Dataset Information

Direct Observation of Photoinduced Charge Separation in Ruthenium Complex/Ni(OH)2 Nanoparticle Hybrid.

ABSTRACT: Ni(OH)2 have emerged as important functional materials for solar fuel conversion because of their potential as cost-effective bifunctional catalysts for both hydrogen and oxygen evolution reactions. However, their roles as photocatalysts in the photoinduced charge separation (CS) reactions remain unexplored. In this paper, we investigate the CS dynamics of a newly designed hybrid catalyst by integrating a Ru complex with Ni(OH)2 nanoparticles (NPs). Using time resolved X-ray absorption spectroscopy (XTA), we directly observed the formation of the reduced Ni metal site (~60?ps), unambiguously demonstrating CS process in the hybrid through ultrafast electron transfer from Ru complex to Ni(OH)2 NPs. Compared to the ultrafast CS process, the charge recombination in the hybrid is ultraslow (?50?ns). These results not only suggest the possibility of developing Ni(OH)2 as solar fuel catalysts, but also represent the first time direct observation of efficient CS in a hybrid catalyst using XTA.

SUBMITTER: Tang Y

PROVIDER: S-EPMC4682087 | biostudies-other | 2015

REPOSITORIES: biostudies-other

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Direct Observation of Photoinduced Charge Separation in Ruthenium Complex/Ni(OH)2 Nanoparticle Hybrid.

Tang Yu Y Pattengale Brian B Ludwig John J Atifi Abderrahman A Zinovev Alexander V AV Dong Bin B Kong Qingyu Q Zuo Xiaobing X Zhang Xiaoyi X Huang Jier J

Scientific reports 20151217

Ni(OH)2 have emerged as important functional materials for solar fuel conversion because of their potential as cost-effective bifunctional catalysts for both hydrogen and oxygen evolution reactions. However, their roles as photocatalysts in the photoinduced charge separation (CS) reactions remain unexplored. In this paper, we investigate the CS dynamics of a newly designed hybrid catalyst by integrating a Ru complex with Ni(OH)2 nanoparticles (NPs). Using time resolved X-ray absorption spectrosc ...[more]

PMID: 26673578

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Project description:Charge separation is one of the most common consequences of the absorption of UV light by DNA. Recently, it has been shown that this process can enable efficient self-repair of cyclobutane pyrimidine dimers (CPDs) in specific short DNA oligomers such as the GAT[double bond, length as m-dash]T sequence. The mechanism was characterized as sequential electron transfer through the nucleobase stack which is controlled by the redox potentials of nucleobases and their sequence. Here, we demonstrate that the inverse sequence T[double bond, length as m-dash]TAG promotes self-repair with higher quantum yields (0.58 ± 0.23%) than GAT[double bond, length as m-dash]T (0.44 ± 0.18%) in a comparative study involving UV-irradiation experiments. After extended exposure to UV irradiation, a photostationary equilibrium between self-repair and damage formation is reached at 33 ± 13% for GAT[double bond, length as m-dash]T and at 40 ± 16% for T[double bond, length as m-dash]TAG, which corresponds to the maximum total yield of self-repair. Molecular dynamics and quantum mechanics/molecular mechanics (QM/MM) simulations allowed us to assign this disparity to better stacking overlap between the G and A bases, which lowers the energies of the key A-˙G+˙ charge transfer state in the dominant conformers of the T[double bond, length as m-dash]TAG tetramer. These conformational differences also hinder alternative photorelaxation pathways of the T[double bond, length as m-dash]TAG tetranucleotide, which otherwise compete with the sequential electron transfer mechanism responsible for CPD self-repair. Overall, we demonstrate that photoinduced electron transfer is strongly dependent on conformation and the availability of alternative photodeactivation mechanisms. This knowledge can be used in the identification and prediction of canonical and modified DNA sequences exhibiting efficient electron transfer. It also further contributes to our understanding of DNA self-repair and its potential role in the photochemical selection of the most photostable sequences on the early Earth.

Dataset Information

Direct Observation of Photoinduced Charge Separation in Ruthenium Complex/Ni(OH)2 Nanoparticle Hybrid.

Publications

Direct Observation of Photoinduced Charge Separation in Ruthenium Complex/Ni(OH)2 Nanoparticle Hybrid.

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