微过氧化物酶-11在碳纳米管/壳聚糖修饰电极上的直接电化学及电催化

Direct electrochemistry and electrocatalytic activity of microperoxidase-11 immobilized on chitosan wrapped single-walled carbon nanotubes

  • 摘要: 采用一步法于室温下有选择性地将小管径的单壁碳纳米管(SWCNTs)分散于生物相容性的聚合物——壳聚糖的水溶液中,并将其滴涂于玻碳电极表面,制备出微过氧化物酶-11(MP-11)修饰电极。循环伏安结果表明SWCNT促进了MP-11在电极表面的直接电子传递,在pH=7.2的磷酸缓冲溶液中,MP-11的式电位为-0.36V(vs.SCE),MP-11在电极表面的直接电子转移表观速率常数和覆盖度分别为78s-1和8.76×10-10mol·cm-2。进一步的研究结果显示,固定在SWCNT表面的MP-11能保持其对氧气和过氧化氢还原的生物电催化活性,适合用作生物燃料电池的阴极和过氧化氢传感器。氧气在该修饰电极上的还原经历一个四电子过程;该过氧化氢生物传感器对过氧化氢还原的检测具有响应灵敏度高(响应时间小于4s),检测线性范围为2.5×10-6~7.0×10-5μM,检测限为0.8μM,相应的米氏常数和检测灵敏度分别为1.0 mM and 22.4μA/mM。

     

    Abstract: One-step aqueous dispersion and diameter-selective separation of HiPco single-walled carbon nanotubes(SWCNTs)has been accomplished through noncovalent complexation of the nanotubes with a water-soluble,biocompatible polymer chitosan(CHI)at room temperature."Smaller-diameter" SWCNTs are preferentially dispersed and wrapped by CHI in the aqueous supernatant that results following noncentrifuged precipitation,while "larger-diameter" SWCNTs exist in the precipitate.Such CHI wrapped small-diameter individual SWCNTs have been used for the immobilization of microperoxidase-11(MP-11)for direct electrochemistry and electrocatalytic purposes.We found that SWCNTs facilitate the direct electron transfer between MP-11 and the electrode surface,with a formal potential of MP-11 at about-0.36 V(vs.SCE)in phosphate buffer solution(pH 7.2).The heterogenous electron transfer rate constant and surface coverage of MP-11 are estimated to be 78 s-1 and 8.76×10-10 mol/cm2,respectively.Further study demonstrates that the modified electrode retains its electrocatalytic activity toward the reduction of both O2 and H2O2.The immobilized MP-11 can catalyze O2 through a four-electron process to water,which could be used as a cathode in a bio fuel cell.Such SWCNT based biosensor exhibits a rapid response time,of less than 4 s,and a good linear detection range for H2O2 concentration,from2.5 μM to 70 μM with a detection limit of 0.8 μM.The apparent Michaelis-Menten constant(Km)and the maximum electrode sensitivity(imax /Km)are evaluated to be 1.0 mM and 22.4 μA/mM,respectively.

     

/

返回文章
返回