二硫键金属卟啉的合成及电催化还原氧气

Preparation of Metalloporphyrin with Disulfide Bond and Electrocatalytic Reduction of Oxygen

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.

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.