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基于聚丙烯酰胺和壳聚糖的半互穿聚合物网络水凝胶中包埋血红蛋白的直接电化学与电催化作用

Direct electrochemistry and electrocatalysis of hemoglobin entrapped in semi-interpenetrating polymer network hydrogel based on polyacrylamide and chitosan.

作者信息

Zeng Xiandong, Wei Wanzhi, Li Xuefang, Zeng Jinxiang, Wu Ling

机构信息

State Key Laboratory of Chemo/Biosensoring and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Hunan, Changsha 410082, P. R. China.

出版信息

Bioelectrochemistry. 2007 Nov;71(2):135-41. doi: 10.1016/j.bioelechem.2007.02.006. Epub 2007 Mar 1.

Abstract

Semi-interpenetrating polymer network (semi-IPN) hydrogel based on polyacrylamide (PAM) and chitosan was prepared to immobilize redox protein hemoglobin (Hb). The Hb-PAM-chitosan hydrogel film obtained has been investigated by scanning electron microscopy (SEM) and UV-VIS spectroscopy. UV-VIS spectroscopy showed that Hb kept its secondary structure similar to its native state in the Hb-PAM-chitosan hydrogel film. Cyclic voltammogram of Hb-PAM-chitosan film-modified glass carbon (GC) electrode showed a pair of well-defined and quasi-reversible redox peaks for Hb Fe(III)/Fe(II), indicating that direct electron transfer between Hb and GC electrode occurred. The electron-transfer rate constant was about 5.51 s(-1) in pH 7.0 buffers, and the formal potential (E degrees ') was -0.324 V (vs. SCE). The dependence of E degrees ' on solution pH indicated that one-proton transfer was coupled to each electron transfer in the direct electron-transfer reaction. Additionally, Hb in the semi-IPN hydrogel film retained its bioactivity and showed excellent electrocatalytic activity toward H(2)O(2). The electrocatalytic current values were linear with increasing concentration of H(2)O(2) in a wide range of 5-420 microM. The unique semi-IPN hydrogel would have wide potential applications in direct electrochemistry, biosensors and biocatalysis.

摘要

制备了基于聚丙烯酰胺(PAM)和壳聚糖的半互穿聚合物网络(semi-IPN)水凝胶,用于固定氧化还原蛋白血红蛋白(Hb)。通过扫描电子显微镜(SEM)和紫外可见光谱对所得的Hb-PAM-壳聚糖水凝胶膜进行了研究。紫外可见光谱表明,Hb在Hb-PAM-壳聚糖水凝胶膜中保持了与其天然状态相似的二级结构。Hb-PAM-壳聚糖膜修饰玻碳(GC)电极的循环伏安图显示出一对明确且准可逆的Hb Fe(III)/Fe(II)氧化还原峰,表明Hb与GC电极之间发生了直接电子转移。在pH 7.0缓冲溶液中,电子转移速率常数约为5.51 s(-1),形式电位(E°')为 -0.324 V(相对于饱和甘汞电极,SCE)。E°'对溶液pH的依赖性表明,在直接电子转移反应中,每一次电子转移伴随着一个质子转移。此外,半互穿聚合物网络水凝胶膜中的Hb保留了其生物活性,并对H₂O₂表现出优异的电催化活性。在5 - 420 μM的宽范围内,电催化电流值与H₂O₂浓度的增加呈线性关系。这种独特的半互穿聚合物网络水凝胶在直接电化学、生物传感器和生物催化领域具有广泛的潜在应用。

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