Probing redox reactions of immobilized cytochrome c using evanescent wave cavity ring-down spectroscopy in a thin-layer electrochemical cell.

Probing redox reactions of immobilized cytochrome c using evanescent wave cavity ring-down spectroscopy in a thin-layer electrochemical cell.
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在薄层电化学电池中使用倏逝波腔衰荡光谱法探测固定化细胞色素 c 的氧化还原反应。

DOI:
10.1002/cphc.201000213
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发表时间:
2010
期刊:
a European journal of chemical physics and physical chemistry
影响因子:
--
通讯作者:
Powell HV
Powell HV
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--
文献类型:
--
作者:
Powell HV

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电子转移(ET)是许多生物过程的基础。特别地,呼吸和光合作用包括涉及氧化还原蛋白的ET事件的级联,以在细胞中产生能量。[1]确定这些过程的速率以及驱动它们的机制对于理解体内代谢途径非常重要。此外,ET到氧化还原蛋白质的知识是优化技术的基础,如生物传感器,[2,3]生物燃料电池,[4]非均相催化剂[5]和生物分子电子元件。[6]传统上,获得蛋白质和氧化还原介体或其他蛋白质之间的ET动力学是在均质溶液中使用停流装置并通过吸收光谱监测蛋白质的氧化还原状态的变化来实现的。[7-11]然而,自从Eddowes和Hill [12]以及Yeh和库瓦纳[13]在1977年独立地首次成功演示了马心细胞色素c的循环伏安法以来,ET蛋白和复合酶的直接和介导电化学领域蓬勃发展。[2,14]蛋白膜伏安法(PFV)[15]被广泛接受为理解蛋白质和电极之间的ET的强大工具,用于制造生物电子和生物燃料电池中的生物传感器[2,16]等设备[8,9],并作为理解体内氧化还原蛋白质之间ET的模型方法。[17]在PFV中,在电极处施加的电势驱动电子进出固定在电极上的电活性蛋白质膜的活性位点,从而允许评估形式电势和ET速率以及其他动力学和热力学参数。[18]此外,PFV已被用来研究吸附的蛋白质和它们的氧化还原伙伴之间的ET的机制和速率。[19]与均相测量相比,这是一个重要的发展,因为在体内,ET经常发生在界面处。尽管PFV在探索这些过程中的许多过程中非常成功,但由于难以以这样的方式将膜中的蛋白质定向,使得其可以与电极进行快速ET并且还与其氧化还原配偶体成功对接,因此它是有限的。扫描电化学显微镜(SECM)[20]也被证明在研究固定化酶的氧化还原性质方面是强大的,包括细胞色素c,[10]葡萄糖氧化酶,[21]和辣根过氧化物酶。[22]使用SECM对表面固定化酶的图案进行成像对于基于酶的传感器的表征和优化以及生物传感器的形成(例如,用于检测乳腺癌标志物)是重要的。[24]SECM方法的吸引力在于酶不必固定在电极表面上,尽管它们可以固定在电极表面上,[10a]从而允许在一系列界面环境中研究ET动力学。
Electron transfer (ET) is fundamental to many biological processes. In particular, respiration and photosynthesis comprise a cascade of ET events involving redox proteins to produce energy in the cell.[1] Determining the rates of these processes, and the mechanisms that drive them, is important for understanding metabolic pathways in vivo. Furthermore, knowledge of ET to redox proteins is fundamental to optimizing technologies such as biosensors,[2, 3] biofuel cells,[4] heterogeneous catalysts [5] and biomolecular electronic components.[6] Traditionally, obtaining the kinetics of ET between proteins and redox mediators or other proteins was achieved in homogeneous solution using stopped flow apparatus and monitoring the change in the redox state of the protein by absorption spectroscopy.[7–11] However, since the first successful demonstrations of cyclic voltammetry of horse heart cytochrome c by Eddowes and Hill [12] and Yeh and Kuwana [13] independently in 1977, the area of the direct and mediated electrochemistry of both ET proteins and complex enzymes has flourished.[2, 14] Protein film voltammetry (PFV)[15] is widely accepted as a powerful tool for understanding ET between proteins and electrodes for the fabrication of devices such as biosensors,[2, 16] in bioelectronics and biofuel cells,[8, 9] and as a model approach for comprehending ET between redox proteins in vivo.[17] In PFV, a potential applied at an electrode drives electrons in and out of the active sites of an electroactive protein film immobilized on the electrode, allowing the evaluation of the formal potentials and the rates of ET and other kinetic and thermodynamic parameters.[18] Moreover, PFV has been employed to investigate the mechanisms and rates of ET between the adsorbed proteins and their redox partners.[19] Compared to homogeneous phase measurements, this was an important development because in vivo, ET often occurs at interfaces. Although PFV has been very successful in exploring many of these processes, it is limited due to the difficulty of orienting the protein in the film in such a way that it can undergo fast ET with the electrode and also dock successfully with its redox partners.Scanning electrochemical microscopy (SECM)[20] has also proved powerful in studying the redox properties of immobilized enzymes, including cytochrome c,[10] glucose oxidase,[21] and horse radish peroxidase.[22] Imaging of patterns of surfaceimmobilized enzymes using SECM is important to the characterization and optimization of enzyme-based sensors [23] and for the formation of biosensors, for example, for the detection of breast cancer markers.[24] An attraction of the SECM approach is that the enzymes do not have to be immobilized on an electrode surface, although they may be,[10a] thereby allowing ET kinetics to be investigated in a range of interfacial environ-
DOI: 10.1021/la026107c
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影响因子: 3.9
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三氟乙酰化马心细胞色素c的电子转移反应
DOI: --
发表时间: 1978
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DOI: --
发表时间: 1974
期刊:
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作者:
Hodges Hl;R. Holwerda;H. Gray
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DOI: 10.1186/1471-2091-4-2
发表时间: 2003-03-11
期刊: BMC biochemistry
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