Rate of Molecular Transfer of Allyl Alcohol across an AOT Surfactant Layer Using Muon Spin Spectroscopy.

Rate of Molecular Transfer of Allyl Alcohol across an AOT Surfactant Layer Using Muon Spin Spectroscopy.
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使用 μ 子自旋光谱法测定烯丙醇穿过 AOT 表面活性剂层的分子转移速率。

DOI:
10.1021/acs.langmuir.5b03482
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发表时间:
2016
期刊:
the ACS journal of surfaces and colloids
影响因子:
--
通讯作者:
Jayasooriya UA
Jayasooriya UA
中科院分区:
--
文献类型:
--
作者:
Jayasooriya UA

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采用横向场μ子自旋旋转(TF-μSR)、避免能级交叉μ子自旋共振(ALC-μSR)和Monte Carlo模拟相结合的方法,研究了探针分子在油包水(W/O)微乳液界面层中的转移速率.反相微乳液是由分散在非极性溶剂中的纳米级水滴组成,它们之间由表面活性剂单层膜隔开。虽然这些系统的热力学、静态模型已经得到很好的描述,但我们对它们的动力学的理解目前还不完整。例如,水溶液和非极性溶剂之间的溶质转移速率是多少,以及界面结构如何影响溶质转移速率?通过适当选择系统和探针分子,μSR提供了直接探测这些界面转移动力学的独特机会。在这里,我们采用了一个良好的表征w/o微乳液稳定的双(2-乙基己基)磺基琥珀酸钠(气溶胶OT),与烯丙醇(CH 2-CH-CH 2-OH,AA)作为探针。由于两个μ离子化的自由基,CMuH 2-C* H-CH 2-OH和C* H 2-CHMu-CH 2-OH,观察到的共振,前者是占主导地位的物种。所有的共振显示溶剂的依赖性,与那些在微乳液中观察到作为一个单一的共振位于中间磁场中的那些存在于任何一种纯溶剂。单共振的观察是界面转移处于快速交换极限的有力证据。Monte Carlo计算的ΔM= 0 ALC共振与实验数据一致,表明交换速率大于109 s-1,将界面转移速率置于扩散极限。
The transfer rate of a probe molecule across the interfacial layer of a water-in-oil (w/o) microemulsion was investigated using a combination of transverse field muon spin rotation (TF-μSR), avoided level crossing muon spin resonance (ALC-μSR), and Monte Carlo simulations. Reverse microemulsions consist of nanometer-sized water droplets dispersed in an apolar solvent separated by a surfactant monolayer. Although the thermodynamic, static model of these systems has been well described, our understanding of their dynamics is currently incomplete. For example, what is the rate of solute transfer between the aqueous and apolar solvents, and how this is influenced by the structure of the interface? With an appropriate choice of system and probe molecule, μSR offers a unique opportunity to directly probe these interfacial transfer dynamics. Here, we have employed a well characterized w/o microemulsion stabilized by bis(2-ethylhexyl) sodium sulfosuccinate (Aerosol OT), with allyl alcohol (CH2CH–CH2–OH, AA) as the probe. Resonances due to both muoniated radicals, CMuH2–C*H–CH2–OH and C*H2–CHMu-CH2–OH, were observed with the former being the dominant species. All resonances displayed solvent dependence, with those in the microemulsion observed as a single resonance located at intermediate magnetic fields to those present in either of the pure solvents. Observation of a single resonance is strong evidence for interfacial transfer being in the fast exchange limit. Monte Carlo calculations of the ΔM= 0 ALC resonances are consistent with the experimental data, indicating exchange rates greater than 109s–1, placing the rate of interfacial transfer at the diffusion limit.
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