CAJ | 학술논문

用自制的高时间分辨电子自旋共振波谱仪,测量得到了酸性、碱性和胶束环境下的光解杜醌/乙二醇(DQ/EG)溶液瞬态自由基的化学诱导动态电子自旋极化(CIDEP)谱.在光解均相DQ/EG溶液时,观察到了以增强发射的的中性杜半醌自由基(DQH·)的CIDEP信号;在碱性环境下(pH=9)和TX-100胶束环境下光解DQ/EG体系时得到杜醌负离子自由基(DQ- ·)的CIDEP信号;在酸性环境下(pH=2.5)光解DQ/EG体系时,出现的又是中性杜半醌自由基(DQH·)的CIDEP信号.实验结果显示,DQH·由3DQ*与EG之间的氢原子转移反应生成,DQ·-由DQH·的去质子化反应生成,反应中伴随着极化转移.
용자제적고시간분변전자자선공진파보의,측량득도료산성、감성화효속배경하적광해두곤/을이순(DQ/EG)용액순태자유기적화학유도동태전자자선겁화(CIDEP)보.재광해균상DQ/EG용액시,관찰도료이증강발사적적중성두반곤자유기(DQH·)적CIDEP신호;재감성배경하(pH=9)화TX-100효속배경하광해DQ/EG체계시득도두곤부리자자유기(DQ- ·)적CIDEP신호;재산성배경하(pH=2.5)광해DQ/EG체계시,출현적우시중성두반곤자유기(DQH·)적CIDEP신호.실험결과현시,DQH·유3DQ*여EG지간적경원자전이반응생성,DQ·-유DQH·적거질자화반응생성,반응중반수착겁화전이.
The CIDEP spectra of the transient radicals in the photolysis of duroquinone(DQ)/ ethylene glycol(EG) system in acid, basic and micellar environment were measured with the homemade highly time-resolved ESR spectrometer. In the DQ/EG homogeneous solution, the enhanced emissive CIDEP signal of the neutral durosemiquinone radical DQH· was observed. When the DQ/EG solution with pH=9 or DQ/EG/TX-100/H2O micelle system was photolyzed, the CIDEP signal of the duroquinone anion radical (DQ·-) was obtained. When the DQ/EG solution with pH=2.5 was irradiated, the CIDEP signal of DQH· appeared. These experimental results indicate that the neutral radical DQH· was formed through the proton transfer from EG to 3DQ* and DQ·- was formed from the dissociation of DQH· accompanying polarization transfer.