高级搜索

基于密度泛函理论揭示Cu2+配位作用对头孢拉定水解反应的影响机制

,  ,  , 

downloadPDF

上一篇

下一篇

张海勤, 谢宏彬, 陈景文, 张树深. 基于密度泛函理论揭示Cu2+配位作用对头孢拉定水解反应的影响机制[J]. 环境化学, 2015, 34(9): 1594-1600. doi: 10.7524/j.issn.0254-6108.2015.09.2015041101
引用本文: 张海勤, 谢宏彬, 陈景文, 张树深. 基于密度泛函理论揭示Cu2+配位作用对头孢拉定水解反应的影响机制[J]. 环境化学, 2015, 34(9): 1594-1600. doi: 10.7524/j.issn.0254-6108.2015.09.2015041101
shu
ZHANG Haiqin, XIE Hongbin, CHEN Jingwen, ZHANG Shushen. Effects of Cu2+ complexation on the structure and hydrolysis of cephradine using density functional theory[J]. Environmental Chemistry, 2015, 34(9): 1594-1600. doi: 10.7524/j.issn.0254-6108.2015.09.2015041101
Citation: ZHANG Haiqin, XIE Hongbin, CHEN Jingwen, ZHANG Shushen. Effects of Cu2+ complexation on the structure and hydrolysis of cephradine using density functional theory[J]. Environmental Chemistry, 2015, 34(9): 1594-1600. doi: 10.7524/j.issn.0254-6108.2015.09.2015041101
shu

基于密度泛函理论揭示Cu2+配位作用对头孢拉定水解反应的影响机制

  • 1.

    工业生态与环境工程教育部重点实验室, 大连理工大学环境学院, 大连, 116024

  • 基金项目:

    国家重点基础研究发展计划(2013CB430403)和国家自然科学基金(21137001,21325729)资助.

Effects of Cu2+ complexation on the structure and hydrolysis of cephradine using density functional theory

  • 1.

    Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian, 116024, China

  • Fund Project:

  • 摘要: 基于密度泛函理论(DFT, Density functional theory),计算了水中Cu2+与抗生素头孢拉定的配位作用,发现Cu2+与头孢拉定可形成1:1配合物,该配合物存在两种形态:Cu2+与头孢拉定分子支链氨基氮原子和羰基氧原子配位,同时结合一个水分子;Cu2+与羧基氧原子和内酰胺氧原子配位,同时结合两个水分子.结果表明,Cu2+的配位作用能增大头孢拉定水解反应位点正电荷量,降低水解前线分子轨道能级差和活化能,从而促进头孢拉定水解,该结果得到了实验证实.因此,DFT可用于预测Mn+配位作用对药物和个人护理用品(PPCPs, Pharmaceutical and personal care products)等有机污染物水解的影响,对于PPCPs类有机污染物的生态风险评价具有重要意义.
    Abstract: Density functional theory (DFT) was employed to investigate the complexation effects of Cu2+ on hydrolysis of cephradine. We found that two complex species were formed, with the binding sites being a) the amino and carbonyl group, and b) the carboxyl group and carbonyl group, respectively. This complexation changed the bond length of lactam, increased the positive charge of the hydrolysis site, and reduced both the energy gap of the frontier molecular orbitals for hydrolysis and the activation energy of base-catalyzed hydrolysis. Thus, the complexation of Cu2+ can catalyze the hydrolysis of cephradine. The prediction was confirmed by experimental results. Thus, the DFT calculation can be employed to predict the effects of metal complexation on the hydrolysis of organic pollutants, which are important in the ecological risk assessment of organic chemicals.
  • 加载中
  • [1] Ternes T A. Occurrence of drugs in German sewage treatment plants and rivers[J]. Water Research, 1998, 32:3245-3260
    [2] Halling S B, Nors N S, et al. Occurrence, Fate and effects of pharmaceutical substances in the environment-a review[J]. Chemosphere, 1998, 36:357-393
    [3] Remington J P, Troy D B, Remington Br P. The science and practice of pharmacy[M]. Maryland:Lippincott Williams & Wilkins, 2006:359-469
    [4] Schwarzenbach R P, Gschwend P M, Imboden D M. Environmental organic chemistry[M]. Canada:John Wiley & Sons, 2003:706-715, 489-554
    [5] Werner J J, Arnold W A, McNeill K. Water hardness as a photochemical parameter:Tetracycline photolysis as a function of calcium concentration,magnesium concentration, and pH[J]. Environmental Science Technology, 2006, 40(23):7236-7241
    [6] Vione D, Feitosa F J, Minero C, et al. Phototransformation of selected human-used macrolides in surface water:Kinetics, model predictions and degradation pathways[J].Water Research, 2009, 43(7):1959-1967
    [7] Najma S, Arayne M S. In vitro activity of cefadroxil, cephalexin, cefatrizine and cefpirome in presence of essential and trace elements[J]. Pakistan Journal of Pharmarmaceutical Sciences, 2007, 20(4):305-310
    [8] Huang C H, Stone A T. Hydrolysis of naptalam and structurally related amides:In hibition by dissolved metal ions and metal(hydr) oxide surafces[J]. Journal of Agricultural and Food Chemistry, 1999, 47:4425-4434
    [9] Eric L H, Stephen H M, Chin L C, et al. Structure-reactivity studies in copper(Ⅱ)-Catalyzed phosphodiester hydrolysis[J]. Inorganic Chemistry, 1999, 38:2961-2968
    [10] Díaz N, Sordo T L, Suárez D, et al. Zn2+ catalysed hydrolysis of β-lactams:Experimental and theoretical studies on the influence of the β-lactam structure[J]. New Journal of Chemistry, 2003, 28:15-25
    [11] 华中师范大学等. 分析化学(下册)[M]. 北京:高等教育出版社, 2001:32-49,242-257
    [12] Hernowo E, Artik E A, Fazary A E, et al. Complex stability and molecular structure studies of divalent metal Ion with L-Norleucine and Vitamin B3[J]. Journal of Chemical & Engineering Data, 2011, 56:4549-4555
    [13] Zhang H, Xie H, Chen J, et al. Prediction of hydrolysis pathways and kinetics for antibiotics under environmental pH conditions:A quantum chemical study on cephradine[J]. Environmental Science Technology, 2015, 49:1552-1558
    [14] Andreozzi R, Caprio V, Ciniglia C, et al. Antibiotics in the environment:Occurrence in Italian STPs, fate, and preliminary assessment on algal toxicity of amoxicillin[J]. Environmental Science Technology, 2004, 38:6832-6838
    [15] Lin A Y C, Yu T H, Lin C F. Pharmaceutical contamination in residential, industrial, and agricultural waste streams:Risk to aqueous environments in Taiwan[J]. Chemosphere, 2008, 74 (1):131-141
    [16] 尉小旋, 陈景文, 王如冰, 等. 氧氟沙星和诺氟沙星的水环境光化学转化:pH值及溶解性物质的影响[J]. 环境化学, 2015, 34(3):448-454
    [17] Lozano M J, Bomi J. Antibiotic as ligand. Coordinating behavior of the cephalexin towards Zn(Ⅱ) and Cd(Ⅱ) ions[J]. Journal of Inorganic Biochemistry, 1987, 9(7):187-195
    [18] Fazakerley G V, Jackson G E. Metal ion coordination by some penicillin and cephalosporin and antibiotics[J]. Journal of Inorganic and Nuclear Chemistry, 1975, 37:2371-2375
    [19] El-Said A I, Aly A A M, EI-Meligy M S, et al. Mixed ligand zinc(Ⅱ) and cadmium(Ⅱ) complexes containing ceftriaxone antibiotics and different donors[J]. J The Journal of the Argentine Chemical Society, 2009, 97(2):149-165
    [20] Bukhari H, Arif M, Akbar J. Preparation, characterization and biological evaluation of Schiff base transition metal complexes with cephradine[J]. Pakistan Journal of Biological Sciences, 2005, 8(4):614-617
    [21] Anacona J R, Faricar A. Synthesis and antibacterial activity of cephradine metal complexes[J]. Journal of Coordination Chemistry, 2006, 59(6):621-627
    [22] Jeffrey H P, Willard W R. Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg[J]. The Journal of Chemical Physics, 1985, 82(1):270-283
    [23] Yang Y, Weaver M N, Merz K M. Assessment of the "6-31+G**+LANL2DZ" mixed basis set coupled with density functional theory methods and the effective core potential:Prediction of heats of formation and ionization potentials for first-row-transition-metal complexes[J]. Journal of Physical Chemistry A, 2009, 113 (36):9843-9851
    [24] Tomasi J, Mennucci B, Cammi R. Quantum mechanical continuum solvation models[J]. Chemical Reviews, 2005, 105(8):2999-3093
    [25] Mennucci B. Continuum solvation models:What else can we learn from them?[J]. The Journal of Physical Chemistry Letters, 2010, 1 (10):1666-1674
    [26] 戴安邦. 配位化学[M]. 北京:科学出版社, 1988:20-40
    [27] Frison G, Ohanessian G. A comparative study of semi empirical, Ab initio, and DFT methods in evaluating metal-ligand bond strength, proton affinity, and interactions between first and second shell ligands in Zn-Biomimetic complexes[J]. Journal of Computational Chemistry, 2008, 29:416-433
    [28] Smith M B. March's advanced organic chemistry:Reactions, mechanisms and structure(7th ed)[M]. New Jersey:John Wiley & Sons, 2013:348-495
  • 加载中
WeChat 点击查看大图
计量
  • 文章访问数:  1138
  • HTML全文浏览数:  1056
  • PDF下载数:  621
  • 施引文献:  0
出版历程
  • 收稿日期:  2015-04-11
  • 刊出日期:  2015-09-15

基于密度泛函理论揭示Cu2+配位作用对头孢拉定水解反应的影响机制

  • 1. 工业生态与环境工程教育部重点实验室, 大连理工大学环境学院, 大连, 116024
  • 收稿日期:  2015-04-11
基金项目:

国家重点基础研究发展计划(2013CB430403)和国家自然科学基金(21137001,21325729)资助.

摘要: 基于密度泛函理论(DFT, Density functional theory),计算了水中Cu2+与抗生素头孢拉定的配位作用,发现Cu2+与头孢拉定可形成1:1配合物,该配合物存在两种形态:Cu2+与头孢拉定分子支链氨基氮原子和羰基氧原子配位,同时结合一个水分子;Cu2+与羧基氧原子和内酰胺氧原子配位,同时结合两个水分子.结果表明,Cu2+的配位作用能增大头孢拉定水解反应位点正电荷量,降低水解前线分子轨道能级差和活化能,从而促进头孢拉定水解,该结果得到了实验证实.因此,DFT可用于预测Mn+配位作用对药物和个人护理用品(PPCPs, Pharmaceutical and personal care products)等有机污染物水解的影响,对于PPCPs类有机污染物的生态风险评价具有重要意义.

English Abstract

    全文HTML

参考文献 (28)

目录

/

返回文章
返回

Copyright © 2019 中国科学院生态环境研究中心