高等学校化学学报 ›› 2013, Vol. 34 ›› Issue (6): 1510.doi: 10.7503/cjcu20120803

• 物理化学 • 上一篇    下一篇

二硫键金属卟啉的合成及电催化还原氧气

黄修友, 胡炳成, 徐士超   

  1. 南京理工大学化工学院, 南京 210094
  • 收稿日期:2012-09-03 出版日期:2013-06-10 发布日期:2013-04-25
  • 通讯作者: 胡炳成,男,博士,研究员,博士生导师,主要从事药物中间体合成研究.E-mail:hubingcheng@yahoo.com E-mail:hubingcheng@yahoo.com
  • 基金资助:

    江苏省自然科学基金(批准号: BK2009386)资助.

Preparation of Metalloporphyrin with Disulfide Bond and Electrocatalytic Reduction of Oxygen

HUANG Xiu-You, HU Bing-Cheng, XU Shi-Chao   

  1. College of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China
  • Received:2012-09-03 Online:2013-06-10 Published:2013-04-25

摘要:

以氯化血红素(Ⅰ) 为原料, 经过脱铁、 酯化、 催化加氢、 水解、 酸胺缩合以及络合金属合成了化合物Co(Ⅱ)-[2,7,12,18-四甲基-3,8-二乙基-13,17-丙酰基氨乙基联二硫基乙氨基甲酰乙基-29,34-二甲氧甲酰基]-卟啉[Co(Ⅱ)MPDTEP, V]. 对产物的结构行了表征, 分析了反应时间和反应温度对化合物[2,7,12,18-四甲基-3,8-二乙基-13,17-丙酰基氨乙基联二硫基乙氨基甲酰乙基-29,34-二甲氧甲酰基]-卟啉(MPDTEP, Ⅳ)产率的影响. 将化合物Ⅴ通过自组装修饰于金电极表面, 修饰的金电极通过傅里叶红外光谱(FTIR)和电化学方法进行表征, 研究了其对氧气的电催化还原效果.

关键词: 氯化血红素, 卟啉, 自组装, 修饰电极, 电催化还原

Abstract:

A novel amino acid derivatised mesoporphyrin Co(Ⅱ)-[2,7,12,18-tetramethyl-3,8-diethyl-13,17-(propionylaminoethyl-dithio-ethyaminoformylethyl)-29, 34-bis-(methoxy-formyl)]-prophyrin[Co(Ⅱ)MPDTEP, Ⅴ] was prepared from hemin by a six-steps reaction including deferrization, esterification, cataly-tic hydrogenation, hydrolyzation, condensation and complexation. The target products were characterized. The effects of the reaction time and temperature on the yields of the product [2,7,12,18-tetramethyl-3,8-diethyl-13,17-(propionylaminoethyl-dithio-ethyaminoformylethyl)-29,34-bis-(methoxy-formyl)]-prophyrin(MPDTEP, Ⅳ) were investigated. A gold electrode modified by Co(Ⅱ)MPDTEP was prepared by self-assembly of disulfide on gold. The properties of the modified electrode were investigated by FTIR as well as electrochemical methods. This modified electrode was successfully used for the electrocatalytic reduction of oxygen.

Key words: Hemin, Porphyrin, Self-assembly, Modified electrode, Electrocatalytic reduction

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