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Ronald Breslow教授将进行研究，这将极大地改善人工酶的特性，增加我们对使酶有效的因素的理解，同时提供信息，可以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在水中的反应是如何利用疏水效应来提高反应速率和选择性的，同时避免水与催化酸、碱和底物基团形成氢键所造成的反应速率减慢效应。布雷斯洛教授将扩展他在之前的资助下发表的初步研究成果，在这项研究中，辅酶模拟物吡哆胺被附着在合成多胺的内部。碳氢化合物链也将被整合到聚合物中，以产生这种“人工酶”的疏水内部。最近发现，与吡哆胺本身在水中相比，用这种酶模拟物在水中合成色氨酸的速度可以加快24万倍。将观察到的效应按速率和结合项进行分类，并观察到附着的烃链的对比效应。这项工作的目标之一是开发一个程序来了解各种聚合物或低聚物在酶模拟物中的作用。有机和大分子化学项目支持哥伦比亚大学的罗纳德·布雷斯洛教授，他将试图展示如何发明实用的合成方法，使其在水溶液中发挥作用，并且在许多方面比传统的有机溶剂更环保。工业可能采用发明的催化剂，或其一些扩展，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是如何起作用的，并可能为开发新的更有效的方法指明道路。

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.