1,3,3,5,2′-五甲基螺吲哚啉萘并噁嗪的合成及时间分辨光谱

合成了标题化合物(Ⅰ),并用纳秒时间分辨吸收光谱技术研究了它的光致变色过程。Ⅰ的溶液用248nm激光脉冲激发后产生两种不同的有色体。其中短寿命的有色体(CT中间体)有两个吸收峰,在乙腈和环已烷中其峰值分别为440nm,640nm和450nm,640nm,寿命分别为12/μs和0.8μs。CT中间体的吸收峰的位置基本不受溶剂极性影响的事实说明其结构可能介于两性离子和醌式结构之间。在乙腈中,CT中间体有较长的寿命,这是5位甲基给电子效应的结果。长寿命的有色体(寿命》80μs)为平面结构的部花青(PMC),其吸收峰在乙腈和环已烷中分别出现于约640nm和600nm。     

DNA碱基激光光解的新颖瞬态产物

本文报道了利用纳秒级激光光解瞬态吸收光谱技术研究DNA碱基光解和光敏作用的结果:发现了胸腺嘧啶的一个新激发三重态和胸腺嘧啶羟基加合物自由基的生成;首次观察到胞嘧啶及其衍生物胞嘧啶核苷、脱氧胞嘧啶核苷酸的激发三重态光吸收谱;确证了鸟嘌呤核苷的激发三重态,其pK_a值为8.7;并研究了上述瞬态产物的动态演变过程,总结了其反应机理。     

Novel Transient Species of DNA Bases From Laser Photolysis

The laser photochemistry and photosensitization of DNA bases were carried out by using a nanosecond kinetic spectroscopy. A novel triplet state of thymine and its OH adduct were observed in N_2 and N_2O saturated aqueous solution respectively. The transient absorption spectra of triplet cytosine, cytidine and deoxycytidine monophosphoric acid were observed for the first time. Triplet guanosine was confirmed and its pK, value, 8.7, was obtained. Kinetic studies of the growth-decay of the above transient species were performed and their reaction mechanisms were elucidated in detail.