In recent years, the development of new approaches allowing for the synthesis of environment-responsive copolymers and their nanomaterials has been considered as a promising platform in materials and pharmaceutical sciences. Herein, we report a carbonylimidazole-hydroxyl coupling chemistry as a robust means to synthesize multifunctional bio-reducible poly(carbonate-disulfide)s (PCss) and their block copolymers bearing both carbonate and disulfide groups on the main chains. Our approach centers on the synthesis of a disulfide-bearing difunctional carbonylimidazole monomer for step-growth polymerization with various diols, enabling the fabrication of functional PCss with various properties. The synthesized PCss copolymers exhibit rapid and tunable degradation in a reducing environment into small hydrophilic molecules. Further, the versatility of our approach is demonstrated with block copolymerization through post-modification to synthesize an amphiphilic triblock copolymer and its nanoassemblies exhibiting dual reduction/acid-responsive degradation useful for intracellular drug delivery. These results suggest that the approach utilizing carbonyl imidazole-hydroxyl coupling chemistry opens new opportunities for the design and development of a broad range of novel main-chain-degradable polymeric nanomaterials with multifunctionalities.

近年来，允许合成环境响应性共聚物及其纳米材料的新方法的开发已被认为是材料和制药科学中有希望的平台。本文中，我们报道了羰基咪唑-羟基偶联化学作为合成多功能生物可还原聚（碳酸二硫化物）（PCss）及其在主链上同时带有碳酸酯基和二硫键基团的嵌段共聚物的稳健手段。我们的方法集中在具有二硫键的双官能羰基咪唑单体的合成上，该单体可与各种二醇逐步聚合，从而能够制造具有各种特性的功能PC。合成的PCss共聚物在还原性环境中表现出快速可调谐的降解，变成小的亲水分子。进一步，我们的方法具有多功能性，可通过后修饰进行嵌段共聚以合成两亲性三嵌段共聚物，并且其纳米组件具有双重还原/酸响应性降解，可用于细胞内药物递送，从而证明了我们方法的多功能性。这些结果表明，利用羰基咪唑-羟基偶联化学的方法为设计和开发多种具有多功能的新型主链可降解聚合物纳米材料提供了新的机会。