谷胱甘肽纳米硒复合物的制备及其特性研究
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摘要
本文以谷胱甘肽(GSH)为还原剂还原亚硒酸钠(Na2Se03),在室温液相条件下,成功制备出了无定形的球型纳米硒复合物(GSH-nanoSe0),平均粒径为50 nm左右,分布范围较窄,体系稳定性良好,说明GSH对纳米硒的形貌和粒径分和存在一定程度的调控作用。从红外图谱可知,GSH-nanoSe0体系存在O-Se-O的键合作用,其中一部分-SH则转化成为-S-S-。GSH-nanoSe0体系在370 nm处有一明显紫外吸收峰。此制备方法无需加入任何的模板剂和修饰剂,在室温液相条件下进行,具有低污染、低能耗、简单易行等优点。
以金电极为基底,将所制备的GSH-nano Se0复合物自组装48 h后,可得到致密稳定的谷胱甘肽纳米硒复合物自组装膜(GSH-nano Se0/SAMs)。考察了其电化学特性,并研究了其对过氧化氢(H2O2)电化学还原的催化作用。
研究发现SeCys SAMs在Pb2+, Cu2+存在下,在静电作用和配位作用的共同协作下,形成了一条离子通道,其他离子比如Fe(CN)64/3-，Cd2+可以更容易通过,即出现了离子门效应。GSH/SAMs在阳离子活性剂HTAB的存在下,受静电作用的影响,探针离子Fe(CN)64/3-的电子传输能力明显提高,即具有离子门效应,而在GSH-nano Se0/SAMs上, Se原子与-COOH的配位作用使得复合物结构发生了变化,空间位阻增加,使得离子传输变得困难且对静电作用造成影响,离子门效应减弱。
采用GSH-nano Se0/SAMs Au电极实现了对H2O2体系的电化学催化,在0.1M KNO3(pH=5.5)电解质中,H2O2的还原峰电位在-320 mV处,峰电流随H2O2增加而增加,并在2×10-5-6×10-3mol／L浓度范围内呈线性关系,检测下限为5×10-7mol／L,不同电极之间平行检测的RSD为2.4%,同一电极平行测定的RSD为2.2%,GSH-nano Se0复合膜电极具有良好的重现性和稳定性,使用寿命较长,可应用于H2O2的测定。
In this study, GSH-nano Se0 was prepared by GSH and Na2SeO3 under room temperature in liquid phase, and characterized by UV-Vis Spectra (UV), Transmission electron microscope (TEM), Scan electron microscope (SEM), Fourier transform infrared spectrometry (FTIR), nano-Zeta Sizer(nano-ZS). The results indicated that GSH-nano Se0 was spheres with the average diameter 50nm, nanoSe0 could coordinate with GSH as O-Se-O bond, and-SH turned into-S-S-. There was an ultraviolet absorption in GSH-nano Se0 system, which was attributed to nano Se0. The preparation method was green, simple, low energy consumption in the absence of any template or modifier.
By taking GSH-nano Se0 system as research object, self-assemble (SAMs) technology was used to prepare GSH-nano Se0 SAMs/Au, which provided an interface to study the electrochemical characteristic and catalysis to the H2O2 system.
In this paper, ion gate response of GSH-nano Se0/SAMs was studied, and also compared with SeCys SAMs and GSH SAMs. It was found that SeCys SAMs revealed ion-gate response in the presence of Cu2+or Pb2+. The electron-transfer ability of Fe(CN)64/3- was improved at SeCys SAMs/Au electrode, which results from the fact that the electrostatic interaction between the monolayer and charged ions Cu2+, Pb2+ changed the conformation of SeCys monolayer. GSH SAMs revealed ion-gate response in the presence of cationic surfactant HTAB. The electron-transfer ability of Fe(CN)64/3- was improved in the presence of HTAB at GSH SAMs/Au electrode, which results from the fact that the electrostatic interaction between GSH SAMs and HTAB changed the conformation of GSH monolayer. The ion-gate response at GSH-nanoSe0/SAMs Au electrode was less remarkable than GSH SAMs. The coordination of Se and-COOH resulted in the change of the conformation, which increased steric hindrance and also affect the electrostatic interaction between GSH-nano Se0 SAMs and HTAB.
Differential pulse stripping voltammetry (DPV) determination of H2O2 using GSH-nano Se0/SAMs Au electrode was presented in 0.1 mol/L KNO3 (pH=5.5) electrolyte solution, an sensitive reduction peak was observed at-320 mV at cyclic voltammetry (CV). The peak current was in a linear relationship with the concentration of H2O2 in the range of 2×10-5-6×10-3 mol/L, and the determination limit was 5×10-7 mol/L. Relative standard deviation (RSD) of the determination results was 2.4% when using three modified electrodes prepared, and RSD was 2.2% when using same modified electrodes prepared at different times. GSH-nanoSe0 SAMs is stable with long using life, which could be applied in H2O2 determination.
以金电极为基底,将所制备的GSH-nano Se0复合物自组装48 h后,可得到致密稳定的谷胱甘肽纳米硒复合物自组装膜(GSH-nano Se0/SAMs)。考察了其电化学特性,并研究了其对过氧化氢(H2O2)电化学还原的催化作用。
研究发现SeCys SAMs在Pb2+, Cu2+存在下,在静电作用和配位作用的共同协作下,形成了一条离子通道,其他离子比如Fe(CN)64/3-，Cd2+可以更容易通过,即出现了离子门效应。GSH/SAMs在阳离子活性剂HTAB的存在下,受静电作用的影响,探针离子Fe(CN)64/3-的电子传输能力明显提高,即具有离子门效应,而在GSH-nano Se0/SAMs上, Se原子与-COOH的配位作用使得复合物结构发生了变化,空间位阻增加,使得离子传输变得困难且对静电作用造成影响,离子门效应减弱。
采用GSH-nano Se0/SAMs Au电极实现了对H2O2体系的电化学催化,在0.1M KNO3(pH=5.5)电解质中,H2O2的还原峰电位在-320 mV处,峰电流随H2O2增加而增加,并在2×10-5-6×10-3mol／L浓度范围内呈线性关系,检测下限为5×10-7mol／L,不同电极之间平行检测的RSD为2.4%,同一电极平行测定的RSD为2.2%,GSH-nano Se0复合膜电极具有良好的重现性和稳定性,使用寿命较长,可应用于H2O2的测定。
In this study, GSH-nano Se0 was prepared by GSH and Na2SeO3 under room temperature in liquid phase, and characterized by UV-Vis Spectra (UV), Transmission electron microscope (TEM), Scan electron microscope (SEM), Fourier transform infrared spectrometry (FTIR), nano-Zeta Sizer(nano-ZS). The results indicated that GSH-nano Se0 was spheres with the average diameter 50nm, nanoSe0 could coordinate with GSH as O-Se-O bond, and-SH turned into-S-S-. There was an ultraviolet absorption in GSH-nano Se0 system, which was attributed to nano Se0. The preparation method was green, simple, low energy consumption in the absence of any template or modifier.
By taking GSH-nano Se0 system as research object, self-assemble (SAMs) technology was used to prepare GSH-nano Se0 SAMs/Au, which provided an interface to study the electrochemical characteristic and catalysis to the H2O2 system.
In this paper, ion gate response of GSH-nano Se0/SAMs was studied, and also compared with SeCys SAMs and GSH SAMs. It was found that SeCys SAMs revealed ion-gate response in the presence of Cu2+or Pb2+. The electron-transfer ability of Fe(CN)64/3- was improved at SeCys SAMs/Au electrode, which results from the fact that the electrostatic interaction between the monolayer and charged ions Cu2+, Pb2+ changed the conformation of SeCys monolayer. GSH SAMs revealed ion-gate response in the presence of cationic surfactant HTAB. The electron-transfer ability of Fe(CN)64/3- was improved in the presence of HTAB at GSH SAMs/Au electrode, which results from the fact that the electrostatic interaction between GSH SAMs and HTAB changed the conformation of GSH monolayer. The ion-gate response at GSH-nanoSe0/SAMs Au electrode was less remarkable than GSH SAMs. The coordination of Se and-COOH resulted in the change of the conformation, which increased steric hindrance and also affect the electrostatic interaction between GSH-nano Se0 SAMs and HTAB.
Differential pulse stripping voltammetry (DPV) determination of H2O2 using GSH-nano Se0/SAMs Au electrode was presented in 0.1 mol/L KNO3 (pH=5.5) electrolyte solution, an sensitive reduction peak was observed at-320 mV at cyclic voltammetry (CV). The peak current was in a linear relationship with the concentration of H2O2 in the range of 2×10-5-6×10-3 mol/L, and the determination limit was 5×10-7 mol/L. Relative standard deviation (RSD) of the determination results was 2.4% when using three modified electrodes prepared, and RSD was 2.2% when using same modified electrodes prepared at different times. GSH-nanoSe0 SAMs is stable with long using life, which could be applied in H2O2 determination.
引文
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