Bioorganic Chemistry Laboratory, New Chemistry Unit and School of Advanced Materials (SAMat), Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur P.O., Bengaluru 560064, Karnataka, India.
ACS Appl Mater Interfaces. 2020 Mar 25;12(12):14057-14063. doi: 10.1021/acsami.0c01803. Epub 2020 Mar 10.
Lewis acidity plays a key role in the catalytic activity of lead ion (Pb) in the hydrolysis of glucose in solution under harsh synthetic conditions. We report a number of structurally similar d-gluconamide amphiphiles as functional organic ligands with active an -NH center capable of coordinating Pb (., Pb-N-C) in basic condition to enhance the catalytic efficiency through the scheme of molecular architectonics. Amphiphiles with different hydrophobic unit form assembly-architectures with a varying second coordination sphere around the active metal ion center. As a result, the active Pb center in each architecture exhibits substantially different efficiency toward catalyzing the glucose hydrolysis under ambient temperature. The catalytic performance of the dynamic and reversible gluconamide-Pb assembly-architectures are highly dependent on their chemical environments in solution. Further, the active Pb center of gluconamide-Pb complex in the assembly architecture and dispersed states exhibits distinct outcomes with the former being a superior catalyst than the latter as well as Pb alone. The current study demonstrates the potential of molecular architectonics that relies on the hydrophobic units of designer functional amphiphiles to enrich surface electron density with enhanced σ-donation ability through space which substantially improves the catalytic efficiency of Pb toward glucose hydrolysis at ambient temperature.
路易斯酸在铅离子（Pb）在苛刻的合成条件下催化溶液中葡萄糖水解的催化活性中起着关键作用。我们报告了一些结构相似的 D-葡萄糖酰胺两亲分子作为功能有机配体，具有活性的 an -NH 中心，能够在碱性条件下与 Pb 配位（...，Pb-N-C），通过分子建筑的方案提高催化效率。具有不同疏水性单元的两亲分子形成组装结构，在活性金属离子中心周围具有不同的第二配位层。结果，每个结构中的活性 Pb 中心在环境温度下催化葡萄糖水解的效率有很大差异。动态和可逆的葡萄糖酰胺-Pb 组装结构的催化性能高度依赖于其在溶液中的化学环境。此外，组装结构和分散状态中葡萄糖酰胺-Pb 配合物的活性 Pb 中心表现出不同的结果，前者是比后者以及单独的 Pb 更好的催化剂。本研究证明了分子建筑的潜力，它依赖于设计功能两亲分子的疏水性单元，通过空间增强 σ-供电子能力来丰富表面电子密度，从而大大提高 Pb 在环境温度下对葡萄糖水解的催化效率。
