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，极大地改善人造酶的性质，增加我们对使酶有效的因素的了解，同时产生信息，从而为重要的合成反应创造更好的催化剂。这项工作将有助于弄清楚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减速效应。布雷斯洛教授将延续他的初步出版工作，这项工作是在之前的拨款下完成的，其中模拟吡哆胺的辅酶被附着在合成多胺的内部。碳氢链也将被结合到聚合物中，以产生这种“人造酶”的疏水内部。最近发现，与在水中的吡哆胺本身相比，在水中模拟这种酶合成色氨酸的速度可以达到24万倍。观察到的影响被分类为速率项和结合项，并看到了连接的碳氢链的对比效果。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中所起的作用。有机和高分子化学项目支持哥伦比亚大学的罗纳德·布雷斯洛教授，他将试图展示发明在水溶液中起作用的实用合成方法如何对环境友好，并在许多方面比传统有机溶剂更方便。工业可以采用发明的催化剂或其延伸，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了解这些复杂的生物催化剂是如何发挥作用的，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.