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Hidden Dynamics of Noble-metal-bound Thiol Monolayers Revealed by SERS-monitored Entropy-driven Exchange of Cysteine Isotopologues

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cris.lastimport.scopus2024-02-12T19:30:26Z
dc.abstract.enVibrational spectroscopy coupled with isotopic labeling provides insight into the dynamics of various molecular processes. Here, a newfound approach in surface-enhanced Raman scattering (SERS) spectroscopy to study noble metal-anchored thiol monolayers is demonstrated for a pair of L-cysteine isotopologues competing for binding to silver nanoparticles (AgNPs): Cys-cabn (all 12C/14N) and Cys-CABN (all 13C/15N). As predicted by our DFT calculations, a distinct difference in the Raman shift value (>50 cm−1) of the ν(C = O) band was observed for these two AgNP-anchored isotopologues. SERS intensity ratio of these two peaks allowed for quantitative monitoring of an exclusively entropy-driven exchange of Cys molecules between the surface and the solution, revealing a reversible and rapid activation after a mild temperature increase (50 °C). This behavior is attributed to the collective phase transition within the monolayer. This work highlights unexplored potential of SERS spectroscopy coupled with isotopic exchange to study dynamic phenomena within a metal-anchored layer.
dc.affiliationUniwersytet Warszawski
dc.contributor.authorKrólikowska, Agata
dc.contributor.authorDzwolak, Wojciech
dc.contributor.authorCukras, Janusz
dc.contributor.authorWitkowski, Marcin
dc.date.accessioned2024-01-25T03:08:11Z
dc.date.available2024-01-25T03:08:11Z
dc.date.issued2023
dc.description.financeNie dotyczy
dc.description.volume623
dc.identifier.doi10.1016/J.APSUSC.2023.156985
dc.identifier.issn0169-4332
dc.identifier.urihttps://repozytorium.uw.edu.pl//handle/item/108426
dc.identifier.weblinkhttps://api.elsevier.com/content/article/PII:S0169433223006621?httpAccept=text/xml
dc.languageeng
dc.pbn.affiliationchemical sciences
dc.relation.ispartofApplied Surface Science
dc.relation.pages156985
dc.rightsClosedAccess
dc.sciencecloudnosend
dc.subject.enIsotopic labeling
dc.subject.enOrganic monolayers
dc.subject.enRaman spectroscopy
dc.subject.enSurface-enhanced Raman scattering
dc.subject.enTemperature-activated collective phase transition
dc.titleHidden Dynamics of Noble-metal-bound Thiol Monolayers Revealed by SERS-monitored Entropy-driven Exchange of Cysteine Isotopologues
dc.typeJournalArticle
dspace.entity.typePublication