Biodesign Center for Bioelectronics and Biosensors, Biodesign Institute, Arizona State University , Tempe, Arizona 85287, United States.
State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210093, China.
J Am Chem Soc. 2017 May 31;139(21):7244-7249. doi: 10.1021/jacs.7b00839. Epub 2017 May 17.
Conformational fluctuations play a central role in the electron transfer reactions of molecules. Because the fluctuations can be extremely fast in kinetics and small in amplitude, a technique with fast temporal resolution and high conformational sensitivity is needed to follow the transient electron transfer processes. Here we report on an electrochemically controlled plasmonic detection technique capable of monitoring conformational changes in redox molecules with ns response time. Using the technique, we study the electron transfer reaction and the associated conformational gating of a redox protein (cytochrome c). The study reveals that the conformational gating takes place over a broad range of time scales, from microsecond to millisecond.
构象波动在分子的电子转移反应中起着核心作用。由于波动在动力学上可能非常快，而在幅度上则非常小，因此需要一种具有快速时间分辨率和高构象灵敏度的技术来跟踪瞬态电子转移过程。在这里，我们报告了一种电化学控制的等离子体检测技术，该技术能够以纳秒的响应时间监测氧化还原分子的构象变化。使用该技术，我们研究了电子转移反应和相关的氧化还原蛋白（细胞色素 c）的构象门控。该研究表明，构象门控发生在从微秒到毫秒的广泛时间尺度上。
