Anushree Dutta, Robin Mathis Schürmann, Ilko Balko

• The localized surface plasmon resonances (LSPRs) of silver nanoparticles (AgNPs) give rise to the generation of so called hot electrons and a high local electric field enhancement, which enable an application of AgNPs in different fields ranging from catalysis to sensing. Hot electrons generated upon the decay of LSPRs are transferred to molecules adsorbed on the surface of the NPs and trigger chemical reactions via dissociative electron attachment (DEA). Herein, we report on the hot electron induced decomposition of the brominated nucleobases – 8-bromoadenine, 8-bromoguanine, 5-bromocytosine and 5-bromouracil on laser illuminated AgNP surfaces. Surface enhanced Raman scattering (SERS) spectra of all canonical nucleobases and their brominated analogues have been recorded at different laser illumination times, and for the very first time we present SERS measurements of 8-bromoguanine and 5-bromocytosine. Reaction products have been identified by their vibrational fingerprint revealing the cleavage of the carbon bromide bond in allThe localized surface plasmon resonances (LSPRs) of silver nanoparticles (AgNPs) give rise to the generation of so called hot electrons and a high local electric field enhancement, which enable an application of AgNPs in different fields ranging from catalysis to sensing. Hot electrons generated upon the decay of LSPRs are transferred to molecules adsorbed on the surface of the NPs and trigger chemical reactions via dissociative electron attachment (DEA). Herein, we report on the hot electron induced decomposition of the brominated nucleobases – 8-bromoadenine, 8-bromoguanine, 5-bromocytosine and 5-bromouracil on laser illuminated AgNP surfaces. Surface enhanced Raman scattering (SERS) spectra of all canonical nucleobases and their brominated analogues have been recorded at different laser illumination times, and for the very first time we present SERS measurements of 8-bromoguanine and 5-bromocytosine. Reaction products have been identified by their vibrational fingerprint revealing the cleavage of the carbon bromide bond in all cases even under mild illumination conditions. These results indicate that the well-known reactions from DEA experiments in the gas phase (i) are also taking place on nanoparticle surfaces under ambient conditions, (ii) can be monitored by SERS, and (iii) are also of importance in analytical SERS applications involving electrophilic molecules, as the bands originating from reaction products need to be identified.…