Photosensitized splitting of cis-syn 1,3-dimethyluracil dimer by tryptophan and its peptides

Photosensitized splitting of cis-syn 1,3-dimethyluracil dimer by tryptophan (Trp) and its peptides (Trp-Tyr and Trp-Phe) is studied by fluorescence quenching experiments and irradiation experiments.It reveals that 1,3-dimethyluracil dimer is mainly split by e?-?aq resulting from two-photon ionization of Trp and its peptides under irradiation with light (λ>290 nm).Moreover,the excited singlet state of Trp and its peptides can transfer an electron to the dimer,which splits and gives two pyrimidines.In addition,because of its lower oxidative potential,the excited triplet state of Trp-Tyr can also split the dimer via transfering an electron to the dimer.     

Stereo- and regio-selectivity in the photosensitized dimerization of 1, 3-dimethylthymine in solution

The effects of reaction pathway and temperature on stereo- and regio-selectivity of photocycloaddition of 1, 3-dimethylthymine (DMT) which gives four cyclobutane type dimers in solution using acetone as the photosensitizer, are investigated by measuring the product distribution. It is demonstrated that the ground-state aggregation between DMT molecules mainly leads to (h-t)dimers, and the diffusion-controlled triplet dimerization is favorable to the formation of (h-h) dimers.     

环丁烷与氟化氢形成氢键络合物的从头算研究

用ab initio能量梯度法(HF/3-21G水平)优化了环丁烷、氟化氢及它们之间的1:1氢键络合物的平衡几何构型,发现这种络合物具有C_(2v)对称性,氰化氢分子中氢原子与环丁烷四元环一边的中点形成氢键,并相距2.199(?).HF/3-21G给出该络合物的稳定化能为7.1kJ/mol,属于较弱的氢键。此外,从能量分解所得的各能量分量看,该络合物的稳定化能主要来自于静电作用和电荷迁移作用。     

DNA光复活过程电子转移机理的脉冲辐解研究

采用脉冲辐解瞬态吸收光谱法研究了水溶液中水合电子引发cis-syn型1,3-二甲基尿嘧啶环丁烷型二聚体(DMUD)裂解,生成嘧啶单体和嘧啶阴离子自由基,以及在维生素K3存在下,嘧啶阴离子自由基和VK3之间的电子转移反应过程,测定了电子转移反应的速率常数.当没有VK3作为电子受体时, 嘧啶阴离子自由基能继续和DMUD进行链反应.