Division of Chemical Engineering, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan.
J Phys Chem A. 2012 Mar 15;116(10):2405-8. doi: 10.1021/jp300814s. Epub 2012 Mar 6.
To investigate the molecular interaction between guest species inside of the small and large cages of methane + propane mixed gas hydrates, thermal stabilities of the methyl radical (possibly induced in small cages) and the normal propyl and isopropyl radicals (induced in large cages) were investigated by means of electron spin resonance measurements. The increase of the total amount of the normal propyl and isopropyl radicals reveals that the methyl radical in the small cage withdraws one hydrogen atom from the propane molecule enclathrated in the adjacent large cage of the structure-II hydrate. A guest species in a hydrate cage has the ability to interact closely with the other one in the adjacent cages. The clathrate hydrate may be utilized as a possible nanoscale reaction field.
为了研究甲烷+丙烷混合气体水合物中小笼和大笼内客体物种之间的分子相互作用,通过电子自旋共振测量研究了甲基自由基(可能在小笼中诱导)和正丙基及异丙基自由基(在大笼中诱导)的热稳定性。正丙基和异丙基自由基总量的增加表明,小笼中的甲基自由基从结构-II 水合物相邻大笼包合的丙烷分子中夺取了一个氢原子。水合物笼中的客体物种具有与相邻笼中的另一个客体物种紧密相互作用的能力。笼型水合物可用作可能的纳米级反应场。