Biomimetic Polymeric Catalysis in Water

在化学系有机动力学项目的支持下，哥伦比亚大学的罗纳德布雷斯洛教授将进行研究，这将大大改善人工酶的特性，增加我们对使酶有效的因素的理解，同时产生可以导致为重要的合成反应创造更好的催化剂的信息。这项工作将有助于澄清水中的反应如何利用疏水效应来提高速率和选择性，同时避免水通过氢键与催化酸、碱和底物基团形成的速率减慢效应。Breslow教授将扩展他在先前资助下完成的初步发表的工作，其中辅酶模拟吡哆胺附着在合成多胺的内部。碳氢化合物链也将被纳入聚合物中，以产生这种“人造酶”的疏水内部。“最近发现，与吡哆胺本身在水中相比，在水中使用这种酶模拟物可以实现色氨酸合成的240，000倍加速。所观察到的效果被分为速率和结合项，并观察到所连接的烃链的对比效果。这项工作的目标之一是开发一个程序，以了解各种聚合物或低聚物在酶模拟物中发挥的作用。有机和高分子化学计划支持哥伦比亚大学的罗纳德布雷斯洛教授，他将试图展示如何在水溶液中发挥作用的实用合成方法的发明将是环境友好的，并且在许多方面比传统的有机溶剂更方便。工业界可能会采用所发明的催化剂，或其某些扩展，生物化学家和学生将从这项工作的发现中学习一般原理。对酶模拟物的研究将有助于我们理解这些复杂的生物催化剂如何发挥作用，并可能为开发新的更有效的方法指明方向。

With the support of the Organic Dynamics Program in the Chemistry Division, Professor Ronald Breslow of Columbia University will perform research that will greatly improve the properties of artificial enzymes adding to our understanding of the factors that make enzymes effective while producing information that can lead to the creation of better catalysts for important synthetic reactions. This work will help make it clear how reactions in water can use the hydrophobic effect to promote rate and selectivity while avoiding the rate-slowing effect that water can impose by hydrogen bonding to catalytic acids and bases and substrate groups. Professor Breslow will extend his preliminary published work, done under the previous grant, in which the coenzyme mimic pyridoxamine is attached in the interior of a synthetic polyamine. Hydrocarbon chains will also be incorporated into the polymer to produce a hydrophobic interior to this "artificial enzyme." It was recently found that a 240,000-fold acceleration of the synthesis of tryptophan with this enzyme mimic in water could be achieved, compared with pyridoxamine itself in water. Effects that were observed were sorted into rate and binding terms, and contrasting effects of the attached hydrocarbon chains were seen. One of the goals of this work is to develop a program to understand the role that various polymers or oligomers play in enzyme mimics. The Organic and Macromolecular Chemistry Program supports Professor Ronald Breslow of Columbia University who will attempt to show how the invention of practical synthetic methods that function in water solution will be environmentally friendly, and in many ways more convenient than traditional organic solvents. Industry may adopt the catalysts invented, or some extensions thereof, and biochemists and students will learn general principles from the findings of this work. The investigation of enzyme mimics will aid in our understanding of how these complex biological catalysts function and perhaps point the way to the development of new and more efficient methodology.