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Modulation of Phenol Oxidation in Cofacial Dyads.


ABSTRACT: The presentation of two phenols on a xanthene backbone is akin to the tyrosine dyad (Y730 and Y731) of ribonucleotide reductase. X-ray crystallography reveals that the two phenol moieties are cofacially disposed at 4.35 Å. Cyclic voltammetry reveals that phenol oxidation is modulated within the dyad, which exhibits a splitting of one-electron waves with the second oxidation of the phenol dyad occurring at larger positive potential than that of a typical phenol. In contrast, a single phenol appended to a xanthene exhibits a two-electron process, consistent with reported oxidation pathways of phenols in acetonitrile. The perturbation of the phenol potential by stacking is reminiscent of a similar effect for guanines stacked within DNA base pairs.

SUBMITTER: Koo BJ 

PROVIDER: S-EPMC4596711 | biostudies-literature | 2015 Sep

REPOSITORIES: biostudies-literature

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Modulation of Phenol Oxidation in Cofacial Dyads.

Koo Bon Jun BJ   Huynh Michael M   Halbach Robert L RL   Stubbe JoAnne J   Nocera Daniel G DG  

Journal of the American Chemical Society 20150909 37


The presentation of two phenols on a xanthene backbone is akin to the tyrosine dyad (Y730 and Y731) of ribonucleotide reductase. X-ray crystallography reveals that the two phenol moieties are cofacially disposed at 4.35 Å. Cyclic voltammetry reveals that phenol oxidation is modulated within the dyad, which exhibits a splitting of one-electron waves with the second oxidation of the phenol dyad occurring at larger positive potential than that of a typical phenol. In contrast, a single phenol appen  ...[more]

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