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Electronic transduction of photostimulated binding interactions atphotoisomerizable monolayer electrodes: Novel approaches foroptobioelectronic systems and reversible immunosensor devices

机译:在光致异构化单层电极上光刺激结合相互作用的电子转导:光生物电子系统和可逆免疫传感器设备的新方法

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Photoisomerizable monolayers assembled onto electrode supports act as "command interfaces" for controlling the binding interactions of biomaterials with the functionalized surfaces. The light-induced binding and dissociation of the biomaterials to and from the electrodes, respectively, are electronically transduced. Two systems,including the photostimulated binding and dissociation of cytochrome c (Cyt c) and of anti-DNP antibody to and from functionalized surfaces, are discussed. The application of the systems as optobioelectronic devices and reversible immunosensors is addressed. A mixed monolayer consisting of pyridine and nitrospiropyran (1a) photoisomerizable units assembled on a Au-electrode acts as a command interface for the light-controlled association and dissociation of Cyt c to and from the monolayer. Cyt c binds to the pyridine/1a-monolayer electrode, resulting in electrical contact between the redox protein and the electrode. Photoisomerization of the mixed monolayer to the pyridine/protonated merocyanine state (Ib) results in the electrostatic repulsion of Cyt c and its dissociation from the electrode support. This blocks the electrical contact between Cyt c and the electrode. By the cyclic photoisomerization of the mixed monolayer between the la and Ib states, reversible "ON"-"OFF" amperometric transduction of the affinity interactions between the redox protein and the interface is accomplished. Coupling of the photostimulated electrical contact between Cyt c and the electrode surface to the Cyt c-mediated bioelectrocatalyzed reduction of O-2 by cytochrome oxidase provides a means to amplify the transduced electronic signal. A photoisomerizable thiolated dinitrospiropyran (2a) monolayer, assembled on solid supports, acts as a light-active antigen interface that enables the photocontrolled binding and dissociation of anti-dinitrophenyl antibody (DNP-Ab) to and from the interface. The dinitrospiropyran (2a) layer acts as an antigen for the DNP-Ab, whereas the protonated dinitromerocyanine (2b) lacks antigen features for the DNP-Ab. By reversible photoisomerization of the monolayer between the 2a and 2b states, cyclic binding and dissociation of DNP-Ab to and from the monolayer interface is accomplished. The association and dissociation of the DNP-Ab to and from the 2a- and 2b-monolayer states are electronically transduced, using amperometric, Faradaic impedance and microgravimetric, quartz crystal microbalance analyses. The photostimulated binding of an antibody to a photoisomerizable antigen monolayer provides a novel method to design reversible immunosensor devices.
机译:组装在电极支架上的可光异构化单层充当“命令界面”,用于控制生物材料与功能化表面的结合相互作用。电子诱导光诱导的生物材料分别与电极的结合和解离。讨论了两个系统,包括光刺激的细胞色素c(Cyt c)和抗DNP抗体与功能化表面的结合和解离。解决了该系统作为光电生物电子设备和可逆免疫传感器的应用。组装在Au电极上的由吡啶和硝基螺吡喃(1a)光致异构化单元组成的混合单层充当Cyt c进出单层的光控缔合和离解的指令界面。 Cyt c结合到吡啶/ 1a单层电极上,导致氧化还原蛋白和电极之间的电接触。混合单层光异构化为吡啶/质子化的花菁状态(Ib)导致Cyt c发生静电排斥,并从电极载体上解离。这阻止了Cyt c和电极之间的电接触。通过1a和1b状态之间的混合单层的循环光异构化,实现了氧化还原蛋白与界面之间的亲和力相互作用的可逆的“ ON”-“ OFF”安培数转导。 Cyt c和电极表面之间的光刺激电接触与Cyt c介导的细胞色素氧化酶对O-2的生物电催化还原O-2的耦合提供了一种放大转导的电子信号的方法。组装在固体支持物上的可光异构化的巯基化的二硝基螺吡喃(2a)单层充当光活性抗原界面,使抗二硝基苯基抗体(DNP-Ab)能够光控制地与该界面结合和解离。二硝基螺吡喃(2a)层充当DNP-Ab的抗原,而质子化的二硝基硫氰酸(2b)缺乏DNP-Ab的抗原特征。通过在2a和2b状态之间对单层进行可逆的光异构化,可以实现DNP-Ab与单层界面之间的循环结合和离解。 DNP-Ab与2a-和2b-单层态之间的缔合和解离通过安培,法拉第阻抗和微重力,石英晶体微天平分析进行电子转换。抗体与光异构化抗原单层的光刺激结合提供了设计可逆免疫传感器装置的新颖方法。

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