Structural Investigation of Molecularly Engineering Polymers Prepared by Enzymatic Polymerization

这项研究的主要目的是利用多核溶液和固体核磁共振波谱来了解电活性聚合物氧化-酶聚合的基本机理。这种方法包括一个简单的，一锅的，环境友好的反应，导致合成一类新型的水溶性，电活性和光活性的聚合物。这种诺贝尔奖生物催化方法提供并避免了以前在传统化学反应中遇到的实验困难，现在为理解这些基本的氧化机制提供了令人兴奋的新机会。核磁共振波谱将在本计划中广泛使用，既作为了解这些氧化偶联机制的探针，也作为优化反应的工具，从而可以增强所得到的聚合物的电学和光学性能。这项工作的主要重点将涉及使用多核溶液和固体核磁共振技术的两个子领域的研究：(A)酚和取代酚的氧化偶联机理；(B)聚苯胺的酶聚合反应机理以及聚阴离子或聚阳离子模板对酶聚合的作用。这项研究将极大地促进对酶催化氧化偶联的机理和性质的基本了解，从而实现反应的受控优化。预计这一新的见解将导致分子工程的能力，广泛的新型电活性聚合物，应该得到广泛的商业应用。这种生物催化合成聚合物的方法是环境友好的，并提供了一种有效的替代方法来合成电活性聚合物。考虑到它们的水溶性，这些酶合成的聚合物的加工也可以以环境友好的方式进行。因此，这一领域研究的进展将有助于减少在合成步骤和加工过程中使用危险化学品。更深入地了解酶合成的分子基础可能会带来潜在的有益于社会的技术创新。

The key objective of the proposed research is to understand the basic mechanisms of the oxidative enzymatic polymerization of electroactive polymers using multi-nuclei solution and solid state NMR spectroscopy. This approach involves a simple, one-pot, environmentally compatible reaction that leads to the synthesis of a new class of water soluble, electrically and photonically active polymers. This nobel biocatalytic approach provides, obviates the experimental difficulties previously encountered with traditional chemical reactions and now affords exciting new opportunities to understand these fundamental oxidative mechanisms. NMR spectroscopy will be used extensively in this program both as a probe to understand these oxidative coupling mechanisms and as a tool to optimize the reactions such that the electrical and optical properties of the resulting polymers may be enhanced. The main focus of this effort will involve two sub areas of investigation using both multi-nuclei solution and solid-state NMR techniques: (a) Oxidative coupling mechanisms for phenols and substituted phenols, and (b) Reaction mechanisms of enzymatic polymerization for polyaniline and the role of polyanionic or polycationic templates on enzymatic polymerization. This study will significantly advance the basic understanding of the mechanisms and nature of enzymatic oxidative coupling and as a result allow for the controlled optimization of the reactions. It is expected that this new insight will led to the ability to molecularly engineer a wide variety of novel electroactive polymers that should find wide commercial application.This biocatalytic approach to polymer synthesis is environmentally friendly and offers an effective alternative approach to the synthesis of electroactive polymers. The processing of these enzymatically-synthesized polymers can also be carried out in an environmentally benign manner given their water solubility. Advancement of research in this area thus will help to reduce the use of hazardous chemicals both during the synthetic steps and processing. A deeper understanding of the molecular basis of the enzymatic synthesis may lead to potential technological innovations beneficial to the society.