Bui Tien Tan, Zhao Yan
Department of Chemistry, Iowa State University, Ames, IA 50011-3111, USA.
Nanomaterials (Basel). 2025 Jan 23;15(3):169. doi: 10.3390/nano15030169.
Aliphatic polycarbonate (PC) can be readily hydrolyzed by lipase, but bisphenol A-derived PC (i.e., BPA-PC) lacks enzyme catalysts for their efficient hydrolysis due to the high hydrophobicity and rigidity of its polymer backbone. This study aims to develop an artificial nanozyme for the selective hydrolysis of small-molecule aromatic carbonates as model substrates for BPA-PC. The catalyst is prepared through molecular imprinting of cross-linkable micelles in a one-pot reaction using a thiourea template and a zinc-containing functional monomer. The resulting water-soluble nanoparticle resembles a hydrolytic metalloenzyme to bind the appropriately shaped aromatic carbonate substrate in the active site, with the nearby zinc acting as a cofactor to activate a water molecule for the nucleophilic attack on the carbonate. Catalytic hydrolysis is observed at room temperature and pH 7, with a rate acceleration of 1 × 10 for diphenyl carbonate.
脂肪族聚碳酸酯（PC）可被脂肪酶轻易水解，但双酚A衍生的聚碳酸酯（即双酚A聚碳酸酯，BPA-PC）由于其聚合物主链的高疏水性和刚性，缺乏使其高效水解的酶催化剂。本研究旨在开发一种人工纳米酶，用于选择性水解小分子芳香族碳酸酯，作为双酚A聚碳酸酯的模型底物。该催化剂是通过使用硫脲模板和含锌功能单体在一锅反应中对可交联胶束进行分子印迹制备的。所得的水溶性纳米颗粒类似于水解金属酶，可在活性位点结合形状合适的芳香族碳酸酯底物，附近的锌作为辅因子激活水分子，对碳酸酯进行亲核攻击。在室温及pH值为7的条件下观察到催化水解，碳酸二苯酯的速率加速了1×10。
