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Environment-sensitive fluorophores with benzothiadiazole and benzoselenadiazole structures as candidate components of a fluorescent polymeric thermometer

机译:具有苯并噻二唑和苯并硒二唑结构作为荧光聚合物温度计候选组分的环境敏感型荧光团

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An environment-sensitive fluorophore can change its maximum emission wavelength (λ _(em)), fluorescence quantum yield (φ _f), and fluorescence lifetime in response to the surrounding environment. We have developed two new intramolecular charge-transfer-type environment-sensitive fluorophores, DBThD-IA and DBSeD-IA, in which the oxygen atom of a well-established 2,1,3-benzoxadiazole environment-sensitive fluorophore, DBD-IA, has been replaced by a sulfur and selenium atom, respectively. DBThD-IA is highly fluorescent in n-hexane (φ _f=0. 81, λ _(em)=537 nm) with excitation at 449 nm, but is almost nonfluorescent in water (φ _f=0.037, λ _(em)=616 nm), similarly to DBD-IA (φ _f=0.91, λ _(em)=520 nm in n-hexane; φ _f=0.027, λ _(em)=616 nm in water). A similar variation in fluorescence properties was also observed for DBSeD-IA (φ _f=0.24, λ _(em)=591 nm in n-hexane; φ _f=0.0046, λ _(em)=672 nm in water). An intensive study of the solvent effects on the fluorescence properties of these fluorophores revealed that both the polarity of the environment and hydrogen bonding with solvent molecules accelerate the nonradiative relaxation of the excited fluorophores. Time-resolved optoacoustic and phosphorescence measurements clarified that both intersystem crossing and internal conversion are involved in the nonradiative relaxation processes of DBThD-IA and DBSeD-IA. In addition, DBThD-IA exhibits a 10-fold higher photostability in aqueous solution than the original fluorophore DBD-IA, which allowed us to create a new robust molecular nanogel thermometer for intracellular thermometry. Sensitive fluorophores: Two new environment-sensitive fluorophores, DBThD-IA and DBSeD-IA (see figure), are reported. Their photophysical and photochemical properties have been investigated by UV/Vis absorption, fluorescence, and phosphorescence spectroscopy, analysis of the fluorescence lifetimes and optoacoustic signals, and by performing photolysis experiments. DBThD-IA has successfully been used to develop a photostable fluorescent nanogel thermometer.
机译:对环境敏感的荧光团可以响应于周围环境而改变其最大发射波长(λ_(em)),荧光量子产率(φ_f)和荧光寿命。我们开发了两种新的分子内电荷转移型环境敏感荧光团DBThD-IA和DBSeD-IA,其中成熟的2,1,3-苯并恶二唑环境敏感荧光团DBD-IA的氧原子分别被硫和硒原子取代。 DBThD-IA在正己烷中(Φ_f = 0。81,λ_(em)= 537 nm)在449 nm激发下具有高荧光性,但在水中几乎无荧光(Φ_f = 0.037,λ_(em) = 616nm),类似于DBD-IA(在正己烷中φ_f= 0.91,λ_(em)= 520nm;在水中φ_f= 0.027,λ_(em)= 616nm)。对于DBSeD-IA也观察到相似的荧光性质变化(在正己烷中,φ_f= 0.24,λ_(em)= 591nm;在水中,φ_f= 0.0046,λ_(em)= 672nm)。对溶剂对这些荧光团的荧光特性的深入研究表明,环境的极性以及与溶剂分子的氢键都加速了激发荧光团的非辐射弛豫。时间分辨的光声和磷光测量结果表明,DBThD-IA和DBSeD-IA的非辐射弛豫过程涉及系统间交叉和内部转换。此外,DBThD-IA在水溶液中的光稳定性比原始荧光团DBD-IA高10倍,这使我们能够创建一种用于细胞内测温的新型坚固的分子纳米凝胶温度计。敏感荧光团:报道了两种新的环境敏感荧光团,DBThD-IA和DBSeD-IA(见图)。通过紫外/可见吸收,荧光和磷光光谱,荧光寿命和光声信号分析以及进行光解实验研究了它们的光物理和光化学性质。 DBThD-IA已成功用于开发光稳定的荧光纳米凝胶温度计。

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