Structure/Function Correlations Over Binuclear non-heme Iron and Related Enzymes

双核铁酶在自然界中广泛分布，催化广泛的医学，工业和环境重要反应。这些反应都涉及通过非常相似的双核铁活性位点活化氧。中间体可以被困在这些反应和小双核铁设计的肽可作为这些酶的活性位点的模型。该研究项目涉及使用各种光谱技术与量子力学计算相结合，以了解这一大类酶的反应机制，以及显然相似的双核铁活性位点如何执行非常不同的功能。这些目标的实现，在某种程度上，需要新的光谱方法的发展和定义其信息内容从量子理论。这些研究定义了几何和电子结构对O-O键断裂的贡献。研究还侧重于确定结构贡献的O-O键形成的互补反应锰簇合物网站在光合作用。更广泛的影响正在研究的酶在工业合成、生物修复、温室气体消除、铁代谢和药物靶点方面都很重要。从这些研究中获得的见解正被应用于开发新的非均相和生物启发的催化剂。作为该研究计划的一部分开发的新光谱方法可应用于化学，生物学，材料和环境科学中的广泛问题。这项研究计划的光谱/电子结构专业知识通过广泛的合作提供给科学界，这也利用了这项研究的影响。这项研究为学生提供了一个独特的机会，使用各种光谱方法，开发新的光谱方法，并学习化学计算方法。这种广泛的技术和理论见解的可用性使学生能够学习整合这些方法来解决科学中的重要问题。在PI实验室（平等的性别组合）培训的学生已成为学术界（40）和工业界（50）的重要贡献者。该研究小组广泛参与本科教学，指导妇女从事科学工作，并深入社区，使低收入地区的小学生和中学女生接触科学和从事科学工作。通过对光谱方法的一般研讨会，编辑大量的书籍和专题卷，课程读者，并在一系列编辑委员会的重要参与，这个研究计划促进了光谱方法的信息内容和实用性，以解决化学和生物化学问题

Intellectual MeritBinuclear iron enzymes are widely distributed in nature and catalyze an extensive range of medically, industrially, and environmentally important reactions. These reactions all involve the activation of oxygen by very similar binuclear iron active sites. Intermediates can be trapped in these reactions and small binuclear iron designed peptides are available as models for these enzyme active sites. This research project involves using a wide variety of spectroscopic techniques combined with quantum mechanical calculations to understand the reaction mechanisms of this large class of enzymes and how apparently similar binuclear iron active sites perform very different functions. The achievement of these goals, in part, requires the development of new spectroscopic methods and definition of their information content from quantum theory. These studies define geometric and electronic structural contributions to O-O bond cleavage. Research also focuses on defining structural contributions to the complementary reaction of O-O bond formation by manganese cluster sites in photosynthesis. Broader ImpactThe enzymes being studied are important in industrial synthesis, bioremediation, greenhouse gas elimination, iron metabolism, and as drug targets. The insights derived from these studies are being applied toward the development of new heterogeneous and bio-inspired catalysts. New spectroscopic methods, developed as part of this research program, have applications to a wide range of problems in chemistry, biology, materials and environmental sciences. The spectroscopic/electronic structure expertise of this research program is made available to the scientific community through a wide range of collaborations, which also leverage the impact of this research. This research provides students with a unique opportunity to use a variety of spectroscopic methods, develop new spectroscopic methodologies, and learn computational approaches to chemistry. The availability of such a wide range of techniques and theoretical insight allows students to learn to integrate these approaches to solve important problems in science. The students trained in the PI's lab (an equal gender mix) have become significant contributors in academics ( 40) and industry ( 50). This research group extensively participates in undergraduate teaching, mentoring women in science and outreach into the community to expose elementary school students in low-income areas and middle school females to science and careers in science. Through general seminars on spectroscopic methods, editing numerous books and thematic volumes, course readers, and significant participation on a range of editorial boards, this research program promotes the information content and utility of spectroscopic methods to problems in chemistry and biochemistry