Enhanced Photoluminescence of the Bi-icosahedral Au25 Nanocluster Using an Anthracene-based Fluorophore
Fluorescent molecules have enabled single-molecule detection of toxins, biomarkers, and pollutants under controlled conditions. Unfortunately, these fluorophores are typically organic molecules that degrade or become photobleached when applied to non-ideal systems. Noble metal nanoclusters, in parti...
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Published in | Journal of cluster science Vol. 35; no. 7; pp. 2437 - 2444 |
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Main Authors | , , , , , , , |
Format | Journal Article |
Language | English |
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01.10.2024
Springer Nature B.V |
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Abstract | Fluorescent molecules have enabled single-molecule detection of toxins, biomarkers, and pollutants under controlled conditions. Unfortunately, these fluorophores are typically organic molecules that degrade or become photobleached when applied to non-ideal systems. Noble metal nanoclusters, in particular gold nanoclusters (AuNCs), pose a solution to the problems of degradation and photobleaching. Despite the low fluorescence quantum yield of AuNCs without thiolated ligands, labeling these clusters with fluorescent ligands allows enhancement of the fluorescence intensity and manipulation of the emission wavelength. In this work, we explore the labeling of the bi-icosahedron Au
25
(bi-Au
25
) nanocluster. The bi-Au
25
nanocluster has unique stability and electrochemical properties making it an attractive, yet poorly studied, candidate for fluorescent labeling. In order to demonstrate its potential as a near-IR emitting nanocluster we synthesized and labeled the bi-Au
25
with the novel fluorophore 6-(9-Anthryl)-5-hexyne-1-thiol, or simply anthracenethiol. Two common ligands used in the synthesis of bi-Au
25
are hexanethiol and phenylethanethiol, and we spectroscopically verify the ability for the straight-chain alkane hexanethiol to block the labeling of bi-Au
25
, while the aromatic phenylethanethiol enables the labeling of the complex. These products are characterized with square wave voltammetry, UV-vis and fluorescence spectrophotometry, and NMR spectrometry. The fluorescently labeled bi-Au
25
nanocluster demonstrates a 25x increase in NIR photoluminescence at ~ 810 nm when originally capped with phenylethanethiol, and not the long-chain alkanethiol. The quantum yield of this cluster has been improved from 0.0786% in the unlabeled cluster to 1.97% in the labeled product. |
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AbstractList | Fluorescent molecules have enabled single-molecule detection of toxins, biomarkers, and pollutants under controlled conditions. Unfortunately, these fluorophores are typically organic molecules that degrade or become photobleached when applied to non-ideal systems. Noble metal nanoclusters, in particular gold nanoclusters (AuNCs), pose a solution to the problems of degradation and photobleaching. Despite the low fluorescence quantum yield of AuNCs without thiolated ligands, labeling these clusters with fluorescent ligands allows enhancement of the fluorescence intensity and manipulation of the emission wavelength. In this work, we explore the labeling of the bi-icosahedron Au
25
(bi-Au
25
) nanocluster. The bi-Au
25
nanocluster has unique stability and electrochemical properties making it an attractive, yet poorly studied, candidate for fluorescent labeling. In order to demonstrate its potential as a near-IR emitting nanocluster we synthesized and labeled the bi-Au
25
with the novel fluorophore 6-(9-Anthryl)-5-hexyne-1-thiol, or simply anthracenethiol. Two common ligands used in the synthesis of bi-Au
25
are hexanethiol and phenylethanethiol, and we spectroscopically verify the ability for the straight-chain alkane hexanethiol to block the labeling of bi-Au
25
, while the aromatic phenylethanethiol enables the labeling of the complex. These products are characterized with square wave voltammetry, UV-vis and fluorescence spectrophotometry, and NMR spectrometry. The fluorescently labeled bi-Au
25
nanocluster demonstrates a 25x increase in NIR photoluminescence at ~ 810 nm when originally capped with phenylethanethiol, and not the long-chain alkanethiol. The quantum yield of this cluster has been improved from 0.0786% in the unlabeled cluster to 1.97% in the labeled product. Fluorescent molecules have enabled single-molecule detection of toxins, biomarkers, and pollutants under controlled conditions. Unfortunately, these fluorophores are typically organic molecules that degrade or become photobleached when applied to non-ideal systems. Noble metal nanoclusters, in particular gold nanoclusters (AuNCs), pose a solution to the problems of degradation and photobleaching. Despite the low fluorescence quantum yield of AuNCs without thiolated ligands, labeling these clusters with fluorescent ligands allows enhancement of the fluorescence intensity and manipulation of the emission wavelength. In this work, we explore the labeling of the bi-icosahedron Au25 (bi-Au25) nanocluster. The bi-Au25 nanocluster has unique stability and electrochemical properties making it an attractive, yet poorly studied, candidate for fluorescent labeling. In order to demonstrate its potential as a near-IR emitting nanocluster we synthesized and labeled the bi-Au25 with the novel fluorophore 6-(9-Anthryl)-5-hexyne-1-thiol, or simply anthracenethiol. Two common ligands used in the synthesis of bi-Au25 are hexanethiol and phenylethanethiol, and we spectroscopically verify the ability for the straight-chain alkane hexanethiol to block the labeling of bi-Au25, while the aromatic phenylethanethiol enables the labeling of the complex. These products are characterized with square wave voltammetry, UV-vis and fluorescence spectrophotometry, and NMR spectrometry. The fluorescently labeled bi-Au25 nanocluster demonstrates a 25x increase in NIR photoluminescence at ~ 810 nm when originally capped with phenylethanethiol, and not the long-chain alkanethiol. The quantum yield of this cluster has been improved from 0.0786% in the unlabeled cluster to 1.97% in the labeled product. |
Author | Reber, Keith Smith, Desmond Raufman, Benjamin Aligholizadeh, Dariush Stevens, Nathaniel Hondrogiannis, Nicole Qureshi, Zaid Shahzad Devadas, Mary Sajini |
Author_xml | – sequence: 1 givenname: Dariush surname: Aligholizadeh fullname: Aligholizadeh, Dariush organization: Department of Chemistry, Towson University – sequence: 2 givenname: Zaid Shahzad surname: Qureshi fullname: Qureshi, Zaid Shahzad organization: Department of Chemistry, Towson University – sequence: 3 givenname: Desmond surname: Smith fullname: Smith, Desmond organization: Department of Chemistry, Towson University – sequence: 4 givenname: Benjamin surname: Raufman fullname: Raufman, Benjamin organization: Department of Chemistry, Towson University – sequence: 5 givenname: Nathaniel surname: Stevens fullname: Stevens, Nathaniel organization: Department of Chemistry, Towson University – sequence: 6 givenname: Nicole surname: Hondrogiannis fullname: Hondrogiannis, Nicole organization: Department of Chemistry, Towson University – sequence: 7 givenname: Keith surname: Reber fullname: Reber, Keith organization: Department of Chemistry, Towson University – sequence: 8 givenname: Mary Sajini surname: Devadas fullname: Devadas, Mary Sajini email: mdevadas@towson.edu organization: Department of Chemistry, Towson University |
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Copyright_xml | – notice: The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2024. Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law. |
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Keywords | Fluorescence Nanocluster Anthracene Quantum yield Ligand Gold nanoparticle |
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Snippet | Fluorescent molecules have enabled single-molecule detection of toxins, biomarkers, and pollutants under controlled conditions. Unfortunately, these... |
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SubjectTerms | Alkanes Anthracene Biomarkers Catalysis Chemical compounds Chemistry Chemistry and Materials Science Clusters Electrochemical analysis Fluorescence Hydrochloric acid Icosahedrons Inorganic Chemistry Labeling Ligands Nanochemistry Nanoclusters Near infrared radiation NMR Noble metals Nuclear magnetic resonance Organic chemistry Original Paper Photoluminescence Physical Chemistry Spectrophotometry Square waves |
Title | Enhanced Photoluminescence of the Bi-icosahedral Au25 Nanocluster Using an Anthracene-based Fluorophore |
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