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Paying Comprehensive Attention to the Temperature-Dependent Dual-Channel Excited-State Intramolecular Proton Transfer Mechanism of Fluorescence Ratio Probe BZ-DAM
The mechanism of fluorescence detection of diethyl chlorophosphate (DCP) based on 2-substituted benzothiazole (BZ-DAM) was studied by a theoretical calculation method. It should not be ignored that both the BZ-DAM and the detection product BZ-CHO have two excited-state intramolecular proton transfer...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10530469/ https://www.ncbi.nlm.nih.gov/pubmed/37762210 http://dx.doi.org/10.3390/ijms241813899 |
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author | Gao, Jiaan Zhang, Yifu Mu, Hongyan Yang, Min Guan, Xiaotong Jin, Guangyong Li, Hui |
author_facet | Gao, Jiaan Zhang, Yifu Mu, Hongyan Yang, Min Guan, Xiaotong Jin, Guangyong Li, Hui |
author_sort | Gao, Jiaan |
collection | PubMed |
description | The mechanism of fluorescence detection of diethyl chlorophosphate (DCP) based on 2-substituted benzothiazole (BZ-DAM) was studied by a theoretical calculation method. It should not be ignored that both the BZ-DAM and the detection product BZ-CHO have two excited-state intramolecular proton transfer (ESIPT) channels. Density functional theory (DFT) and time-dependent DFT (TDDFT) theory were used to study the photophysical mechanism of two compounds in two channels in (acetonitrile) ACN solvent, and the temperature dependence of the two channels was given. Channel 1 is more likely to exist at low temperatures and channel 2 is more likely to exist at high temperatures. By theoretical analysis of the constructed potential energy curve, the hydrogen bond energy and electron-hole analysis, we confirmed that both molecules undergo ESIPT and intramolecular charge transfer (ICT) processes in channel 1 and ESIPT and twisted intramolecular charge transfer (TICT) coupling processes in channel 2. The formation of product BZ-CHO molecules led to a significant fluorescence blue-shift phenomenon and inhibited the ICT process, which confirmed that BZ-DAM could be used as a fluorescence probe for fluorescence detection. We sincerely hope that this work will not only help to clarify the excited-state dynamics behavior of the BZ-DAM probe but also provide a new idea for designing and optimizing a new chemical dosimeter. |
format | Online Article Text |
id | pubmed-10530469 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-105304692023-09-28 Paying Comprehensive Attention to the Temperature-Dependent Dual-Channel Excited-State Intramolecular Proton Transfer Mechanism of Fluorescence Ratio Probe BZ-DAM Gao, Jiaan Zhang, Yifu Mu, Hongyan Yang, Min Guan, Xiaotong Jin, Guangyong Li, Hui Int J Mol Sci Article The mechanism of fluorescence detection of diethyl chlorophosphate (DCP) based on 2-substituted benzothiazole (BZ-DAM) was studied by a theoretical calculation method. It should not be ignored that both the BZ-DAM and the detection product BZ-CHO have two excited-state intramolecular proton transfer (ESIPT) channels. Density functional theory (DFT) and time-dependent DFT (TDDFT) theory were used to study the photophysical mechanism of two compounds in two channels in (acetonitrile) ACN solvent, and the temperature dependence of the two channels was given. Channel 1 is more likely to exist at low temperatures and channel 2 is more likely to exist at high temperatures. By theoretical analysis of the constructed potential energy curve, the hydrogen bond energy and electron-hole analysis, we confirmed that both molecules undergo ESIPT and intramolecular charge transfer (ICT) processes in channel 1 and ESIPT and twisted intramolecular charge transfer (TICT) coupling processes in channel 2. The formation of product BZ-CHO molecules led to a significant fluorescence blue-shift phenomenon and inhibited the ICT process, which confirmed that BZ-DAM could be used as a fluorescence probe for fluorescence detection. We sincerely hope that this work will not only help to clarify the excited-state dynamics behavior of the BZ-DAM probe but also provide a new idea for designing and optimizing a new chemical dosimeter. MDPI 2023-09-09 /pmc/articles/PMC10530469/ /pubmed/37762210 http://dx.doi.org/10.3390/ijms241813899 Text en © 2023 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 Gao, Jiaan Zhang, Yifu Mu, Hongyan Yang, Min Guan, Xiaotong Jin, Guangyong Li, Hui Paying Comprehensive Attention to the Temperature-Dependent Dual-Channel Excited-State Intramolecular Proton Transfer Mechanism of Fluorescence Ratio Probe BZ-DAM |
title | Paying Comprehensive Attention to the Temperature-Dependent Dual-Channel Excited-State Intramolecular Proton Transfer Mechanism of Fluorescence Ratio Probe BZ-DAM |
title_full | Paying Comprehensive Attention to the Temperature-Dependent Dual-Channel Excited-State Intramolecular Proton Transfer Mechanism of Fluorescence Ratio Probe BZ-DAM |
title_fullStr | Paying Comprehensive Attention to the Temperature-Dependent Dual-Channel Excited-State Intramolecular Proton Transfer Mechanism of Fluorescence Ratio Probe BZ-DAM |
title_full_unstemmed | Paying Comprehensive Attention to the Temperature-Dependent Dual-Channel Excited-State Intramolecular Proton Transfer Mechanism of Fluorescence Ratio Probe BZ-DAM |
title_short | Paying Comprehensive Attention to the Temperature-Dependent Dual-Channel Excited-State Intramolecular Proton Transfer Mechanism of Fluorescence Ratio Probe BZ-DAM |
title_sort | paying comprehensive attention to the temperature-dependent dual-channel excited-state intramolecular proton transfer mechanism of fluorescence ratio probe bz-dam |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10530469/ https://www.ncbi.nlm.nih.gov/pubmed/37762210 http://dx.doi.org/10.3390/ijms241813899 |
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