White Ryan C, Gorelik Vitaly, Bagryanskaya Elena G, Forbes Malcolm D E
Caudill Laboratories, CB#3290, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, USA.
Langmuir. 2007 Apr 10;23(8):4183-91. doi: 10.1021/la063322a. Epub 2007 Mar 8.
Time-resolved magnetic resonance experiments (TREPR and CIDNP) are used to investigate previously unobserved redox chemistry of the surfactant dioctyl sulfosuccinate ester (AOT) using the photoexcited triplet state of anthraquinone 2,6-disulfonate (3AQDS*). Several different free radicals resulting from two independent oxidation pathways (electron transfer and hydrogen abstraction) are observed. These include the radical ions of AQDS and sulfite from electron-transfer processes, carbon-centered radicals from H-atom abstraction reactions, and an additional carbon-centered radical formed by electron transfer from the AOT sulfonate head group followed by the loss of SO3. The radicals exhibit intense chemically induced dynamic electron spin polarization (CIDEP) in their TREPR spectra. The intensity ratios of the observed TREPR signals for each radical depend on the water pool size and temperature, which in turn affect the predominant CIDEP mechanism. All signal carriers are accounted for by simulation, and CIDNP results provide strong supporting evidence for the assignments.
时间分辨磁共振实验（TREPR和CIDNP）用于利用蒽醌-2,6-二磺酸盐的光激发三重态（3AQDS*）研究表面活性剂二辛基磺基琥珀酸酯（AOT）以前未观察到的氧化还原化学。观察到由两种独立氧化途径（电子转移和氢原子提取）产生的几种不同自由基。这些包括电子转移过程中AQDS和亚硫酸盐的自由基离子、氢原子提取反应产生的碳中心自由基，以及由AOT磺酸盐头部基团进行电子转移随后失去SO3形成的另一种碳中心自由基。这些自由基在其TREPR光谱中表现出强烈的化学诱导动态电子自旋极化（CIDEP）。每个自由基观察到的TREPR信号的强度比取决于水池大小和温度，这反过来又影响主要的CIDEP机制。通过模拟对所有信号载体进行了分析，CIDNP结果为这些归属提供了有力的支持证据。
