二茂铁-肽Fc-Gly-Pro-Arg(NO_2)-OMe的合成及其与Cu(Ⅱ)作用

Synthesis of Ferrocenoyl-Labeled Tripeptide Fc-Gly-Pro-Arg(NO_2)-OMe and Its Interaction with Cu(Ⅱ)

以二茂铁甲酸、甘氨酸(H-Gly-OMe)、脯氨酸(Boc-Pro-OH)、精氨酸(H-Arg(NO2)-OMe)等为原料,苯并三唑-1-四甲基六磷酸酯(HBTU)和1-羟基苯并三唑(HOBT)为缩合剂,采用液相法合成了二茂铁-肽Fc-Gly-Pro-Arg(NO2)-OMe(简称Fc-GPR),其总收率为48.1%.并对目标产物进行了红外(IR)光谱、核磁共振氢谱(1H-NMR)、质谱(ESI-MS)等表征.通过电化学方法研究了目标产物与Cu(Ⅱ)之间的相互作用.结果表明:目标产物在溶液中的电化学行为表现为可逆氧化还原反应,氧化和还原峰电位分别为0.624和0.552V(vsAg/AgCl),氧化和还原峰电流之比Ipa/Ipc为1.13,电极反应过程为扩散控制.目标产物与Cu(Ⅱ)形成配位比为2∶1的配合物.Fc-GPR与Cu(Ⅱ)的电极反应过程符合电化学-化学-电化学(ECE)历程.

N-ferrocenoyl-labeled tripeptide Fc-Gly-Pro-Arg（NO2）-OMe（Fc-GPR） was synthesized from ferrocenecarboxylic acid,glycine（H-Gly-OMe）,proline（Boc-Pro-OH） and arginine（H-Arg（NO2）-OMe） by solution synthesis with a yield of 48.1%.The synthesized Fc-GPR was characterized by infrared spectroscopy（IR）,proton nuclear magnetic resonance spectroscopy（1H-NMR） and electrospray ionization mass spectroscopy（ESI-MS）.The electrochemical behavior of Fc-GPR was investigated using electrochemical methods.We observed a pair of well-defined voltammetric peaks with cathodic Epc and anodic peak potentials Epa,at 0.552 and 0.624 V（vs Ag/AgCl）,respectively.The ratio of oxidative to reductive peak current is 1.13 and the peak currents were found to be proportional to the square root of the scan rates suggesting that Fc-GPR undergoes a reversible electron transfer reaction.The molar ratio of Fc-GPR to Cu（Ⅱ） was found to be 2：1 by the molar ratio method.Furthermore,the electrode reaction of Fc-GPR with Cu（Ⅱ） is an electrochemicalchemical-electrochemical（ECE） process.