Hong Young Hyun, Nilajakar Madhuri, Lee Yong-Min, Nam Wonwoo, Fukuzumi Shunichi
Department of Chemistry and Nano Science, Ewha Womans University, Seoul 03760, Korea.
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China.
J Am Chem Soc. 2024 Feb 28;146(8):5152-5161. doi: 10.1021/jacs.3c10369. Epub 2024 Feb 13.
In photosynthesis, four electrons and four protons taken from water in photosystem II (PSII) are used to reduce NAD(P) to produce NAD(P)H in photosystem I (PSI), which is the most important reductant to reduce CO. Despite extensive efforts to mimic photosynthesis, artificial photosynthesis to produce NAD(P)H using water electron and proton sources has yet to be achieved. Herein, we report the photocatalytic reduction of NAD(P) to NAD(P)H and its analogues in a molecular model of PSI, which is combined with water oxidation in a molecular model of PSII. Photoirradiation of a toluene/trifluoroethanol (TFE)/borate buffer aqueous solution of hydroquinone derivatives (X-QH), 9-mesityl-10-methylacridinium ion, cobaloxime, and NAD(P) (PSI model) resulted in the quantitative and regioselective formation of NAD(P)H and -benzoquinone derivatives (X-Q). X-Q was reduced to X-QH, accompanied by the oxidation of water to dioxygen under the photoirradiation of a toluene/TFE/borate buffer aqueous solution of [(N4Py)Fe] (PSII model). The PSI and PSII models were combined using two glass membranes and two liquid membranes to produce NAD(P)H using water as an electron and proton source with the turnover number (TON) of 54. To the best of our knowledge, this is the first time to achieve the stoichiometry of photosynthesis, photocatalytic reduction of NAD(P) by water to produce NAD(P)H and O.
在光合作用中，来自光系统II（PSII）中水分子的四个电子和四个质子用于将烟酰胺腺嘌呤二核苷酸磷酸（NAD(P)）还原，从而在光系统I（PSI）中产生还原型烟酰胺腺嘌呤二核苷酸磷酸（NAD(P)H），而NAD(P)H是还原二氧化碳的最重要还原剂。尽管人们为模拟光合作用付出了巨大努力，但利用水作为电子和质子源进行人工光合作用以产生NAD(P)H的目标仍未实现。在此，我们报道了在PSI的分子模型中光催化将NAD(P)还原为NAD(P)H及其类似物，该模型与PSII的分子模型中的水氧化相结合。对苯二酚衍生物（X-QH）、9-均三甲苯基-10-甲基吖啶离子、钴肟和NAD(P)（PSI模型）的甲苯/三氟乙醇（TFE）/硼酸盐缓冲水溶液进行光照射，导致NAD(P)H和对苯醌衍生物（X-Q）的定量和区域选择性形成。在[(N4Py)Fe]（PSII模型）的甲苯/TFE/硼酸盐缓冲水溶液光照射下，X-Q被还原为X-QH，同时水被氧化为氧气。PSI和PSII模型通过两个玻璃膜和两个液膜结合起来，以水作为电子和质子源产生NAD(P)H，周转数（TON）为54。据我们所知，这是首次实现光合作用的化学计量，即通过水将NAD(P)光催化还原以产生NAD(P)H和氧气。
