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香豆素 153 在胆碱氯盐基深共熔溶剂中的旋转和平移动力学。

Rotation and translation dynamics of coumarin 153 in choline chloride-based deep eutectic solvents.

机构信息

Department of Physics, Sogang University, Seoul, South Korea.

出版信息

J Chem Phys. 2018 Nov 7;149(17):174503. doi: 10.1063/1.5038067.

Abstract

The equilibrium and dynamic solvation responses of coumarin 153 (C153) in a range of deep eutectic solvents (DESs) based on choline chloride with either urea (molar ratio 1:2, ChCl:U), glycerol (1:2, ChCl:G), ethylene glycol (1:2, ChCl:E), or malonic acid (1:1, ChCl:Mal) were investigated using both steady-state and time-resolved fluorescence emission spectroscopy at room temperature (298 K). From steady-state fluorescence data, "red-edge effects" were observed in all the DESs studied, attributed to spatial heterogeneity of the DES matrix. Time-resolved Stokes shifts were used to quantify dynamic solvation with the solvation response function in DES found to be a biexponential function of time, which were used to obtain average solvation times (⟨ ⟩) which are generally faster in DES than in ionic liquids of comparable viscosity. Average solvation times showed a partial correlation with viscosity between different DESs. The choline chloride-glycerol DES showed deviation from the viscosity trend observed in the other DES for both dynamic and steady-state results. Rotational reorientation times obtained from dynamic anisotropy (()) measured for these DESs showed a partial correlation with viscosity between different DESs. Determination of the DES rotational coupling with C153 showed more "slip"-like behavior than the previously reported ionic liquids and dipolar solvents.

摘要

采用稳态和时间分辨荧光发射光谱法,在室温(298 K)下研究了香豆素 153(C153)在一系列基于氯化胆碱的深共晶溶剂(DES)中的平衡和动态溶剂化响应,这些 DES 分别为:尿素(摩尔比 1:2,ChCl:U)、甘油(1:2,ChCl:G)、乙二醇(1:2,ChCl:E)或丙二酸(1:1,ChCl:Mal)。从稳态荧光数据中,观察到所有研究的 DES 中都存在“红移效应”,这归因于 DES 基质的空间异质性。时间分辨斯托克斯位移用于量化动态溶剂化,发现 DES 中的溶剂化响应函数是时间的双指数函数,可用于获得平均溶剂化时间( ⟨ ⟩),这些时间通常比具有可比粘度的离子液体更快。平均溶剂化时间与不同 DES 之间的粘度之间存在部分相关性。在其他 DES 中,氯化胆碱-甘油 DES 的动态和稳态结果都偏离了观察到的粘度趋势。这些 DES 的动态各向异性(())测量得到的旋转重取向时间与不同 DES 之间的粘度之间存在部分相关性。与 C153 确定的 DES 旋转偶联显示出比以前报道的离子液体和偶极溶剂更“滑动”的行为。

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