Kinetics and mechanism of plasmon-driven dehalogenation reaction of brominated purine nucleobases on Ag and Au

  • Plasmon-driven photocatalysis is an emerging and promising application of noble metal nanoparticles (NPs). An understanding of the fundamental aspects of plasmon interaction with molecules and factors controlling their reaction rate in a heterogeneous system is of high importance. Therefore, the dehalogenation kinetics of 8-bromoguanine (BrGua) and 8-bromoadenine (BrAde) on aggregated surfaces of silver (Ag) and gold (Au) NPs have been studied to understand the reaction kinetics and the underlying reaction mechanism prevalent in heterogeneous reaction systems induced by plasmons monitored by surface enhanced Raman scattering (SERS). We conclude that the time-average constant concentration of hot electrons and the time scale of dissociation of transient negative ions (TNI) are crucial in defining the reaction rate law based on a proposed kinetic model. An overall higher reaction rate of dehalogenation is observed on Ag compared with Au, which is explained by the favorable hot-hole scavenging by the reaction product and the byproduct.Plasmon-driven photocatalysis is an emerging and promising application of noble metal nanoparticles (NPs). An understanding of the fundamental aspects of plasmon interaction with molecules and factors controlling their reaction rate in a heterogeneous system is of high importance. Therefore, the dehalogenation kinetics of 8-bromoguanine (BrGua) and 8-bromoadenine (BrAde) on aggregated surfaces of silver (Ag) and gold (Au) NPs have been studied to understand the reaction kinetics and the underlying reaction mechanism prevalent in heterogeneous reaction systems induced by plasmons monitored by surface enhanced Raman scattering (SERS). We conclude that the time-average constant concentration of hot electrons and the time scale of dissociation of transient negative ions (TNI) are crucial in defining the reaction rate law based on a proposed kinetic model. An overall higher reaction rate of dehalogenation is observed on Ag compared with Au, which is explained by the favorable hot-hole scavenging by the reaction product and the byproduct. We therefore arrive at the conclusion that insufficient hole deactivation could retard the reaction rate significantly, marking itself as rate-determining step for the overall reaction. The wavelength dependency of the reaction rate normalized to absorbed optical power indicates the nonthermal nature of the plasmon-driven reaction. The study therefore lays a general approach toward understanding the kinetics and reaction mechanism of a plasmon-driven reaction in a heterogeneous system, and furthermore, it leads to a better understanding of the reactivity of brominated purine derivatives on Ag and Au, which could in the future be exploited, for example, in plasmon-assisted cancer therapy.show moreshow less

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Author details:Anushree DuttaORCiD, Robin SchürmannORCiDGND, Sergio Kogikoski JuniorORCiD, Niclas S. MuellerORCiD, Stephanie ReichORCiD, Ilko BaldORCiDGND
DOI:https://doi.org/10.1021/acscatal.1c01851
ISSN:2155-5435
Pubmed ID:https://pubmed.ncbi.nlm.nih.gov/34239772
Title of parent work (English):ACS catalysis / American Chemical Society
Publisher:American Chemical Society
Place of publishing:Washington
Publication type:Article
Language:English
Date of first publication:2021/06/23
Publication year:2021
Release date:2023/09/06
Tag:SERS; brominated; fractal kinetics; hole scavengers; hot-electrons; plasmon-driven catalysis; purines
Volume:11
Issue:13
Number of pages:12
First page:8370
Last Page:8381
Funding institution:European Research Council (ERC)European Research Council (ERC)European Commission [772752]; Focus Area NanoScale of Freie Universitaet Berlin; European Research Council (ERC) within the project DarkSERSEuropean Research Council (ERC) [772108]
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
DDC classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften
Peer review:Referiert
Publishing method:Open Access / Hybrid Open-Access
License (German):License LogoCC-BY-NC-ND - Namensnennung, nicht kommerziell, keine Bearbeitungen 4.0 International
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