山西师范大学 化学与材料科学学院,山西 太原 030006
温晓烨,博士,副教授,研究方向:聚集诱导功能发光材料的设计,E-mail:wenxiaoye84@163.com
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刘芙蓉,闫丽,范哲锋等.基于激发态分子内质子转移的新型聚集诱导荧光探针用于硫化氢的检测及细胞成像[J].分析测试学报,2022,41(05):701-709.
LIU Fu-rong,YAN Li,FAN Zhe-feng,et al.Monitoring and Cell Imaging of H2S Using an Aggregation Induced Fluorescence Probe Based on Excited Intramolecular Proton Transfer[J].Journal of Instrumental Analysis,2022,41(05):701-709.
刘芙蓉,闫丽,范哲锋等.基于激发态分子内质子转移的新型聚集诱导荧光探针用于硫化氢的检测及细胞成像[J].分析测试学报,2022,41(05):701-709. DOI: 10.19969/j.fxcsxb.21092805.
LIU Fu-rong,YAN Li,FAN Zhe-feng,et al.Monitoring and Cell Imaging of H2S Using an Aggregation Induced Fluorescence Probe Based on Excited Intramolecular Proton Transfer[J].Journal of Instrumental Analysis,2022,41(05):701-709. DOI: 10.19969/j.fxcsxb.21092805.
该文使用4-乙酰氨基苯甲醛和碳酸肼一步法合成了一种具有聚集诱导荧光(AIE)特性的高效新型荧光探针1。通过荧光发射光谱、紫外光谱、粒度粒径分析、扫描电子显微镜和DFT理论计算讨论了探针1的AIE特性,证明了探针的发光机理是激发态分子内质子转移(ESIPT)效应。探针1在DMSO-H,2,O(1∶9,体积比),pH 7.4(PBS,0.2 mol/L)体系中可定量检测0~25 µmol/L范围内的H,2,S,检出限为0.27 µmol/L。此外,探针1不仅成功用于实际样品中H,2,S的检测,还可应用于活HeLa细胞中外源性H,2,S的荧光成像。并将其用于构建超灵敏逻辑门。利用探针1制备的简单便携经济的检测试纸,能够实时有效地视觉检测H,2,S。该研究有望为各种生理过程和食品样品中H,2,S的检测提供可靠有效的新思路与新方法。
As one endogenous gas in organisms,abnormal H,2,S is critically involved in various diseases and pathology research.Hence,high-sensitivity and high-selectivity methods for real-time monitoring of H,2,S molecule level ,in vivo, are significantly demanded.In this paper,given the excellent performances of aggregation and enhanced fluorescence,aggregation-induced emission(AIE) fluorescence molecular in the field of biological imaging,a high-efficiency and novel probe 1 based AIE was synthesized via one-step method with 4-acetamidobenzaldehyde and carbohydrazide.The AIE characteristic,luminescence mechanism and sensing mechanism of the probe 1 were discussed by emission spectrum,ultraviolet spectrum,particle size molecules analysis,scanning electron microscopy and theoretical calculation.The AIE properties of the probe may be attributed to the effects of excited-state intramolecular proton transfer(ESIPT) and restricted intramolecular rotation(RIR).Given the“alcohol-ketone”tautomerism,the probe molecule mainly exists in the keto form mediated by intramolecular hydrogen bonding between hydroxyl and carbonyl groups in water medium—a poor solvent,which indicates that the ESIPT process is activated.Meanwhile,the intramolecular single bond rotation is hindered and the molecular planarity is enhanced due to the orderly alignment between molecules.These two features both facilitate the radiative pathway,thus resulting in remarkable green-emissive.On the other hand,the probe 1 with Schiff base structure can specififically bind with Cu,2+,.The fluorescence of the probe would be essentially quenched due to the blocked ESIPT.When the probe 1 with Cu,2+, is exposed to HS,-,,the green-emissive could be restored based on the strong binding of HS,-, and Cu,2+,.Herein,a fast and sensitive“turn-on”H,2,S fluorescent probe was successfully designed.Probe 1 + Cu,2+, features a high selectivity towards H,2,S,after adding HS,-, to probe 1 + Cu,2+,,the fluorescence intensity at 500 nm gradually increases within 30 s and tends to stable.The detection limit of the probe 1 over H,2,S in containing 10% DMSO solution(PBS buffer,pH 7.4) was 0.27 µmol/L.The outstanding optical properties and biocompatibility made the probe 1 applicable to detecting exogenous H,2,S concentration in cells and H,2,S concentration in liquors.The applicability of probe 1 in detecting H,2,S in liquids,living cells and logic gate programs was further evaluated.The evaluation results showed that the probe is suitable for detecting the concentration of H,2,S in wine samples,and the probe has very low toxicity.Successfully applied to biofluorescence imaging of exogenous H,2,S in living cells.In addition,probe 1 was also used to construct an ultra-sensitive logic gate.Importantly,qualitative H,2,S detection was realized by using commercial filter paper.This research provides a new clue for exploring the functions of H,2,S in various physiological processes and food samples.
硫化氢激发态分子内质子转移聚集诱导荧光(AIE)食品样品细胞成像
H2Sexcited-state intramolecular proton transfer (ESIPT)aggregation-induced emission (AIE)food samplescell imaging
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