Theoretical Investigations on Electronic Structures and Absorption Spectra of Unsymmetrical Metal-coordinated Neo-confused Porphyrin in Various Solvents

Though the photo-physical properties of free base porphyrin are attractive, there are still problems for the materials with weak and narrow range absorption of visible light. The unsymmetrical neo-confused porphyrin derivatives were introduced as novel materials for the improvement of photo-chemical and photo-physical properties. The density function theory(DFT)and time dependent density function theory(TDDFT) were applied to calculate the absorption spectrum of unsymmetrical neo-confused porphyrin(N-CP) and metal-coordinated N-CP in various solutions. The Ni and Zn coordinated neo-confused porphyrin dipole moment values are smaller than the values of prototype porphyrin(Pro P) and N–CP. According to the electrophilicity index ω, Ni coordinated N–CP(Ni–N–CP) is susceptible to the polarity of solvents, while the Zn coordinated derivative(Zn–N–CP) is more immune to the solvent environment. Unlike the Gouterman's four frontier orbital model of common porphyrin materials, the electron transitions of N–CPs and metalcoordinated N–CPs from H–2 or lower molecular orbitals also contribute to ultraviolet and visible absorption. Most of oscillator strength f values of Zn–N–CP are significantly higher than the values of Ni–N–CP, which reflects the higher absorption intensity of Q and Soret bands. The maximum wavelength at 702.2 nm in vacuum drew our attention to the novel material. The broad absorption range, intense red-shifted Q band and higher stability in solvents suggest that N–CPs, especially Zn–N–CP, can be one class of new candidate dye-sensitized materials.     

基于光谱法研究盐酸胍诱导的人血红蛋白去折叠过程

借助于紫外-可见吸收光谱法、荧光光谱法以及停流-荧光光谱法研究了盐酸胍(GdmHcl)诱导人血红蛋白的去折叠过程。实验发现,盐酸胍诱导的血红蛋白去折叠有两个不同的过程,即随着GdmHcl浓度增加到1.0 mol·L-1左右时,血红蛋白亚基发生解聚,形成中间态;持续增加其浓度时,各亚基发生内部去折叠,最终导致血红素发生崩解。加入还原剂(β-巯基乙醇)对血红蛋白亚基解聚、血红素崩解有协同作用且直接引起亚基和全分子同步变构。血红蛋白去折叠过程从“三态模型”转变为“二态模型”。     

秋水仙碱与人血清白蛋白相互作用的谱学研究

采用紫外、荧光和圆二色光谱研究了秋水仙碱与人血清白蛋白之间的相互作用。结果发现秋水仙碱使人血清白蛋白的紫外吸收增强,特征荧光峰猝灭,并且随温度升高猝灭常数K_SV降低。求算了不同温度下秋水仙碱与人血清白蛋白相互作用的平衡常数与结合位点数。根据Van’t Hoff方程计算出ΔH=-11.66 kJ·mol-1,ΔS=51.507 J·(mol·K)-１,得出二者之间的作用力主要是静电作用力。圆二色光谱测得加入秋水仙碱后人血清白蛋白的α-螺旋降低,二级结构改变,表明秋水仙碱对人血清白蛋白的荧光猝灭机制属于形成配合物所引起的静态猝灭。