Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, United States.
Department of Chemical and Biomolecular Engineering, University of California, Berkeley, Berkeley, California 94720, United States.
Nano Lett. 2024 Oct 23;24(42):13269-13276. doi: 10.1021/acs.nanolett.4c03528. Epub 2024 Oct 14.
The photochemical generation of nicotinamide cofactor 1,4-NADH, facilitated by inorganic photosensitizers, emerges as a promising model system for investigating charge transfer phenomena at the interface of semiconductors and bacteria, with implications for enhancing photosynthetic biohybrid systems (PBSs). However, extant semiconductor nanocrystal model systems suffer from achieving optimal conversion efficiency under visible light. This study investigates quasi-one-dimensional CdS nanorods as superior light absorbers, surface modified with catalyst Cp*Rh(4,4'-COOH-bpy)Cl to produce enzymatically active NADH. This model subsystem facilitates easy product isolation and achieves a turnover frequency (TOF) of 175 h, one of the highest efficiencies reported for inorganic photosensitizer-based nicotinamide cofactor generation. Charge transfer kinetics, fundamental for catalytic solar energy conversion, range from 10 to 10 s for this system highlighting the superior electron transfer capabilities of NRs. This model ensures efficient cofactor production and offers critical insights into advancing systems that mimic natural photosynthesis for sustainable solar-to-chemical synthesis.
无机光敏剂促进烟酰胺辅酶 1,4-NADH 的光化学生成，为研究半导体和细菌界面的电荷转移现象提供了一个很有前途的模型体系，这对增强光合生物杂种系统（PBS）具有重要意义。然而，现有的半导体纳米晶体模型体系在可见光下实现最佳转化率仍存在困难。本研究以具有优越吸光性能的准一维 CdS 纳米棒为研究对象，其表面修饰有催化剂 Cp*Rh(4,4'-COOH-bpy)Cl，以产生具有酶活性的 NADH。该模型子系统便于产物的分离，并实现了 175 h 的周转频率（TOF），这是报道的基于无机光敏剂的烟酰胺辅酶生成中最高效率之一。对于这种体系，对于催化太阳能转化至关重要的电荷转移动力学范围为 10 到 10 s，这突出了 NRs 的优越的电子转移能力。该模型确保了辅酶的高效生成，并为推进模拟自然光合作用的可持续太阳能-化学合成系统提供了关键见解。
