Cargando…

Combined spectroscopic studies on post-functionalized Au(25) cluster as an ATR-FTIR sensor for cations

Recently, significant research activity has been devoted to thiolate-protected gold clusters due to their attractive optical and electronic properties. These properties as well as solubility and stability can be controlled by post-synthetic modification strategies. Herein, the ligand exchange reacti...

Descripción completa

Detalles Bibliográficos
Autores principales: Baghdasaryan, Ani, Brun, Elodie, Wang, Yuming, Salassa, Giovanni, Lacour, Jérôme, Bürgi, Thomas
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8171333/
https://www.ncbi.nlm.nih.gov/pubmed/34163832
http://dx.doi.org/10.1039/d1sc01654g
_version_ 1783702407900823552
author Baghdasaryan, Ani
Brun, Elodie
Wang, Yuming
Salassa, Giovanni
Lacour, Jérôme
Bürgi, Thomas
author_facet Baghdasaryan, Ani
Brun, Elodie
Wang, Yuming
Salassa, Giovanni
Lacour, Jérôme
Bürgi, Thomas
author_sort Baghdasaryan, Ani
collection PubMed
description Recently, significant research activity has been devoted to thiolate-protected gold clusters due to their attractive optical and electronic properties. These properties as well as solubility and stability can be controlled by post-synthetic modification strategies. Herein, the ligand exchange reaction between Au(25)(2-PET)(18) cluster (where 2-PET is 2-phenylethanethiol) and di-thiolated crown ether (t-CE) ligands bearing two chromophores was studied. The post-functionalization aimed to endow the cluster with ion binding properties. The exchange reaction was followed in situ by UV-vis, (1)H NMR and HPLC. MALDI mass analysis revealed the incorporation of up to 5 t-CE ligands into the ligand shell. Once functionalized MALDI furthermore showed complexation of sodium ions to the cluster. ATR-FTIR spectroscopic studies using aqueous solutions of K(+), Ba(2+), Gd(3+) and Eu(3+) showed noticeable spectral shifts of the C–O stretching band around 1100 cm(−1) upon complexation. Further spectral changes point towards a conformational change of the two chromophores that are attached to the crown ether. Density functional theory calculations indicate that the di-thiol ligand bridges two staple units on the cluster. The calculations furthermore reproduce the spectral shift of the C–O stretching vibrations upon complex formation and reveal a conformational change that involves the two chromophores attached to the crown ether. The functionalized clusters have therefore attractive ion sensing properties due to the combination of binding properties, mainly due to the crown ether, and the possibility for signal transduction via an induced conformational change involving chromophore units.
format Online
Article
Text
id pubmed-8171333
institution National Center for Biotechnology Information
language English
publishDate 2021
publisher The Royal Society of Chemistry
record_format MEDLINE/PubMed
spelling pubmed-81713332021-06-22 Combined spectroscopic studies on post-functionalized Au(25) cluster as an ATR-FTIR sensor for cations Baghdasaryan, Ani Brun, Elodie Wang, Yuming Salassa, Giovanni Lacour, Jérôme Bürgi, Thomas Chem Sci Chemistry Recently, significant research activity has been devoted to thiolate-protected gold clusters due to their attractive optical and electronic properties. These properties as well as solubility and stability can be controlled by post-synthetic modification strategies. Herein, the ligand exchange reaction between Au(25)(2-PET)(18) cluster (where 2-PET is 2-phenylethanethiol) and di-thiolated crown ether (t-CE) ligands bearing two chromophores was studied. The post-functionalization aimed to endow the cluster with ion binding properties. The exchange reaction was followed in situ by UV-vis, (1)H NMR and HPLC. MALDI mass analysis revealed the incorporation of up to 5 t-CE ligands into the ligand shell. Once functionalized MALDI furthermore showed complexation of sodium ions to the cluster. ATR-FTIR spectroscopic studies using aqueous solutions of K(+), Ba(2+), Gd(3+) and Eu(3+) showed noticeable spectral shifts of the C–O stretching band around 1100 cm(−1) upon complexation. Further spectral changes point towards a conformational change of the two chromophores that are attached to the crown ether. Density functional theory calculations indicate that the di-thiol ligand bridges two staple units on the cluster. The calculations furthermore reproduce the spectral shift of the C–O stretching vibrations upon complex formation and reveal a conformational change that involves the two chromophores attached to the crown ether. The functionalized clusters have therefore attractive ion sensing properties due to the combination of binding properties, mainly due to the crown ether, and the possibility for signal transduction via an induced conformational change involving chromophore units. The Royal Society of Chemistry 2021-04-20 /pmc/articles/PMC8171333/ /pubmed/34163832 http://dx.doi.org/10.1039/d1sc01654g Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Baghdasaryan, Ani
Brun, Elodie
Wang, Yuming
Salassa, Giovanni
Lacour, Jérôme
Bürgi, Thomas
Combined spectroscopic studies on post-functionalized Au(25) cluster as an ATR-FTIR sensor for cations
title Combined spectroscopic studies on post-functionalized Au(25) cluster as an ATR-FTIR sensor for cations
title_full Combined spectroscopic studies on post-functionalized Au(25) cluster as an ATR-FTIR sensor for cations
title_fullStr Combined spectroscopic studies on post-functionalized Au(25) cluster as an ATR-FTIR sensor for cations
title_full_unstemmed Combined spectroscopic studies on post-functionalized Au(25) cluster as an ATR-FTIR sensor for cations
title_short Combined spectroscopic studies on post-functionalized Au(25) cluster as an ATR-FTIR sensor for cations
title_sort combined spectroscopic studies on post-functionalized au(25) cluster as an atr-ftir sensor for cations
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8171333/
https://www.ncbi.nlm.nih.gov/pubmed/34163832
http://dx.doi.org/10.1039/d1sc01654g
work_keys_str_mv AT baghdasaryanani combinedspectroscopicstudiesonpostfunctionalizedau25clusterasanatrftirsensorforcations
AT brunelodie combinedspectroscopicstudiesonpostfunctionalizedau25clusterasanatrftirsensorforcations
AT wangyuming combinedspectroscopicstudiesonpostfunctionalizedau25clusterasanatrftirsensorforcations
AT salassagiovanni combinedspectroscopicstudiesonpostfunctionalizedau25clusterasanatrftirsensorforcations
AT lacourjerome combinedspectroscopicstudiesonpostfunctionalizedau25clusterasanatrftirsensorforcations
AT burgithomas combinedspectroscopicstudiesonpostfunctionalizedau25clusterasanatrftirsensorforcations