Structural Investigation of Molecularly Engineering Polymers Prepared by Enzymatic Polymerization

拟议的研究的主要目标是了解的基本机制的氧化酶聚合的电活性聚合物使用多核溶液和固态NMR光谱。 这种方法涉及一个简单的，一锅，环境相容的反应，导致一类新的水溶性，电和光活性聚合物的合成。 这种诺贝尔生物催化方法提供了，消除了以前遇到的实验困难与传统的化学反应，现在提供了令人兴奋的新的机会，了解这些基本的氧化机制。 NMR光谱将被广泛用于该计划中，既作为探针，以了解这些氧化偶联机制，并作为一种工具，以优化反应，使所得聚合物的电学和光学性能可以得到增强。 这项工作的主要重点将涉及两个子领域的调查使用多核溶液和固态NMR技术：（a）酚类和取代酚的氧化偶联机制，和（B）酶促聚合聚苯胺的反应机理和作用的聚阴离子或聚阳离子模板酶促聚合。 这项研究将显着推进酶促氧化偶联的机制和性质的基本理解，并因此允许控制优化的反应。 这一新的认识将导致分子工程的能力，各种各样的新型电活性聚合物，应该找到广泛的商业应用。这种生物催化聚合物合成的方法是环境友好的，并提供了一个有效的替代方法来合成电活性聚合物。 考虑到这些酶促合成的聚合物的水溶性，它们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在合成步骤和加工过程中减少危险化学品的使用。 对酶促合成的分子基础的更深入理解可能会导致有益于社会的潜在技术创新。

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.