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Electrochemical SEIRAS Analysis of Imidazole-Ring-Functionalized Self-Assembled Monolayers
An essential amino acid, histidine, has a vital role in the secondary structure and catalytic activity of proteins because of the diverse interactions its side chain imidazole (Im) ring can take part in. Among these interactions, hydrogen donating and accepting bonding are often found to operate at...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9610120/ https://www.ncbi.nlm.nih.gov/pubmed/36295289 http://dx.doi.org/10.3390/ma15207221 |
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author | Pudžaitis, Vaidas Talaikis, Martynas Sadzevičienė, Rita Labanauskas, Linas Niaura, Gediminas |
author_facet | Pudžaitis, Vaidas Talaikis, Martynas Sadzevičienė, Rita Labanauskas, Linas Niaura, Gediminas |
author_sort | Pudžaitis, Vaidas |
collection | PubMed |
description | An essential amino acid, histidine, has a vital role in the secondary structure and catalytic activity of proteins because of the diverse interactions its side chain imidazole (Im) ring can take part in. Among these interactions, hydrogen donating and accepting bonding are often found to operate at the charged interfaces. However, despite the great biological significance, hydrogen-bond interactions are difficult to investigate at electrochemical interfaces due to the lack of appropriate experimental methods. Here, we present a surface-enhanced infrared absorption spectroscopy (SEIRAS) and density functional theory (DFT) study addressing this issue. To probe the hydrogen-bond interactions of the Im at the electrified organic layer/water interface, we constructed Au-adsorbed self-assembled monolayers (SAMs) that are functionalized with the Im group. As the prerequisite for spectroelectrochemical investigations, we first analyzed the formation of the monolayer and the relationship between the chemical composition of SAM and its structure. Infrared absorption markers that are sensitive to hydrogen-bonding interactions were identified. We found that negative electrode polarization effectively reduced hydrogen-bonding strength at the Im ring at the organic layer–water interface. The possible mechanism governing such a decrease in hydrogen-bonding interaction strength is discussed. |
format | Online Article Text |
id | pubmed-9610120 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-96101202022-10-28 Electrochemical SEIRAS Analysis of Imidazole-Ring-Functionalized Self-Assembled Monolayers Pudžaitis, Vaidas Talaikis, Martynas Sadzevičienė, Rita Labanauskas, Linas Niaura, Gediminas Materials (Basel) Article An essential amino acid, histidine, has a vital role in the secondary structure and catalytic activity of proteins because of the diverse interactions its side chain imidazole (Im) ring can take part in. Among these interactions, hydrogen donating and accepting bonding are often found to operate at the charged interfaces. However, despite the great biological significance, hydrogen-bond interactions are difficult to investigate at electrochemical interfaces due to the lack of appropriate experimental methods. Here, we present a surface-enhanced infrared absorption spectroscopy (SEIRAS) and density functional theory (DFT) study addressing this issue. To probe the hydrogen-bond interactions of the Im at the electrified organic layer/water interface, we constructed Au-adsorbed self-assembled monolayers (SAMs) that are functionalized with the Im group. As the prerequisite for spectroelectrochemical investigations, we first analyzed the formation of the monolayer and the relationship between the chemical composition of SAM and its structure. Infrared absorption markers that are sensitive to hydrogen-bonding interactions were identified. We found that negative electrode polarization effectively reduced hydrogen-bonding strength at the Im ring at the organic layer–water interface. The possible mechanism governing such a decrease in hydrogen-bonding interaction strength is discussed. MDPI 2022-10-17 /pmc/articles/PMC9610120/ /pubmed/36295289 http://dx.doi.org/10.3390/ma15207221 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Pudžaitis, Vaidas Talaikis, Martynas Sadzevičienė, Rita Labanauskas, Linas Niaura, Gediminas Electrochemical SEIRAS Analysis of Imidazole-Ring-Functionalized Self-Assembled Monolayers |
title | Electrochemical SEIRAS Analysis of Imidazole-Ring-Functionalized Self-Assembled Monolayers |
title_full | Electrochemical SEIRAS Analysis of Imidazole-Ring-Functionalized Self-Assembled Monolayers |
title_fullStr | Electrochemical SEIRAS Analysis of Imidazole-Ring-Functionalized Self-Assembled Monolayers |
title_full_unstemmed | Electrochemical SEIRAS Analysis of Imidazole-Ring-Functionalized Self-Assembled Monolayers |
title_short | Electrochemical SEIRAS Analysis of Imidazole-Ring-Functionalized Self-Assembled Monolayers |
title_sort | electrochemical seiras analysis of imidazole-ring-functionalized self-assembled monolayers |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9610120/ https://www.ncbi.nlm.nih.gov/pubmed/36295289 http://dx.doi.org/10.3390/ma15207221 |
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