{"title":"Theoretical Investigations on the Sensing Mechanism of Dicyanoisophorone Fluorescent Probe for the Detection of Hydrogen Sulfide","authors":"Zhicheng Xia, Honghong Xu, Anran Huang, Wenxuan Hao, Dongxia Wu, Shibin Yin, Haixiang He","doi":"10.1007/s10895-024-03911-6","DOIUrl":null,"url":null,"abstract":"<p>As one of the biomolecules, hydrogen sulfide (H<sub>2</sub>S) has received a lot of attention. Recent studies have shown that endogenous hydrogen sulfide plays different roles in different organs in biological systems. Fluorescent probe technology has been widely adopted due to its many advantages such as low cost, simple operation, and high sensitivity. Among many probes, dicyanoisophorone fluorophore is often used in probe design for real-time detection of endogenous H<sub>2</sub>S due to the large Stokes shift and long fluorescence emission wavelength. In this paper, the fluorescence sensing mechanism of dicyanoisophorone-like probe L and its product 3 with near-infrared fluorescence emission has been theoretically investigated by using theory methods. The analysis of infrared (IR) vibration spectra and reduced density gradient (RDG) showed that the hydrogen bond of the enolic structure of product 3 was significantly enhanced in the S<sub>1</sub> state. The spectroscopic information revealed that the emission of NIR fluorescence originated from the keto structure of the product. Finally, potential energy curves and frontier molecular orbitals diagrams showed that the fluorescence quenching phenomenon of the probe L was attributed to the photoinduced electron transfer (PET) process, whereas the product 3 generated after the detection of H<sub>2</sub>S undergoes the excited state intramolecular proton transfer (ESIPT) process.</p>","PeriodicalId":15800,"journal":{"name":"Journal of Fluorescence","volume":null,"pages":null},"PeriodicalIF":2.6000,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Fluorescence","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1007/s10895-024-03911-6","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"BIOCHEMICAL RESEARCH METHODS","Score":null,"Total":0}
引用次数: 0
Abstract
As one of the biomolecules, hydrogen sulfide (H2S) has received a lot of attention. Recent studies have shown that endogenous hydrogen sulfide plays different roles in different organs in biological systems. Fluorescent probe technology has been widely adopted due to its many advantages such as low cost, simple operation, and high sensitivity. Among many probes, dicyanoisophorone fluorophore is often used in probe design for real-time detection of endogenous H2S due to the large Stokes shift and long fluorescence emission wavelength. In this paper, the fluorescence sensing mechanism of dicyanoisophorone-like probe L and its product 3 with near-infrared fluorescence emission has been theoretically investigated by using theory methods. The analysis of infrared (IR) vibration spectra and reduced density gradient (RDG) showed that the hydrogen bond of the enolic structure of product 3 was significantly enhanced in the S1 state. The spectroscopic information revealed that the emission of NIR fluorescence originated from the keto structure of the product. Finally, potential energy curves and frontier molecular orbitals diagrams showed that the fluorescence quenching phenomenon of the probe L was attributed to the photoinduced electron transfer (PET) process, whereas the product 3 generated after the detection of H2S undergoes the excited state intramolecular proton transfer (ESIPT) process.
期刊介绍:
Journal of Fluorescence is an international forum for the publication of peer-reviewed original articles that advance the practice of this established spectroscopic technique. Topics covered include advances in theory/and or data analysis, studies of the photophysics of aromatic molecules, solvent, and environmental effects, development of stationary or time-resolved measurements, advances in fluorescence microscopy, imaging, photobleaching/recovery measurements, and/or phosphorescence for studies of cell biology, chemical biology and the advanced uses of fluorescence in flow cytometry/analysis, immunology, high throughput screening/drug discovery, DNA sequencing/arrays, genomics and proteomics. Typical applications might include studies of macromolecular dynamics and conformation, intracellular chemistry, and gene expression. The journal also publishes papers that describe the synthesis and characterization of new fluorophores, particularly those displaying unique sensitivities and/or optical properties. In addition to original articles, the Journal also publishes reviews, rapid communications, short communications, letters to the editor, topical news articles, and technical and design notes.