Aggregation in Deep Eutectic Solvents (DESs): Formation of Polar DES-in-Nonpolar DES Microemulsions

Anushis Patra,  Anjali and Siddharth Pandey*, 
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Abstract

The versatility of environmentally benign and inexpensive deep eutectic solvents (DESs) lies in their widely varying physicochemical properties. Depending on its constituents, a DES may be highly polar or nonpolar in nature. This offers an enticing possibility of formation of novel nonaqueous microemulsions (MEs). Evidence of the presence of polar DES-in-nonpolar DES MEs is presented with reline (formed by mixing choline chloride and urea in 1 : 2 mol ratio) as the polar DES forming the ME pools, Thy : DA [formed by mixing thymol (Thy) and n-decanoic acid (DA) in 1 : 1 mol ratio] nonpolar DES as the bulk oil phase and nonionic surfactant Brij-35 as the emulsifying agent. While only sparingly miscible in Thy : DA, as high as 2.5 M reline can be solubilized in this DES in the presence of 100 mM Brij-35; reline loading (wRel = [reline]/[Brij-35]) as high as 25 can be achieved. The ternary phase diagram of the Thy : DA/Brij-35/reline system reveals a clear and transparent single-phase region where MEs may be forming. Dynamic light scattering confirms the presence of MEs of 2–10 nm size. Even as up to 2.5 M (ca. 0.35 mole fraction) reline, whose dynamic viscosity (η) and electrical conductivity (κ) are very high, is added to 100 mM Brij-35 solution of Thy : DA, the η and κ values of the solution increase insignificantly, thus conforming to the formation of MEs in the solution. Fourier transform infrared (FTIR) absorbance spectra and fluorescence probe responses further indicate that reline is not dispersed in the medium but rather forms polar pools of the MEs. These novel nonaqueous polar DES-in-nonpolar DES MEs will not only expand the application potential of DESs but also offer a new class of organized media with widespread potential.

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深共晶溶剂 (DES) 中的聚合:极性 DES-非极性 DES 微乳液的形成
对环境无害且价格低廉的深共晶溶剂(DES)的多功能性在于其理化性质千差万别。根据其成分的不同,DES 可能具有高极性或非极性。这为形成新型非水微乳(ME)提供了诱人的可能性。有证据表明存在极性 DES 包非极性 DES 的微乳液,其中 Reline(由氯化胆碱和尿素以 1 : 2 的摩尔比混合而成)为极性 DES,形成微乳液池;Thy : DA(由百里酚(Thy)和正癸酸(DA)以 1 : 1 的摩尔比混合而成)为非极性 DES,作为主体油相;非离子表面活性剂 Brij-35 为乳化剂。虽然在 Thy : DA 中只有少量混溶,但在 100 mM Brij-35 的存在下,高达 2.5 M reline 可溶解于 DES 中;reline 负荷(wRel = [reline]/[Brij-35] )可高达 25。Thy : DA/Brij-35/reline 体系的三元相图显示了一个清晰透明的单相区域,在该区域可能正在形成 ME。动态光散射证实了 2-10 纳米大小的 ME 的存在。即使将动态粘度(η)和电导率(κ)都很高的 2.5 M(约 0.35 摩尔分数)reline 加入 Thy : DA 的 100 mM Brij-35 溶液中,溶液的 η 和 κ 值也不会显著增加,因此符合在溶液中形成 ME 的情况。傅立叶变换红外线(FTIR)吸收光谱和荧光探针反应进一步表明,reline 并未分散在介质中,而是形成了极性 MEs 池。这些新型非水性极性 DES-非极性 DES ME 不仅将扩大 DES 的应用潜力,还将提供一类具有广泛潜力的新型有组织介质。
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3.70
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期刊介绍: ACS Physical Chemistry Au is an open access journal which publishes original fundamental and applied research on all aspects of physical chemistry. The journal publishes new and original experimental computational and theoretical research of interest to physical chemists biophysical chemists chemical physicists physicists material scientists and engineers. An essential criterion for acceptance is that the manuscript provides new physical insight or develops new tools and methods of general interest. Some major topical areas include:Molecules Clusters and Aerosols; Biophysics Biomaterials Liquids and Soft Matter; Energy Materials and Catalysis
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