : 2018-07-09 00:00:00 , DOI: 10.1021/acsmacrolett.8b00465
Jingsong Yuan ₁ , Yi Zhang ₁ , Zezhou Li ₁ , Yaoyi Wang ₁ , Hua Lu ₁

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The rapid and controlled generation of polypeptides with ultrahigh molecular weight (MW) and well-defined chain end functionality has been a great challenge. To tackle this problem, we report here an initiation system based on a S-Sn Lewis pair, trimethylstannyl phenyl sulfide (PhS-SnMe₃), for the ring-opening polymerization (ROP) of α-amino acid N-carboxyanhydrides (NCAs). This initiator displays a strong solvent effect, and can yield polypeptides with high MW (>1.0 × 10⁵ g·mol^–1) and low polydispersity index within a few hours. The MWs of the obtained polypeptides are strongly dependent on the THF/DMF ratio. The polymerization follows a typical first-order kinetic character with respect to the monomer concentration in mixed THF and DMF. Moreover, a highly reactive phenyl thioester is in situ generated at the C-terminus of the polypeptides, which is readily accessible for native chemical ligation affording high MW and site-specific protein–polypeptide conjugates. Together, this initiator sheds light on regulating the ROP of NCAs via appropriate Lewis pair and solvent selection, and is particularly useful in preparing ultrahigh MW polypeptides within a short period of time.

中文翻译：

α-氨基酸 N-羧酸酐的 S-Sn Lewis 对介导的开环聚合：快速动力学、高分子量和简便的生物共轭

具有超高分子量 (MW) 和明确链端功能的多肽的快速和可控生成一直是一个巨大的挑战。为了解决这个问题，我们在此报告了一种基于 S-Sn Lewis 对三甲基甲锡烷基苯硫醚 (PhS-SnMe ₃ ) 的引发系统，用于 α-氨基酸N-羧酸酐 (NCA) 的开环聚合 (ROP) . 该引发剂具有很强的溶剂效应，可以产生高分子量的多肽（>1.0 × 10 ⁵ g·mol ^–1) 和几个小时内的低多分散指数。获得的多肽的分子量强烈依赖于 THF/DMF 比率。就混合 THF 和 DMF 中的单体浓度而言，聚合遵循典型的一级动力学特征。此外，在多肽的 C 末端原位产生高反应性苯基硫酯，这很容易用于天然化学连接，提供高分子量和位点特异性的蛋白质-多肽缀合物。总之，该引发剂揭示了通过适当的路易斯对和溶剂选择调节 NCA 的 ROP，并且特别适用于在短时间内制备超高分子量多肽。

更新日期：2018-07-09

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