Robert Raphaël, Barbati Stéphane, Ricq Natacha, Ambrosio Maurice
Laboratoire de Chimie & Environnement, Université de Provence, Marseille, France.
Water Res. 2002 Nov;36(19):4821-9. doi: 10.1016/s0043-1354(02)00205-1.
Some intermediates were identified during the course of non-catalytic wet air oxidation (WAO) of cellulose. Concentrations of by-products were determined in function of temperature and reaction time. This study also showed that hydroxyl radicals (HO*) and hydrogen peroxide (H2O2) play the role of intermediates in the initial phase of the oxidation reactions. Hydroxyl radicals were detected by the electron spin resonance spectroscopy coupled to the spin trapping technique using the 5,5-dimethyl 1-pyrroline N-oxide (DMPO) as spin trap agent. The spin adduct (DMPO/ HO*), resulting from the trapping of HO* with DMPO, showed a characteristic electron spin resonance signal which was inhibited when catalase was added, indicating that HO* was provided from H2O2. These transient species were only observed at the beginning of the reaction and were not oxygen dependent.
在纤维素的非催化湿式空气氧化(WAO)过程中鉴定出了一些中间体。测定了副产物浓度随温度和反应时间的变化。该研究还表明,羟基自由基(HO*)和过氧化氢(H2O2)在氧化反应的初始阶段起中间体的作用。使用5,5-二甲基-1-吡咯啉N-氧化物(DMPO)作为自旋捕获剂,通过电子自旋共振光谱结合自旋捕获技术检测羟基自由基。DMPO捕获HO形成的自旋加合物(DMPO/HO)显示出特征性的电子自旋共振信号,当加入过氧化氢酶时该信号受到抑制,表明HO*由H2O2产生。这些瞬态物种仅在反应开始时观察到,且不依赖于氧气。