Study of O2 Activation by Mossbauer Spectroscopy

穆斯堡尔谱研究 O2 活化

• 批准号: 8019536
• 负责人: ECKARD MUNCK
• 金额: $ 31.84万
• 依托单位: CARNEGIE-MELLON UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 1990
• 资助国家: 美国
• 起止时间: 1990-05-01 至 2012-06-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/8019536
• 关键词: Active Sites; Address; Affect; Amino Acids; Anabolism; Antibiotics; Aromatic Compounds; Bacillus anthracis spore; Biochemical; Biochemical Reaction; Biochemistry; Biodegradation; Chemicals; Chemistry; Collaborations; Complement; Complex; Coupled; Dioxygen; Dioxygenases; Electron Spin Resonance Spectroscopy; Electronics; Enzymes; Family; Fatty Acids; Health; Investigation; Iron; Ligands; Methane hydroxylase; Minnesota; Mitochondria; Modeling; Mononuclear; Mossbauer Spectroscopy; Neurodegenerative Disorders; Oxygen; Proteins; Reader; Research; Saccharomyces cerevisiae; Spectrum Analysis; Structure; System; Techniques; Texas; Theoretical Studies; Universities; Water Supply; Work; Yeasts; base; biological systems; catalyst; density; electronic structure; killings; mutant; novel; nucleic acid metabolism; oxidation; pathogen; pollutant; research study; synthetic enzyme; theories; tool

DESCRIPTION (provided by applicant): The proposed research seeks to elucidate the structure and function of iron-containing enzymes involved in a diverse range of biochemical reactions in the metabolism of nucleic acids, amino acids, fatty acids, biodegradation of aromatic compounds, and the biosynthesis of antibiotics. This research will be complemented by the study of high-valent synthetic complexes that can serve as structural or electronic models of the biological systems. The studies will focus on preparing and characterizing high-valent states of iron such as FeIV and FeV. It is also proposed to continue studies of yeast mitochondria, in particular of deletion mutants that produce aggregates of ferric iron which have been implicated in various neurodegenerative diseases. The experimental techniques employed are M"ssbauer spectroscopy and electron paramagnetic resonance. The research plan also includes theoretical studies based on density functional theory calculations. Specifically the following systems will be studied: (1) Homoprotochatechuate 2,3 dioxygenase, three Rieske dioxygenases, and methane monooxygenase. (2) Synthetic mononuclear FeIV and FeV complexes as well as dinuclear FeIVFeIII, and FeIVFeIV complexes that can serve as structural and/or electronic models for the active sites of iron proteins. (3) Activators involving Fe-tetraamido macrocyclic ligands that have a demonstrated potential in green chemistry and have proven very potent in killing anthrax spores and eliminating pollutants from our water supply. (4) Intact mitochondria from S. cerevisiae, to identify conditions where the particular strength of M"ssbauer spectroscopy can be employed to address important health problems. PUBLIC HEALTH RELEVANCE Iron-containing enzymes involved in oxygen activation affect numerous chemical transformations in all biological systems. The proposed studies of these enzymes, coupled with investigations of novel synthetic complexes that mimic structural and functional features of the biological systems, will reveal how these important enzymes function. The research will be complemented by studies of a family of synthetic complexes that have proven to be effective in green chemistry and extremely potent in killing pathogens such as anthrax spores.

描述（由申请人提供）：拟议的研究旨在阐明在核酸、氨基酸、脂肪酸代谢、芳香族化合物的生物降解和抗生素的生物合成等多种生化反应中涉及的含铁酶的结构和功能。这项研究将由高价合成复合物的研究来补充，这些复合物可以作为生物系统的结构模型或电子模型。研究将集中在制备和表征铁的高价态，如FeIV和FeV。还建议继续研究酵母线粒体，特别是产生铁铁聚集体的缺失突变体，这与各种神经退行性疾病有关。实验技术采用了斯堡尔谱和电子顺磁共振。研究计划还包括基于密度泛函理论计算的理论研究。具体来说，将研究以下体系：(1)同原生chatechuate 2,3双加氧酶，三种Rieske双加氧酶和甲烷单加氧酶。(2)合成单核FeIV和FeV配合物以及双核FeIVFeIII和FeIVFeIV配合物，这些配合物可以作为铁蛋白活性位点的结构和/或电子模型。(3)含有铁-四胺基大环配体的活化剂，在绿色化学中已被证明具有潜力，并且在杀死炭疽孢子和消除供水中的污染物方面非常有效。(4)完整的酿酒酵母线粒体，以确定特定强度的M”斯堡尔光谱可用于解决重要健康问题的条件。参与氧活化的含铁酶影响所有生物系统中的许多化学转化。对这些酶的拟议研究，加上对模拟生物系统结构和功能特征的新型合成复合物的研究，将揭示这些重要酶的功能。这项研究将得到对一系列合成复合物的研究的补充，这些复合物已被证明在绿色化学中是有效的，并且在杀死炭疽孢子等病原体方面非常有效。

项目成果

Mössbauer, electron paramagnetic resonance, and magnetic susceptibility studies on members of a new family of cyano-bridged 3d-4f complexes. Demonstration of anisotropic exchange in a Fe-Gd complex.

• DOI: 10.1021/ic902516r
• 发表时间: 2010-04-05
• 期刊: INORGANIC CHEMISTRY
• 影响因子: 4.6
• 作者: Stoian, Sebastian A.;Paraschiv, Carmen;Kiritsakas, Nathalie;Lloret, Francesc;Munck, Eckard;Bominaar, Emile L.;Andruh, Marius
• 通讯作者: Andruh, Marius

Sc3+-triggered oxoiron(IV) formation from O2 and its non-heme iron(II) precursor via a Sc3+-peroxo-Fe3+ intermediate.

• DOI: 10.1021/ja402645y
• 发表时间: 2013-07-17
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Li, Feifei;Van Heuvelen, Katherine M.;Meier, Katlyn K.;Muenck, Eckard;Que, Lawrence, Jr.
• 通讯作者: Que, Lawrence, Jr.

Xanthene-modified and hangman iron corroles.

• DOI: 10.1021/ic101943h
• 发表时间: 2011-01
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: M. Schwalbe;Dilek K Dogutan;S. Stoian;Thomas S. Teets;D. Nocera

The crystal structure of a high-spin oxoiron(IV) complex and characterization of its self-decay pathway.

• DOI: 10.1021/ja100366c
• 发表时间: 2010-06-30
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: England, Jason;Guo, Yisong;Farquhar, Erik R.;Young, Victor G., Jr.;Muenck, Eckard;Que, Lawrence, Jr.
• 通讯作者: Que, Lawrence, Jr.

Modeling the cis-oxo-labile binding site motif of non-heme iron oxygenases: water exchange and oxidation reactivity of a non-heme iron(IV)-oxo compound bearing a tripodal tetradentate ligand.

• DOI: 10.1002/chem.201002297
• 发表时间: 2011-02-01
• 期刊: CHEMISTRY-A EUROPEAN JOURNAL
• 影响因子: 4.3
• 作者: Company, Anna;Prat, Irene;Frisch, Jonathan R.;Mas-Balleste, Ruben;Gueell, Mireia;Juhasz, Gergely;Ribas, Xavi;Muenck, Eckard;Luis, Josep M.;Que, Lawrence, Jr.;Costas, Miquel
• 通讯作者: Costas, Miquel