周朝晖
配位催化和酶催化,包括催化剂制备方法研究、多相不对称催化、固氮酶催化作用机理及其化学模拟。
个性化签名
- 姓名:周朝晖
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学术头衔:
博士生导师
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学科领域:
催化化学
- 研究兴趣:配位催化和酶催化,包括催化剂制备方法研究、多相不对称催化、固氮酶催化作用机理及其化学模拟。
周朝晖,1979年起就读于厦门大学化学系;1989年于厦门大学获理学博士学位;1990-1992年公派赴香港中文大学化学系学习;1996-1997年在北京语言文化大学德语系进修;1997-1998年获瑞士联邦政府奖学金(ESKAS)赴瑞士弗里堡大学语言培训部和苏黎士联邦工学院技术化学研究所学习。现任厦门大学化学化工学院教授,中国化工学会化肥专业委员会委员,Inorg. Chem.、Inorg. Chem. Comm.、Inorg. Chim. Acta等杂志评审员,中国化学会和材料学会会员。
研究方向:配位催化和酶催化,包括催化剂制备方法研究、多相不对称催化、固氮酶催化作用机理及其化学模拟。主持完成首批高等学校骨干教师资助计划"复氧化物的设计合成及性能研究"、主持国家自然科学基金项目"柠檬酸配合物制备复氧化物选择氧化催化剂研究"、"新型多相不对称加氢催化剂的设计合成和性能研究"和"配位保护在有机多羧酸合成中的新方法研究";参加国家重点基础研究发展规划"高效生物固氮作用机理及其在农业中的应用"、"天然气及合成气高效催化转化的基础研究-催化过程的微观机制和反应中间体鉴定"等项目的研究实施。正式发表论文106篇,其中80篇被国际重要学术期刊SCI收录, 发表论文被国际同行引用320次。作为第五完成人获1995年度教育部科技进步一等奖,个人获1999年度中国化学会青年化学奖。
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周朝晖, Zhao-Hui Zhou *, Hong Zhao, Khi-Rui Tsai
Journal of Inorganic Biochemistry 98(2004)1787-1794,-0001,():
-1年11月30日
The stereospecific formation and absolute configuration of R-homocitrate coordinated FeMo-co in nitrogenase was mimicked through the structural analyses of a collection of enantiomeric and mesomeric mandelato molybdenum complexes, i.e., (NH4)2[MoDO2(R-mand)2]·3H2O (1a), (NH4)2[MoKO2(S-mand)2]·3H2O (1b), (NH4)4[MoDO2(RS-mand)2][MoKO2(RS-mand)2]·8H2O (2), (NH4)2[WDO2(R-mand)2]·2H2O (3a), (NH4)2[WKO2(S-mand)2] Æ 2H2O (3b) (H2mand=mandelic acid, C8H8O3), which have been characterized by elemental analyses, optical rotation, circular dichroism, IR, NMR spectroscopes and X-ray single crystal studies. The R and S chiral mandelic acids induce the formations of the enantiomeric pair of chiral complexes, which are supported by the characterizations of optical rotation and circular dichroism. The configuration of the resulted metal center could be assigned as D or K. While the RS racemic reagent yields only mesomeric compound. The DR,R-complexes 1a and 3a are enantiomers of KS,S-1b and 3b, respectively. Of the five complexes, Mo and W atoms are all hexa-coordinated by two cis-oxo groups and two bidentate mandelate ligands through the deprotonated a-alkoxyl and α-carboxyl groups, forming a stable five-membered chelated rings. The average Mo(VI)–O bond distances with α-alkoxyl and α-carboxyl are 1.944 and 2.210 Å, respectively. Further omparison indicates that bonds of α-alkoxyl groups in the hydroxycarboxylato molybdenum complexes are much sensitive to the change in the oxidation state of molybdenum, which support the possible Mo activation model in FeMo-co through the protonation and cleavage of α-alkoxyl group in homocitrate ligand.
Molybdate, Tungstate, Mandelic acid, Mandelate, Crystal structure, Stereospecific, FeMo-cofactor
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【期刊论文】Syntheses, crystal structures and biological relevance of glycolato and S-lactato molybdates☆
周朝晖, Zhao-Hui Zhou a, *, Shu-Ya Hou a, Ze-Xing Cao a, Hui-Lin Wan a, Seik-Weng Ng b
Journal of Inorganic Biochemistry 98(2004)1037-1044,-0001,():
-1年11月30日
Glycolato and S-lactato complexes containing the dioxomolybdenum (VI) moiety have been synthesized for studies on the role of the α-hydroxycarboxylato anion in the iron molybdenum cofactor of nitrogenase. The ligands in these complexes, vis K2[MoO2(glyc)2] H2O (H2glyc¼glycolic acid, C2H4O3) (1) and {Na2[MoO2(S-lact)2]}3 13H2O (H2lact¼lactic acid, C3H6O3) (2) chelate through their α-alkoxyl and α-carboxyl oxygen atoms. In contrast, octanuclear K6[(MoO2)8(glyc)6(Hglyc)2] 10H2O (3) formed by the reduction of the glycolato complex (1), features three different ligand binding modes: (i) non-bridging and bridging bidentate coordination of α-alkoxyl and α-carboxyl groups, and (ii) bidentate bridging using α-carboxyl group, leaving the α-alkoxyl group free. The octanuclear skeleton shows strong metal–metal interactions. The coordination modes in (1) and (2) mimic that of homocitrate to the iron molybdenum cofactor (FeMo-co) of nitrogenase. The bidentate coordination of α-alkoxyl and α-carboxyl groups shows that bond of α-carboxyl group to Mo is less susceptible to the oxidation state of molybdenum compared with the Mo-α-alkoxyl bond. This is supported by the dinuclear coordination of α-carboxyl group with free α-alkoxyl group in glycolato molybdate(V) (3).
Dioxomolybdate, Glycolic acid, S-Lactic acid, Cofactor biosynthesis
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周朝晖, Zhao-Hui Zhou, Wen-Bin Yan, Hui-Lin Wan, Khi-Rui Tsai*
Journal of Inorganic Biochemistry 90(2002)137-143,-0001,():
-1年11月30日
Reaction of sodium or potassium molybdate and excess malic acid in a wide range of pH values (pH 4.0-7.0) resulted in the isolation of two cis-dioxo-bis (malato)-Mo (VI) complexes, viz. Na [MoO2 H(S-mal)2] and K [MoO2 H(S-mal2)]·H2O (H3 mal=malic acid). The sodium complex is also characterized by an X-ray structure analysis, showing that the mononuclear Mo units are linked together via very strong symmetric CO2 …H… O2C-hydrogen bond [2.432(5) Å], forming a polymeric chain. The molybdenum atoms are quasi-octahedrally coordinated by two cis-oxo groups and two bidentate malate ligands via its alkoxy and α-carboxyl groups, while the β-carboxylic and carboxylate groups remain uncomplexed, as the coordination of vicinal carboxylate and alkoxide of homocitrate in FeMo cofactor of nitrogenase. The absolute configuration of the metal center in this S-malato complex is assigned as Λ and the homochirality within the chain is established as a homochiral form …Λs-Λs-Λs-Λs…. It is proposed that the chiral configuration of the metal center in wild-type FeMo-co biosynthesis might be induced by the early coordination of the chiral R-homocitric acid, while a 2 mixture of raceme might be obtained in the biosynthesis of NifV FeMo-cofactor. The absolute configuration of wild-type FeMo-cofactor is assigned as ΔR.
Stereospecific, Absolute configuration, Malic acid, Malate, Molybdate (, VI), , Nitrogenase, Cofactor biosynthesis, Crystal structure
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