Reactivities of 1,2-, 1,3-, and 1,4-Dihydroxynaphthalenes toward Electrogenerated Superoxide in N,N-Dimethylformamide through Proton-coupled Electron Transfer
Reactivities of 1,2-, 1,3-, and 1,4-Dihydroxynaphthalenes toward Electrogenerated Superoxide in N,N-Dimethylformamide through Proton-coupled Electron Transfer
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1,2-、1,3-和 1,4-二羟基萘通过质子耦合电子转移在 N,N-二甲基甲酰胺中对电生成超氧化物的反应性
DOI：
10.1016/j.electacta.2022.141467
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发表时间：
2022
影响因子：
6.6
通讯作者：
B. Uno
中科院分区：
文献类型：
--
作者：
Tatsushi Nakayama;B. Uno
We have carried out an electrochemical and theoretical study on the reactivity of 1,2-, 1,3-, and 1,4-dihydroxynaphthalenes (1nH2NQ,n= 2, 3, 4) toward electrogenerated superoxide radical anion (O2•−) inN,N-dimethylformamide. Cyclicvoltammetry and in situ electrolytic electron spin resonance measurements revealed that the quinone–hydroquinone π-conjugation plays an important role in a successful O2•−scavenging by 12H2NQ and 14H2NQ through proton-coupled electron transfer (PCET) reaction. The reactivities of 12H2NQ and 14H2NQ toward O2•−were mediated by the ortho- (catechol) or para-diphenol (hydroquinone) moieties, as experimentally confirmed in comparative analyses with catechol, hydroquinone, and 13H2NQ, aided by density functional theory (DFT) calculations. The electrochemical and DFT results suggested that a concerted PCET mechanism involving two-proton transfers and one-electron transfer proceeds, demonstrating a successful O2•−scavenging by 12H2NQ and 14H2NQ. Furthermore, a subsequent electron transfer between molecular dioxygen and product-naphthoquinone-radicals was observed, where O2•−was regenerated. The DFT analysis suggested that the spin distribution on the planar naphthalene ring embodies the superior kinetics of the PCET and the subsequent generation of O2•−from dioxygen demonstrated in the electrochemical results.
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DOI：
10.3390/antiox11010009
发表时间：
2021-12-22
期刊：
Antioxidants (Basel, Switzerland)
影响因子：
--
作者：
Nakayama T;Honda R;Kuwata K;Usui S;Uno B
通讯作者：
Uno B
影响因子：
3.2
作者：
Murakami, Keiko;Haneda, Miyako;Yoshino, Masataka
通讯作者：
Yoshino, Masataka
N,N-二甲基甲酰胺中邻苯三酚通过质子耦合电子转移清除超氧化物的电化学及机理研究
影响因子：
--
作者：
Nakayama Tatsushi;Honda Ryo;Kuwata Kazuo;Usui Shigeyuki;Uno Bunji
通讯作者：
Uno Bunji
DOI：
10.3390/ph14020120
发表时间：
2021-02-04
期刊：
Pharmaceuticals (Basel, Switzerland)
影响因子：
--
作者：
Nakayama T;Honda R
通讯作者：
Honda R