Interaction Mechanisms and Interface Configuration of Cysteine Adsorbed on Gold, Silver, and Copper Nanoparticles
Por:
Rodriguez-Zamora, Penelope, Cordero-Silis, Cedric A., Fabila, Jorge, Luque-Ceballos J.C., Buendia, Fernando, Heredia-Barbero, Alejandro, Garzon, Ignacio L.
Publicada:
1 ene 2022
Resumen:
Cysteine-protected metal nanoparticles (NPs) have shown interesting physicochemical properties of potential utility in biomedical applications and in the understanding of protein folding. Herein, cysteine interaction with gold, silver, and copper NPs is characterized by Raman spectroscopy and density functional theory calculations to elucidate the molecular conformation and adsorption sites for each metal. The experimental analysis of Raman spectra upon adsorption with respect to free cysteine indicates that while the C-S bond and carboxyl group are similarly affected by adsorption on the three metal NPs, the amino group is sterically influenced by the electronegativity of each metal, causing a greater modification in the case of gold NPs. A theoretical approach that takes into consideration intermolecular interactions using two cysteine molecules is proposed using a S-metal-S interface motif anchored to the metal surface. These interactions generate the stabilization of an organo-metallic complex that combines gauche (PH) and anti (PC) rotameric conformers of cysteine on the surface of all three metals. Similarities between the calculated Raman spectra and experimental data confirm the thiol and carboxyl as adsorption groups for gold, silver, and copper NPs and suggest the formation of monomeric "staple motifs" that have been found in the protecting monolayer of atomic-precise thiolate-capped metal nanoclusters. © 2022 American Chemical Society. All rights reserved.
Filiaciones:
Rodriguez-Zamora, Penelope:
Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Mexico City, 04510, Mexico
Cordero-Silis, Cedric A.:
Instituto de Física, Universidad Nacional Autónoma de México, Mexico City, 04510, Mexico
Fabila, Jorge:
Instituto de Física, Universidad Nacional Autónoma de México, Mexico City, 04510, Mexico
Luque-Ceballos J.C.:
Instituto de Física, Universidad Nacional Autónoma de México, Mexico City, 04510, Mexico
Buendia, Fernando:
Instituto de Física, Universidad Nacional Autónoma de México, Mexico City, 04510, Mexico
Department of Chemical and Biomolecular Engineering, Faculty of Engineering, National University of Singapore, 10 Kent Ridge Crescent, Singapore, 119260, Singapore
Heredia-Barbero, Alejandro:
Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Mexico City, 04510, Mexico
Garzon, Ignacio L.:
Instituto de Física, Universidad Nacional Autónoma de México, Mexico City, 04510, Mexico
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