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

双核铁酶广泛存在于自然界中，并催化了广泛的医学、工业和环境重要反应。这些反应都涉及到由非常相似的双核铁活性位点激活氧。中间体可以被困在这些反应中，小的双核铁设计肽可以作为这些酶活性位点的模型。该研究项目涉及使用各种光谱技术结合量子力学计算来了解这类酶的反应机制，以及如何明显相似的双核铁活性位点执行非常不同的功能。实现这些目标，在一定程度上需要发展新的光谱学方法，并从量子理论中定义其信息内容。这些研究定义了几何和电子结构对O-O键解理的贡献。研究还侧重于确定光合作用中锰簇位点形成O-O键的互补反应的结构贡献。广泛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具有重要意义。从这些研究中获得的见解正被应用于开发新的异相和生物启发催化剂。作为该研究项目的一部分，新的光谱方法在化学、生物、材料和环境科学等领域有着广泛的应用。该研究项目的光谱/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来使用各种光谱方法，开发新的光谱方法，并学习化学的计算方法。如此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（男女比例相等）接受培训的学生已成为学术界（40人）和工业界（50人）的重要贡献者。该研究小组广泛参与本科教学，指导女性科学，并向社区推广，使低收入地区的小学生和中学生接触科学和科学事业。通过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，以及在一系列编辑委员会的重要参与，该研究计划促进了光谱方法对化学和生物化学问题的信息内容和效用

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