X-Ray Raman and Vibrational Mossbauer of Metalloproteins
X-Ray Raman and Vibrational Mossbauer of Metalloproteins
批准号:
6874836
负责人:
Stephen P. Cramer
金额:
$20.05万
依托单位国家:
美国
项目类别:
财政年份:
2002
资助国家:
美国
项目状态:
已结题
起止时间:
2002-03-01 至 2007-09-14
中文摘要
描述(由申请人提供):我们的长期目标是更好的
了解含金属酶的重要作用。在这一提议中,
我们关注的是含有Fe和不同金属(Ni,Mo,
(5)在活性部位。三个酶活性位点(NiFe氢化酶,CO
脱氢酶和乙酰辅酶A合酶)含有Fe和Ni的组合。的
另一种酶,固氮酶,在MFe 7S 8簇的一端使用V或Mo。
尽管X射线衍射(或电子显微镜)技术取得了进展,但许多
关于分子和电子结构的问题需要解决。的
催化机制仍然知之甚少。
将使用扩展X射线研究Ni位点的分子结构
H2酶和CODH晶体的吸收精细结构(EXAFS)分析。
仅含CO氧化(C-簇)和ACS(A-簇)位点的样品
也将被审查。虽然这些酶已经被研究,
EXAFS、建议的样品和范围扩展分析技术应产生
更多关于Ni网站的信息
将使用X射线探测Ni和V位点的电子结构
共振拉曼光谱(XRRS或RIXS)。对这些光谱的分析将
揭示了Ni和V的氧化和自旋状态下的最佳描述
各种条件。铁心和镍心振动态密度
将使用振动穆斯堡尔光谱学进行研究。这种方法
将有助于确定重要的M-H和金属基板相互作用的网站。
将建立一个仪器,以允许在校园实验。
上述酶对维持我们的环境很重要。铁蛋白
也在人类健康和疾病中发挥着关键作用。拟议的工作将加强
我们的铁生物化学知识,和光谱技术下,
发展将有应用到广泛的生物无机问题。
英文摘要
DESCRIPTION (provided by applicant): Our long-term goal is a better
understanding of how important metal containing enzymes work. In this proposal,
we focus on metalloenzymes that contain both Fe and a different metal (Ni, Mo,
V) at the active site. Three of the enzyme active sites (NiFe hydrogenase, CO
dehydrogenase, and acetyl-CoA synthase) contain combinations of Fe and Ni. The
other enzyme, nitrogenase, employs V or Mo at one end of a MFe7S8 cluster.
Despite progress by x-ray diffraction (or electron microscopy) techniques, many
questions about the molecular and electronic structure need to be resolved. The
catalytic mechanisms are still poorly understood.
The molecular structure of the Ni sites will be studied using extended x-ray
absorption fine structure (EXAFS) analysis of crystals of H2ase and CODH.
Samples containing only the CO oxidation (C-cluster) and ACS (A-cluster) sites
will also be examined. Although these enzymes have already been studied by
EXAFS, the proposed samples and range-extended analysis techniques should yield
more details about the Ni sites.
The electronic structure of the Ni and V sites will be probed using x-ray
resonance Raman spectroscopy (XRRS or RIXS). Analysis of these spectra will
reveal the best description of the Ni and V oxidation and spin states under a
variety of conditions. The Fe- and Ni-centered vibrational density of states
will be studied using the vibrational Mossbauer spectroscopy. This approach
will help identify the sites of important M-H and metal-substrate interactions.
An instrument will be built to allow on-campus experiments.
The above enzymes are important for maintaining our environment. Fe proteins
also play key roles in human health and disease. The proposed work will enhance
our knowledge of Fe biochemistry, and the spectroscopic techniques under
development will have applications to a wide range of bioinorganic problems.
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会议论文
A HIGH MAGNETIC FIELD MOSSBAUER INSTRUMENT
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批准号:7390087
-
项目类别:
-
资助金额:$26.37万
-
财政年份:2008
-
负责人:Stephen P. Cramer
-
依托单位:
SITE SELECTIVE EXAFS AND RIXS OF FE-ONLY HYDROGENASE AND RELATED MODELS
-
批准号:7369147
-
项目类别:
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资助金额:$2.81万
-
财政年份:2006
-
负责人:Stephen P. Cramer
-
依托单位:
SPHERICALLY BENT SI ANALYSER CRYSTALS FOR RIXS WITH INTRENSIC RESOL OF 150 MEV
-
批准号:7369172
-
项目类别:
-
资助金额:$2.36万
-
财政年份:2006
-
负责人:Stephen P. Cramer
-
依托单位:
THE CORE HOLE EFFECT IN TRANSITION METAL INER-SHELL SPECTROSCOPY
-
批准号:7182117
-
项目类别:
-
资助金额:$2.06万
-
财政年份:2005
-
负责人:Stephen P. Cramer
-
依托单位:
RIXS OF NICKEL CONTAINING METALLOENZYMES AND MODEL COMPOUNDS
-
批准号:7182118
-
项目类别:
-
资助金额:$3.39万
-
财政年份:2005
-
负责人:Stephen P. Cramer
-
依托单位:
EXAFS OF THE METALLOPROTEINS CODH AND ACS
-
批准号:6975538
-
项目类别:
-
资助金额:$1.52万
-
财政年份:2004
-
负责人:Stephen P. Cramer
-
依托单位:
ULTRA LOW TEMPERATURE XMCD OF BIOLOGICAL SAMPLES
-
批准号:6658641
-
项目类别:
-
资助金额:$14.32万
-
财政年份:2002
-
负责人:Stephen P. Cramer
-
依托单位:
SOFT XRAY MAGNETIC CIRCULAR DICHROISM OF PARAMAGNETIC BIOLOGICAL SYSTEMS
-
批准号:6658645
-
项目类别:
-
资助金额:$14.32万
-
财政年份:2002
-
负责人:Stephen P. Cramer
-
依托单位:
HIGH RESOLUTION MN KB FLUORESCENCE
-
批准号:6586706
-
项目类别:
-
资助金额:$14.32万
-
财政年份:2002
-
负责人:Stephen P. Cramer
-
依托单位:
HIGH RESOLUTION MN KB FLUORESCENCE
-
批准号:6658673
-
项目类别:
-
资助金额:$14.32万
-
财政年份:2002
-
负责人:Stephen P. Cramer
-
依托单位:
Spectroscopy of Fe-S Cluster Proteins -- Information for Structure and Function
-
批准号:10523030
-
项目类别:
-
资助金额:$49.27万
-
财政年份:2002
-
负责人:Stephen P. Cramer
-
依托单位:
X-Ray Raman and Vibrational Mossbauer of Metalloproteins
-
批准号:6623398
-
项目类别:
-
资助金额:$19.46万
-
财政年份:2002
-
负责人:Stephen P. Cramer
-
依托单位:
SOFT XRAY ABSORPTION SPECTROSCOPY OF MN PROTEINS
-
批准号:6586707
-
项目类别:
-
资助金额:$14.32万
-
财政年份:2002
-
负责人:Stephen P. Cramer
-
依托单位:
Synchrotron NRVS and Campus Spectroscopy of Multinuclear Fe Proteins: N2ase, H2as
-
批准号:8461540
-
项目类别:
-
资助金额:$32.14万
-
财政年份:2002
-
负责人:Stephen P. Cramer
-
依托单位:
CRAMER PRT TIME (LBNL)
-
批准号:6586796
-
项目类别:
-
资助金额:$14.32万
-
财政年份:2002
-
负责人:Stephen P. Cramer
-
依托单位:
CRAMER PRT TIME (LBNL)
-
批准号:6658763
-
项目类别:
-
资助金额:$14.32万
-
财政年份:2002
-
负责人:Stephen P. Cramer
-
依托单位:
Spectroscopy of Fe-S Cluster Proteins -- Information for Structure and Function
-
批准号:10701904
-
项目类别:
-
资助金额:$58.68万
-
财政年份:2002
-
负责人:Stephen P. Cramer
-
依托单位:
SOFT XRAY ABSORPTION SPECTROSCOPY OF MN PROTEINS
-
批准号:6658674
-
项目类别:
-
资助金额:$14.32万
-
财政年份:2002
-
负责人:Stephen P. Cramer
-
依托单位:
Synchrotron NRVS and Campus Spectroscopy of Multinuclear Fe Proteins: N2ase, H2as
-
批准号:8796719
-
项目类别:
-
资助金额:$29.1万
-
财政年份:2002
-
负责人:Stephen P. Cramer
-
依托单位:
Spectroscopy of Fe-S Cluster Proteins -- Information for Structure and Function
-
批准号:10797984
-
项目类别:
-
资助金额:$4.0万
-
财政年份:2002
-
负责人:Stephen P. Cramer
-
依托单位:
海外基金