Allison Stettler, Piyuni Ishtaweera, Gary A Baker, Gary J Blanchard
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引用次数: 0
Abstract
Deep eutectic solvents (DESs) exhibit dynamic heterogeneity, where the intricate and dynamic hydrogen bonding within the DES mediates dynamic spatial variation in the DES local environment. The Type III DES composed of choline chloride and glycerol (ChCl:Gly) exhibits this effect prominently, and we report on the observed local organization and its dependence on system composition using the time-resolved reorientation dynamics of three illustrative chromophores of different polarities: perylene (neutral, nonpolar), oxazine 725 (cation, polar) and rose bengal (dianion, polar). Our findings demonstrate that the environments sensed by all three chromophores are markedly different than that predicted by the bulk viscosity of the DES, and that these local environments exhibit remarkably little change as the mole ratio of the DES constituents is varied. Taken collectively, these data provide clear evidence of short-range organization that bears very little resemblance to the longer-range structural organization that determines DES bulk properties.
深共晶溶剂(DES)表现出动态异质性,DES内部错综复杂的动态氢键介导了DES局部环境的动态空间变化。由氯化胆碱和甘油(ChCl:Gly)组成的 III 型 DES 具有显著的这种效应,我们通过对三种不同极性的发色团(过烯(中性,非极性)、噁嗪 725(阳离子,极性)和玫瑰红(二离子,极性))进行时间分辨的重新定向动力学研究,报告了观察到的局部组织及其对系统组成的依赖性。我们的研究结果表明,这三种发色团所感应到的环境与 DES 体积粘度所预测的环境明显不同,而且随着 DES 成分摩尔比的变化,这些局部环境的变化非常小。综合来看,这些数据清楚地证明了短程组织与决定 DES 体积特性的长程结构组织几乎没有相似之处。
期刊介绍:
Applied Spectroscopy is one of the world''s leading spectroscopy journals, publishing high-quality peer-reviewed articles, both fundamental and applied, covering all aspects of spectroscopy. Established in 1951, the journal is owned by the Society for Applied Spectroscopy and is published monthly. The journal is dedicated to fulfilling the mission of the Society to “…advance and disseminate knowledge and information concerning the art and science of spectroscopy and other allied sciences.”