Bioorganometallic Chemistry of Enzyme Active Sites with Focus on Hydrogenase

无机、生物无机和金属有机化学项目的研究奖支持德克萨斯州A&A；M大学的Marcetta Darensburg教授开展基础研究，对负责控制自然界氢代谢的酶活性部位的小分子模型进行研究。在这项研究中，我们制备了氢酶酶中发现的独特金属-有机片段的合成类似物，并测试了它们模拟在依靠微型氢经济生存的生物体中发现的产氢和耗氢催化的能力。这些天然催化剂的原子-原子连接、几何结构和光谱足迹在小分子中重现。通过将新分子嵌入到聚合物微珠和环糊精中，探讨了周围蛋白质基质的复杂和促进作用。通过这种方法，我们加深了对大自然如何将氢处理能力工程化为铁和镍的贱金属结构的理解，而商业燃料电池必须依赖昂贵且资源有限的铂。各级学生(毕业生和本科生)都对燃料电池的化学感到兴奋，对氢作为能源载体的兴趣也很高。在让年轻人对替代能源和挑战进行必要的研究的过程中，来自自然的灵感进入了生物学、生物化学、生物物理学以及合成无机化学的文献中。我们文化多元的研究小组在鼓励文法学校儿童对科学的兴趣的项目中合作；来自历史上主要是黑人学院和大学的本科生以及来自南得克萨斯州的本科生，主要是西语裔大学，加入了研究小组，通过暑期研究来帮助项目。这项工作的成功将产生足够可行的氢处理催化剂，作为分子燃料电池电极，取代铂作为燃料电池电极，并使节能燃料电池技术在更广泛的应用中可行。

The Research award in the Inorganic, Bioinorganic and Organometallic Chemisry program supports work by Professor Marcetta Darensbourg at the Texas A&M University in College Station, TX, to carry out fundamental studies on small molecule models of enzyme active sites responsible for controlling hydrogen metabolism in nature. In this research, synthetic analogues of the unique metal-organic fragments found in hydrogenase enzymes are prepared and assayed for their ability to mimic the hydrogen-producing and hydrogen-consuming catalysis found in organisms that subsist on a micro-hydrogen economy. The atom-atom connections, the geometrical structure, and spectroscopic footprints of these natural catalysts are reproduced in the small molecules. The intricate and facilitating role of the surrounding protein matrix is approached by imbedding the new molecules in polymer beads and cyclodextrins. By this approach we develop understanding of the way Nature has engineered hydrogen processing ability into base metal constructs of iron and nickel, whereas commercial fuel cells must rely on expensive and resource-limited platinum. Students at all levels (graduates and undergraduates) are excited by the chemistry of fuel cells and interest in hydrogen as an energy carrier is high. In the process of opening young minds to the needed research in alternative energy sources and challenges, inspiration from nature leads into the literature of biology, biochemistry, biophysics, as well as synthetic inorganic chemistry. Our culturally diverse research group works as a team in projects to encourage interest in science in grammar school children; undergraduates from historically black colleges and universities and from South Texas, largely Hispanic colleges, join the research group to help in the projects through summer research. A home-run from this work would result in hydrogen processing catalysts feasible enough to serve as a molecular fuel cell electrode, replacing platinum as a fuel cell electrode, and to make energy-efficient fuel cell technology feasible for a broader range of applications.