Tuning the Photoinduced Electron-Transfer Thermodynamics in 1,3,5-Triaryl-2-pyrazoline Fluorophores: X-ray Structures, Photophysical Characterization, Computational Analysis, and in Vivo Evaluation
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- 作者：Christoph J. Fahrni ; Liuchun Yang ; and Donald G. VanDerveer
- 刊名：Journal of the American Chemical Society
- 出版年：2003
- 出版时间：April 2, 2003
- 年：2003
- 卷：125
- 期：13
- 页码：3799 - 3812
- 全文大小：639K
- 年卷期：v.125,no.13(April 2, 2003)
- ISSN：1520-5126
文摘
A series of donor-substituted 1,3,5-triaryl-2-pyrazoline fluorophores were structurally characterizedby X-ray analysis, and their photophysical properties studied by steady-state absorption and emissionspectroscopy. The photoinduced electron-transfer thermodynamics of the derivatives was estimated onthe basis of the spectroscopic data and redox potentials of the fluorophores. The aryl substituents in the1- and 3-position of the pyrazoline ring influence the photophysical properties of the fluorophores in distinctlydifferent ways. The excited-state equilibrium energy 
E00 is primarily influenced by changes of the substituentin the 1-position, whereas the reduction potential of the fluorophore is essentially determined by the 3-arylgroup. Density functional calculations were used to probe the electronic structure and energy ordering ofthe emissive and the electron-transfer state. The results from the computational analysis agree qualitativelywell with the experimental data. In addition, we have evaluated a water soluble pyrazoline derivative invivo as a potential intracellular pH probe. Membrane permeability, low toxicity, and high quantum yieldrender the fluorophore attractive for biological applications.
E00 is primarily influenced by changes of the substituentin the 1-position, whereas the reduction potential of the fluorophore is essentially determined by the 3-arylgroup. Density functional calculations were used to probe the electronic structure and energy ordering ofthe emissive and the electron-transfer state. The results from the computational analysis agree qualitativelywell with the experimental data. In addition, we have evaluated a water soluble pyrazoline derivative invivo as a potential intracellular pH probe. Membrane permeability, low toxicity, and high quantum yieldrender the fluorophore attractive for biological applications.