Regulating proton-coupled electron transfer for efficient water splitting by manganese oxides at neutral pH.
Regulating proton-coupled electron transfer for efficient water splitting by manganese oxides at neutral pH.
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DOI：
10.1038/ncomms5256
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发表时间：
2014-06-30
影响因子：
16.6
通讯作者：
Nakamura, Ryuhei
中科院分区：
文献类型：
--
作者：
Yamaguchi, Akira;Inuzuka, Riko;Takashima, Toshihiro;Hayashi, Toru;Hashimoto, Kazuhito;Nakamura, Ryuhei
锰氧化物作为光系统II的出氧复合体的模型系统已被广泛研究。然而，大多数生物激发催化剂在中性pH下效率低下，并且与锰的进化氧络合物功能相似的情况很少实现。本文报道了锰氧化物对水氧化过程中质子耦合电子转移的调控。吡啶及其衍生物的pKa值介于与锰（II）和锰（III）结合的水配体之间，被用作质子偶联电子转移诱导试剂。通过氘同位素动力学效应的检测和反应符合力比多规则，证明了质子耦合电子转移的诱导。尽管质子耦合电子转移调控是光系统II中锰表面氧化还原变化的必要条件，但大多数锰氧化物破坏了这些调控机制。因此，目前的研究结果可能为在中性ph下高效分解水的出氧络合物的功能类似物提供了新的设计理论依据。锰氧化物作为自然出氧络合物的类似物被广泛研究，但它们很少在中性ph下起作用。在这里，作者研究了锰氧化物在水氧化中涉及的质子耦合电子转移机制的诱导和调控。
Manganese oxides have been extensively investigated as model systems for the oxygen-evolving complex of photosystem II. However, most bioinspired catalysts are inefficient at neutral pH and functional similarity to the oxygen-evolving complex has been rarely achieved with manganese. Here we report the regulation of proton-coupled electron transfer involved in water oxidation by manganese oxides. Pyridine and its derivatives, which have pKa values intermediate to the water ligand bound to manganese(II) and manganese(III), are used as proton-coupled electron transfer induction reagents. The induction of concerted proton-coupled electron transfer is demonstrated by the detection of deuterium kinetic isotope effects and compliance of the reactions with the libido rule. Although proton-coupled electron transfer regulation is essential for the facial redox change of manganese in photosystem II, most manganese oxides impair these regulatory mechanisms. Thus, the present findings may provide a new design rationale for functional analogues of the oxygen-evolving complex for efficient water splitting at neutral pH. Manganese oxides are extensively investigated as analogues of nature's oxygen-evolving complex, but they rarely function at neutral pH. Here, the authors investigate the induction and regulation of the proton-coupled electron-transfer mechanism involved in water oxidation by manganese oxides.
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DOI：
10.1073/pnas.0905020106
发表时间：
2009-07-21
影响因子：
11.1
作者：
Costentin, Cyrille;Robert, Marc;Teillout, Anne-Lucie
通讯作者：
Teillout, Anne-Lucie
影响因子：
5.4
作者：
El-Deab, Mohamed S.;Awad, Mohamed I.;Ohsaka, Takeo
通讯作者：
Ohsaka, Takeo
影响因子：
2.9
作者：
Geijer, P;Morvaridi, F;Styring, S
通讯作者：
Styring, S
影响因子：
4.9
作者：
Jiao, Feng;Frei, Heinz
通讯作者：
Frei, Heinz
影响因子：
16.6
作者：
Brimblecombe, Robin;Swiegers, Gerhard F.;Spiccia, Leone
通讯作者：
Spiccia, Leone