{"title":"二噻吩二亚胺衍生物作为2,4,6-三硝基苯酚荧光传感器的理论研究","authors":"Leixing Luo, Mingxuan Dang, Xiaoming Song, Qingxia Zhao, Shuo Yang, Xiufang Hou, Shuai Liu, Yixia Ren","doi":"10.1007/s00894-025-06366-z","DOIUrl":null,"url":null,"abstract":"<div><h3>Context</h3><p>This study explored the geometry, aromaticity, electrostatic potential, and fluorescence sensing capability of N,N′-dimethyl naphthodithiophene diimide (C<sub>1</sub>-NDTI-S) and its derivatives (C<sub>1</sub>-NDFI-O and C<sub>1</sub>-NDPI-N), where thiophene rings were substituted with furan and pyrrole, respectively. Theoretical calculations revealed that C<sub>1</sub>-NDTI-S had the most negative adsorption energy for 2,4,6-trinitrophenol (TNP), and its electronic absorption spectrum and fluorescence spectrum decreased considerably upon TNP adsorption. Through FMO, hole–electron, independent gradient model, and energy decomposition analysis, it was revealed that the essence of fluorescence quenching is the intermolecular weak π–π interaction driving photo-induced electron transfer. Furthermore, C<sub>1</sub>-NDFI-O and C<sub>1</sub>-NDPI-N generated by modifying the structure of C<sub>1</sub>-NDTI-S have the potential to serve as more efficient fluorescent sensors for TNP detection. The fluorescence recovery times confirmed the suitability of the three compounds as fluorescence probes.</p><h3>Methods</h3><p>In this study, the Gaussian 09 software package at B3LYP-D3(BJ)/6–311 + + G** level was applied to optimize the structure, energy, and fluorescence recovery time. Multiwfn combined with VMD software package was used to analyze the aromaticity of compounds using LOL-π and HOMA, with a focus on the differences in aromaticity after thiophene was substituted with different rings. Using AMBER force field for energy decomposition analysis based on force field (EDA-FF), the weak intermolecular interaction components are decomposed. The independent gradient model analysis based on Hirshfeld partition analysis clearly demonstrates the π–π interactions between molecules, with the δ<sub>g</sub><sup>inter</sup> parameter set to 0.005 a.u. Electron absorption spectroscopy, charge-transfer spectra spectroscopy, molecular interactions, and hole electron interactions were all completed with the help of Multifwn software.</p><h3>Graphical Abstract</h3>\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":651,"journal":{"name":"Journal of Molecular Modeling","volume":"31 5","pages":""},"PeriodicalIF":2.1000,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Theoretical investigation of naphthodithiophene diimide derivatives as fluorescent sensors for 2,4,6-trinitrophenol detection\",\"authors\":\"Leixing Luo, Mingxuan Dang, Xiaoming Song, Qingxia Zhao, Shuo Yang, Xiufang Hou, Shuai Liu, Yixia Ren\",\"doi\":\"10.1007/s00894-025-06366-z\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><h3>Context</h3><p>This study explored the geometry, aromaticity, electrostatic potential, and fluorescence sensing capability of N,N′-dimethyl naphthodithiophene diimide (C<sub>1</sub>-NDTI-S) and its derivatives (C<sub>1</sub>-NDFI-O and C<sub>1</sub>-NDPI-N), where thiophene rings were substituted with furan and pyrrole, respectively. Theoretical calculations revealed that C<sub>1</sub>-NDTI-S had the most negative adsorption energy for 2,4,6-trinitrophenol (TNP), and its electronic absorption spectrum and fluorescence spectrum decreased considerably upon TNP adsorption. Through FMO, hole–electron, independent gradient model, and energy decomposition analysis, it was revealed that the essence of fluorescence quenching is the intermolecular weak π–π interaction driving photo-induced electron transfer. Furthermore, C<sub>1</sub>-NDFI-O and C<sub>1</sub>-NDPI-N generated by modifying the structure of C<sub>1</sub>-NDTI-S have the potential to serve as more efficient fluorescent sensors for TNP detection. The fluorescence recovery times confirmed the suitability of the three compounds as fluorescence probes.</p><h3>Methods</h3><p>In this study, the Gaussian 09 software package at B3LYP-D3(BJ)/6–311 + + G** level was applied to optimize the structure, energy, and fluorescence recovery time. Multiwfn combined with VMD software package was used to analyze the aromaticity of compounds using LOL-π and HOMA, with a focus on the differences in aromaticity after thiophene was substituted with different rings. Using AMBER force field for energy decomposition analysis based on force field (EDA-FF), the weak intermolecular interaction components are decomposed. The independent gradient model analysis based on Hirshfeld partition analysis clearly demonstrates the π–π interactions between molecules, with the δ<sub>g</sub><sup>inter</sup> parameter set to 0.005 a.u. Electron absorption spectroscopy, charge-transfer spectra spectroscopy, molecular interactions, and hole electron interactions were all completed with the help of Multifwn software.</p><h3>Graphical Abstract</h3>\\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>\",\"PeriodicalId\":651,\"journal\":{\"name\":\"Journal of Molecular Modeling\",\"volume\":\"31 5\",\"pages\":\"\"},\"PeriodicalIF\":2.1000,\"publicationDate\":\"2025-04-29\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Molecular Modeling\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s00894-025-06366-z\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"BIOCHEMISTRY & MOLECULAR BIOLOGY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Molecular Modeling","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s00894-025-06366-z","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"BIOCHEMISTRY & MOLECULAR BIOLOGY","Score":null,"Total":0}
Theoretical investigation of naphthodithiophene diimide derivatives as fluorescent sensors for 2,4,6-trinitrophenol detection
Context
This study explored the geometry, aromaticity, electrostatic potential, and fluorescence sensing capability of N,N′-dimethyl naphthodithiophene diimide (C1-NDTI-S) and its derivatives (C1-NDFI-O and C1-NDPI-N), where thiophene rings were substituted with furan and pyrrole, respectively. Theoretical calculations revealed that C1-NDTI-S had the most negative adsorption energy for 2,4,6-trinitrophenol (TNP), and its electronic absorption spectrum and fluorescence spectrum decreased considerably upon TNP adsorption. Through FMO, hole–electron, independent gradient model, and energy decomposition analysis, it was revealed that the essence of fluorescence quenching is the intermolecular weak π–π interaction driving photo-induced electron transfer. Furthermore, C1-NDFI-O and C1-NDPI-N generated by modifying the structure of C1-NDTI-S have the potential to serve as more efficient fluorescent sensors for TNP detection. The fluorescence recovery times confirmed the suitability of the three compounds as fluorescence probes.
Methods
In this study, the Gaussian 09 software package at B3LYP-D3(BJ)/6–311 + + G** level was applied to optimize the structure, energy, and fluorescence recovery time. Multiwfn combined with VMD software package was used to analyze the aromaticity of compounds using LOL-π and HOMA, with a focus on the differences in aromaticity after thiophene was substituted with different rings. Using AMBER force field for energy decomposition analysis based on force field (EDA-FF), the weak intermolecular interaction components are decomposed. The independent gradient model analysis based on Hirshfeld partition analysis clearly demonstrates the π–π interactions between molecules, with the δginter parameter set to 0.005 a.u. Electron absorption spectroscopy, charge-transfer spectra spectroscopy, molecular interactions, and hole electron interactions were all completed with the help of Multifwn software.
期刊介绍：
The Journal of Molecular Modeling focuses on "hardcore" modeling, publishing high-quality research and reports. Founded in 1995 as a purely electronic journal, it has adapted its format to include a full-color print edition, and adjusted its aims and scope fit the fast-changing field of molecular modeling, with a particular focus on three-dimensional modeling.
Today, the journal covers all aspects of molecular modeling including life science modeling; materials modeling; new methods; and computational chemistry.
Topics include computer-aided molecular design; rational drug design, de novo ligand design, receptor modeling and docking; cheminformatics, data analysis, visualization and mining; computational medicinal chemistry; homology modeling; simulation of peptides, DNA and other biopolymers; quantitative structure-activity relationships (QSAR) and ADME-modeling; modeling of biological reaction mechanisms; and combined experimental and computational studies in which calculations play a major role.
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