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Electrochemical Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy of Imidazole Ring Functionalized Monolayer on Smooth Gold Electrode.
Zdaniauskiene, Agne; Talaikis, Martynas; Charkova, Tatjana; Sadzeviciene, Rita; Labanauskas, Linas; Niaura, Gediminas.
Afiliación
  • Zdaniauskiene A; Center for Physical Sciences and Technology (FTMC), Department of Organic Chemistry, Sauletekio Ave. 3, LT-10257 Vilnius, Lithuania.
  • Talaikis M; Life Sciences Center, Institute of Biochemistry, Department of Bioelectrochemistry and Biospectroscopy, Vilnius University, Sauletekio Ave. 7, LT-10257 Vilnius, Lithuania.
  • Charkova T; Center for Physical Sciences and Technology (FTMC), Department of Organic Chemistry, Sauletekio Ave. 3, LT-10257 Vilnius, Lithuania.
  • Sadzeviciene R; Center for Physical Sciences and Technology (FTMC), Department of Organic Chemistry, Sauletekio Ave. 3, LT-10257 Vilnius, Lithuania.
  • Labanauskas L; Center for Physical Sciences and Technology (FTMC), Department of Organic Chemistry, Sauletekio Ave. 3, LT-10257 Vilnius, Lithuania.
  • Niaura G; Center for Physical Sciences and Technology (FTMC), Department of Organic Chemistry, Sauletekio Ave. 3, LT-10257 Vilnius, Lithuania.
Molecules ; 27(19)2022 Oct 03.
Article en En | MEDLINE | ID: mdl-36235068
The imidazole ring (Im) of histidine side chains plays a unique role in the function of proteins through covalent bonding with metal ions and hydrogen bonding interactions with adjusted biomolecules and water. At biological interfaces, these interactions are modified because of the presence of an electric field. Self-assembled monolayers (SAMs) with the functional Im group mimic the histidine side chain at electrified interfaces. In this study, we applied in-situ shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) to probe the structure and hydrogen bonding of Im-functionalized SAM on smooth Au at the electrochemical interface. The self-assembly of molecules on the Au induced the proton shift from N1 atom (Tautomer-I), which is the dominant form of Im in the bulk sample, to N3 atom (Tautomer-II). The impact of electrode potential on the hydrogen bonding interaction strength of the Im ring was identified by SHINERS. Temperature-Raman measurements and density functional theory (DFT) analysis revealed the spectral marker for Im ring packing (mode near 1496-1480 cm-1) that allowed us to associate the confined and strongly hydrogen bonded interfacial Im groups with electrode polarization at -0.8 V. Reflection adsorption IR (RAIR) spectra of SAMs with and without Im revealed that the bulky ring prevented the formation of a strongly hydrogen bonded amide group network.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Nanopartículas / Oro Idioma: En Revista: Molecules Asunto de la revista: BIOLOGIA Año: 2022 Tipo del documento: Article País de afiliación: Lituania Pais de publicación: Suiza
Texto completo
Añadir a Mi BVS
Imprimir
XML
PubMed Links
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Nanopartículas / Oro Idioma: En Revista: Molecules Asunto de la revista: BIOLOGIA Año: 2022 Tipo del documento: Article País de afiliación: Lituania Pais de publicación: Suiza