调控氟硼荧染料构型动力学行为以提高荧光寿命成像性能  

Manipulating Conformational Dynamics of BODIPY to Improve Fluorescence Lifetime Imaging

作　　者：江琳 苗笑飞 吴姿姿 贾明轩 范曲立 胡文博 Jiang Lin;Miao Xiaofei;Wu Zizi;Jia Mingxuan;Fan Quli;Hu Wenbo(State Key Laboratory of Organic Electronics and Information Displays&Institute of Advanced Materials(IAM),Nanjing University of Posts&Telecommunications,Nanjing 210023,Jiangsu,China;Frontiers Science Center for Flexible Electronics,Xi’an Institute of Flexible Electronics(IFE),Northwestern Polytechnical University,Xi’an 710129,Shaanxi,China;Institute of Advanced Materials,Nanjing Tech University,Nanjing 210003,Jiangsu,China)

机构地区：[1]南京邮电大学材料科学与工程学院,有机电子与信息显示国家重点实验室,江苏南京210023 [2]西北工业大学柔性电子研究院,柔性电子前沿科学中心,陕西西安710129 [3]南京工业大学先进材料研究院,江苏南京210003

出　　处：《中国激光》2024年第21期196-204,共9页Chinese Journal of Lasers

基　　金：国家自然科学基金(62175201);宁波市自然科学基金重点项目(2021J043);西北工业大学中央高校建设经费项目;江苏省自然科学基金(BK20220404)。

摘　　要：荧光寿命成像(FLIM)技术基于时间分辨检测模式,能够有效消除组织自体荧光干扰,提升成像质量。氟硼荧染料以其优异的光学特性在荧光寿命成像领域极具应用潜力,但其在生物环境中的聚集猝灭效应限制了它的实际应用。本研究利用空间位阻策略设计合成了荧光染料MP-BDP。通过在氟硼荧染料的meso位引入具有大空间位阻的三甲基苯,同时实现了MP-BDP荧光寿命(4.3 ns vs 2.8 ns)和发光效率(76.7%vs 41.1%)的提升。并且,通过量子化学计算和飞秒瞬态吸收光谱进一步阐明了分子构型对染料发光激发态行为的影响,证明了大空间位阻不仅能够有效抑制构型相关的振动弛豫,提升发光性能,还能够抑制聚集诱导的发光猝灭,使氟硼荧染料在双光子活体荧光寿命成像方面表现出优异的性能。Objective Fluorescence lifetime imaging(FLIM)technology utilizes photoluminescence lifetime instead of intensity as a detection signal to effectively avoid autofluorescence interference from tissues,thereby providing enhanced imaging accuracy and comprehensive information regarding biochemical and cellular environments.The development of high-performance contrast agents is crucial for advancing FLIM technology.Currently,organic dye molecules are highly favored in FLIM owing to their tunable optical properties,good biocompatibility,and low synthesis costs.However,organic molecules tend to aggregate in biological environments,which renders it difficult to maintain a high fluorescence quantum yield and a long fluorescence lifetime,thus limiting their practical application.Therefore,high-performance dye molecules with satisfactory anti-quenching properties are urgently required to advance FLIM imaging in biomedical research.However,the rational molecular design of optimized fluorescence performance remains challenging owing to insufficient understanding regarding the excited-state dynamics within organic dye molecules.Excited-state dynamics is a critical aspect that correlates the dye molecule structure and macroscopic performance;thus,it determines the photophysical properties of the dye molecules.A comprehensive understanding and elucidation of the excited-state dynamics of dye molecules is crucial for guiding the design of high-performance fluorescent agents for FLIM applications.Methods Molecular steric hindrance was increased to optimize fluorescence performance.Nonetheless,comprehensive investigations into conformation-related excited-state dynamics allow one to elucidate the fundamental factors affecting fluorescence performance.Two boron-dipyrromethene(BODIPY)dyes with different steric hindrances were synthesized in this study.The core of classical BODIPY was decorated at the meso position with p-methylbenzene and trimethylbenzene to prepare P-BDP and MP-BDP,respectively.The optical properties of P-BDP and MP

关 键 词：位阻效应 氟硼荧染料 激发态动力学 双光子荧光寿命成像 

分 类 号：O644.1[理学—物理化学]