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利用 PRODAN 的双重发射特性来监测 BHDC 与外部有机溶剂组成之间的界面性质变化。

PRODAN dual emission feature to monitor BHDC interfacial properties changes with the external organic solvent composition.

机构信息

Departamento de Química, Universidad Nacional de Río Cuarto, Agencia Postal # 3, C.P X5804BYA Río Cuarto, Argentina.

出版信息

Langmuir. 2013 Mar 19;29(11):3556-66. doi: 10.1021/la304951f. Epub 2013 Mar 7.

Abstract

We have investigated the water/benzyl-n-hexadecyldimethylammonium chloride (BHDC)/n-heptane:benzene reverse micelles (RMs) interfaces properties using 6-propionyl-2-(N,N-dimethyl)aminonaphthalene, PRODAN, as molecular probe. We have used absorption and emission (steady-state and time-resolved) spectroscopy of PRODAN to monitor the changes in the RMs interface functionalities upon changing the external organic solvent blend. We demonstrate that PRODAN is a useful probe to investigate how the external solvent composition affects the micelle interface properties. Our results show that changes in the organic solvent composition in water/BHDC/n-heptane:benzene RMs have a dramatic effect on the photophysics of PRODAN. Thus, increasing the aliphatic solvent content over the aromatic one produces PRODAN partition and PRODAN intramolecular electron transfer (ICT) processes. Additionally, the water presence in these RMs makes the PRODAN ICT process favored with the consequent decreases in the LE emission intensity and a better definition of the charge transfer (CT) band. All this evidence suggests that the benzene molecules are expelled out of the interface, and the water-BHDC interactions are stronger with more presence of water molecules in the polar part of the interface. Thus, we demonstrate that a simple change in the composition of the external phase promotes remarkable changes in the RMs interface. Finally, the results obtained with PRODAN together with those reported in a previous work in our lab reveal that the external phase is important when trying to control the properties of RMs interface. It should be noted that the external phase itself, besides the surfactant and the polar solvent sequestrated, is a very important control variable that can play a key role if we consider smart application of these RMs systems.

摘要

我们使用 6-丙酰基-2-(N,N-二甲基)氨基萘,PRODAN,作为分子探针,研究了水/苄基-N-十六烷基二甲基氯化铵(BHDC)/正庚烷:苯反胶束(RM)界面的性质。我们利用 PRODAN 的吸收和发射(稳态和时间分辨)光谱来监测 RM 界面功能在改变外部有机溶剂混合物时的变化。我们证明 PRODAN 是一种有用的探针,可以研究外部溶剂组成如何影响胶束界面性质。我们的结果表明,水/BHDC/正庚烷:苯 RM 中有机溶剂组成的变化对 PRODAN 的光物理性质有显著影响。因此,增加脂肪族溶剂的含量而减少芳香族溶剂的含量会产生 PRODAN 分配和 PRODAN 分子内电子转移(ICT)过程。此外,这些 RM 中的水使 PRODAN ICT 过程占优势,导致 LE 发射强度降低,电荷转移(CT)带的定义更好。所有这些证据表明,苯分子被逐出界面,并且随着界面极性部分中水分子的存在,水-BHDC 相互作用更强。因此,我们证明了外部相组成的简单变化可以促进 RM 界面的显著变化。最后,PRODAN 获得的结果以及我们实验室以前的工作中报告的结果表明,当试图控制 RM 界面的性质时,外部相是很重要的。应该注意的是,外部相本身,除了被隔离的表面活性剂和极性溶剂之外,是一个非常重要的控制变量,如果我们考虑这些 RM 系统的智能应用,它可以发挥关键作用。

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