Department of Chemistry, University of Colorado Boulder, Boulder, Colorado 80309, USA; email:
Current affiliation: Department of Chemistry, University of California, Berkeley, California 94720, USA; email:
Annu Rev Phys Chem. 2020 Apr 20;71:335-359. doi: 10.1146/annurev-physchem-050317-014232. Epub 2020 Feb 25.
This review summarizes progress in understanding electron transfer from photoexcited nanocrystals to redox enzymes. The combination of the light-harvesting properties of nanocrystals and the catalytic properties of redox enzymes has emerged as a versatile platform to drive a variety of enzyme-catalyzed reactions with light. Transfer of a photoexcited charge from a nanocrystal to an enzyme is a critical first step for these reactions. This process has been studied in depth in systems that combine Cd-chalcogenide nanocrystals with hydrogenases. The two components can be assembled in close proximity to enable direct interfacial electron transfer or integrated with redox mediators to transport charges. Time-resolved spectroscopy and kinetic modeling have been used to measure the rates and efficiencies of the electron transfer. Electron transfer has been described within the framework of Marcus theory, providing insights into the factors that can be used to control the photochemical activity of these biohybrid systems. The range of potential applications and reactions that can be achieved using nanocrystal-enzyme systems is expanding, and numerous fundamental and practical questions remain to be addressed.
这篇综述总结了人们在理解将光激发的纳米晶体中的电子转移到氧化还原酶这方面的进展。将纳米晶体的光收集特性与氧化还原酶的催化特性相结合，已经成为一个通用的平台，可以利用光来驱动各种酶催化反应。对于这些反应来说，从纳米晶体到酶的光激发电荷的转移是至关重要的第一步。在将 Cd-硫属化物纳米晶体与氢化酶结合的系统中，已经对这一过程进行了深入研究。这两个组件可以组装在一起，以实现直接的界面电子转移，或者与氧化还原介体集成，以传输电荷。时间分辨光谱和动力学模型已被用于测量电子转移的速率和效率。电子转移已在 Marcus 理论的框架内进行了描述，为可以用于控制这些生物杂化系统的光化学活性的因素提供了深入的了解。利用纳米晶体-酶系统可以实现的潜在应用和反应的范围正在扩大，还有许多基础和实际问题需要解决。
