Presidential Young Investigators Award

在有机溶剂中使用酶是一种相对较新的技术，它大大扩展了传统的水基生物催化。然而，在有机合成和基于酶的分析等领域的大量应用仅为阐明有机介质中控制酶催化的原理和参数提供了框架。两个长期研究方向将在PYI奖的过程中进行，包括：1)理解和控制非水介质中决定酶催化的参数；2)在有机合成中使用酶作为催化剂的方法的发展。第一个目标是研究溶剂对酶结构和功能的作用。EPR自旋标记将用于在非水介质催化过程中探测酶的活性位点和表面微环境。第二个目标对区域和立体选择性生物转化具有深远的影响。需要研究的具体反应包括合成用于生物可降解聚合物的含糖聚酯，作为无甲醛塑料替代品的过氧化物酶产生的酚醛树脂，选择性合成低聚糖。酶是自然界的催化剂，在温和的条件下表现出敏锐的反应特异性和快速的催化速率。传统上，酶被认为是水基催化剂。由于酶在活组织的水（水）环境中起作用，酶在生物催化中的几乎所有应用都涉及水溶液。不幸的是，对于大多数具有商业利益的反应（例如，制药、合成中间体、塑料生产等），水不是合适的反应介质。合成化学家很久以前就认识到了这一点，而且大多数有机反应通常是在有机（非水）溶剂中进行的。最近，一些研究小组已经表明，酶可以在有机溶剂中起作用。在这个PYI奖项的过程中，研究方向涉及有机介质中酶催化的基础和应用方面。从基本观点出发，研究控制酶在溶剂中的功能的因素。

The use of enzymes in organic solvents is a relatively new technology that significantly extends conventional aqueous- based biocatalysis. However, the multitude of applications in areas such as organic synthesis and enzyme-based analyses have provided only the framework for elucidating the principles and parameters that govern enzymatic catalysis in organic media. Two long-term research directions will be pursued during the course of the PYI award and include l) the understanding and control of the parameters that dictate enzymatic catalysis in non-aqueous media; and 2) the development of methodologies for the use of enzymes as catalysts in organic synthesis. The first goal involves studying the role of the solvent on enzyme structure and function. EPR spin labeling will be performed to probe enzymic active site and surface microenvironments during catalysis in non-aqueous media. The second goal has far reaching implications for regio-and stereoselective biotransformations. Specific reactions to be studied include the synthesis of sugar-containing polyesters for biodegradable polymers, peroxidase-produced phenolic resins as formaldehyde-free plastics replacements, and selective synthesis of oligosaccharides. Enzymes are nature's catalysts that exhibit keen reaction specificities and fast rates of catalysis under mild conditions. Traditionally, enzymes have been thought of as water-based catalysts. Because enzymes function in a water (aqueous) environment within living tissues, nearly all applications of enzymes in biocatalysis has involved aqueous solutions. Unfortunately, for most reactions of commercial interest (e.g., pharmaceutical manufacture, synthetic intermediates, plastics production, etc.), water is not a suitable reaction medium. Synthetic chemists had realized this long ago, and most organic reactions are routinely performed in organic (non-aqueous) solvents. Recently, a number of research groups have shown that enzymes can function in organic solvents. The research directions being targeted during the course of this PYI award involve both fundamental and applied aspects of enzymatic catalysis in organic media. From a fundamental standpoint, the factors that control enzyme function in solvents will be studied.