Theoretical investigation of naphthodithiophene diimide derivatives as fluorescent sensors for 2,4,6-trinitrophenol detection

IF 2.1 4区化学 Q4 BIOCHEMISTRY & MOLECULAR BIOLOGY

Journal of Molecular Modeling Pub Date : 2025-04-29 DOI:10.1007/s00894-025-06366-z

Leixing Luo, Mingxuan Dang, Xiaoming Song, Qingxia Zhao, Shuo Yang, Xiufang Hou, Shuai Liu, Yixia Ren

{"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}

引用次数: 0

Abstract

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 δ_g^inter 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.

Graphical Abstract

查看原文本刊更多论文

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

本研究探讨了N，N ' -二甲基萘二噻吩二亚胺（C1-NDTI-S）及其衍生物（C1-NDFI-O和C1-NDPI-N）的几何结构、芳构性、静电电位和荧光传感能力，其中噻吩环分别被呋喃和吡咯取代。理论计算表明，C1-NDTI-S对2,4,6-三硝基苯酚（TNP）具有最大的负吸附能，其电子吸收光谱和荧光光谱在TNP吸附后明显下降。通过FMO、空穴-电子、独立梯度模型和能量分解分析，揭示了荧光猝灭的本质是分子间弱π -π相互作用驱动光致电子转移。此外，通过修饰C1-NDTI-S结构产生的C1-NDFI-O和C1-NDPI-N有可能作为更有效的TNP检测荧光传感器。荧光恢复次数证实了这三种化合物作为荧光探针的适用性。方法采用B3LYP-D3(BJ)/ 6-311 + + G**水平的Gaussian 09软件包对其结构、能量和荧光恢复时间进行优化。采用Multiwfn结合VMD软件包，利用LOL-π和HOMA分析化合物的芳构性，重点研究噻吩被不同环取代后芳构性的差异。利用AMBER力场进行基于力场（EDA-FF）的能量分解分析，对弱分子间相互作用组分进行分解。基于Hirshfeld配分分析的独立梯度模型分析清晰地展示了分子间的π -π相互作用，δginter参数设置为0.005 a.u。电子吸收谱、电荷转移谱谱、分子相互作用、空穴电子相互作用均借助Multifwn软件完成。图形抽象

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Journal of Molecular Modeling 化学-化学综合

CiteScore

3.50

自引率

4.50%

发文量

362

审稿时长

2.9 months

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.