• 更多栏目

    张建军

    • 教授     博士生导师   硕士生导师
    • 性别:男
    • 毕业院校:南京大学
    • 学位:博士
    • 所在单位:化学学院
    • 学科:无机化学
    • 办公地点:化工综合楼D411
    • 联系方式:0411-84986036
    • 电子邮箱:zhangjj@dlut.edu.cn

    访问量:

    开通时间:..

    最后更新时间:..

    Set of Fe(II)-3-Hydroxyflavonolate Enzyme-Substrate Model Complexes of Atypically Coordinated Mononuclear Non-Heme Fe(II)-Dependent Quercetin 2,4-Dioxygenase

    点击次数:

    论文类型:期刊论文

    第一作者:Sun, Ying-Ji

    通讯作者:Sun, YJ (reprint author), Dalian Univ Technol, Sch Chem, 2 Linggong Rd, Dalian 116024, Peoples R China.

    合写作者:Huang, Qian-Qian,Zhang, Jian-Jun

    发表时间:2017-09-01

    发表刊物:ACS OMEGA

    收录刊物:SCIE

    卷号:2

    期号:9

    页面范围:5850-5860

    ISSN号:2470-1343

    摘要:With the aim of revealing the catalytic role of atypically coordinated (3His-1Glu) active site mononuclear non-heme Fe(II)-dependent quercetin 2,4-dioxygenase (Fe-2,4-QD) and the electronic effects of the model ligands on the reactivity toward dioxygen, a set of p/m-R-substituted carboxylate-containing ligand-supported Fe(II)-3-hydroxyflavonolate complexes, [(FeLR)-L-II(fla)] ((LH)-H-R: 2-{[bis(pyridin-2-ylmethyl) amino] methyl}-p / m-R-benzoic acid; R: p-OMe (1), p-Me (2), m-Br (4), and m-NO2 (5); fla: 3-hydroxyflavonolate), were synthesized and characterized as structural and functional models for the ES (enzyme-substrate) complexes of Fe-2,4-QD. [FeIILR(fla)] show relatively high enzyme-type reactivity (dioxygenative ring opening of the coordinated substrate fla, single-turnover reaction) at low temperatures (30-65 degrees C). The reaction shows a linear Hammett plot (rho = -1.21), and electron donating groups enhance the reaction rates. The notable difference on the reactivity can be rationalized from the electronic nature of the substituent in the ligands, which could tune the reactivity via tuning Lewis acidity of the Fe(II) ion, electron density, and the redox potential of fla. The properties and the reactivity show approximately linear correlations between lambda(max) or E-1/2 of fla and the reaction rate constant k. This work sheds light not only on understanding of electronic effects of the ligands and the property-reactivity relationship but also on the role of the catalytic reaction by Fe-2,4-QD.