Four polyoxometalates (POMs) were combined with an artificial reductase based on polyethyleneimine (PEI) and flavin mononucleotide (FMN) which is capable of delivering single electrons upon addition of nicotinamide adenine dinucleotide (NADH). The efficiency of this system for sulfoxidation reactions in water, at room temperature, under atmospheric pressure and with dioxygen as an oxidant was demonstrated, with yields up to 82% in sulfoxide. Mechanistic investigations allowed proposing two different catalytic pathways, depending on the nature of the POM. For the polyoxotungstates Na₁₂[(ZnW₉O₃₄)₂WZn₃(H₂O)₂]·46H₂O and Na₇K₇[{(PW₉O₃₄)Ni₃(OH)(H₂O)₂(Ale)}₂Ni]·34H₂O (Ale = alendronate = [O₃PC(O)(C₃H₆NH₃)PO₃]⁴⁻), the in situ production of H₂O₂ by the artificial reductase that activates the POM was evidenced. Alternatively, for the polyoxomolybdates H₃[PMo₁₂O₄₀]·14H₂O and H₄[PMo₁₁VO₄₀]·14H₂O, the reduction of the POM by the artificial reductase, followed by the reductive activation of O₂, led to the sulfoxidation reaction.

中文翻译：

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在室温和水中与人工还原酶相关的多金属氧酸盐催化的好氧氧化

将四种多金属氧酸盐（POM）与基于聚乙烯亚胺（PEI）和黄素单核苷酸（FMN）的人工还原酶结合，该黄酮单核苷酸在添加烟酰胺腺嘌呤二核苷酸（NADH）后能够传递单电子。证明了该系统在水中，室温，大气压下和以二氧为氧化剂进行亚硫酸氧化反应的效率，亚砜的收率高达82％。机械研究允许根据POM的性质提出两种不同的催化途径。对于多氧钨酸盐Na ₁₂ [（ZnW ₉ O ₃₄）₂ WZn ₃（H ₂ O）₂ ]·46H ₂ O和Na₇ K ₇ [{（PW ₉ O ₃₄）Ni ₃（OH）（H ₂ O） ₂（Ale）} ₂ Ni]·34H ₂ O（Ale =阿仑膦酸盐= [O ₃ PC（O）（C ₃ H ₆ NH ₃）PO ₃ ] ⁴⁻），证明了通过激活POM的人工还原酶原位产生H ₂ O ₂。或者，对于聚氧钼酸盐，H ₃ [PMo ₁₂ O ₄₀ ]·14H ₂ O和H ₄ [PMo₁₁ VO ₄₀ ]·14H ₂ O，由人工还原酶还原POM，然后O ₂还原活化，导致了亚砜氧化反应。