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甘醇类深共晶溶剂的二核子磁共振研究:胆碱和甘油动力学的选择性探测。

Deuteron magnetic resonance study of glyceline deep eutectic solvents: Selective detection of choline and glycerol dynamics.

机构信息

Experimental Physics III, Technical University Dortmund, D-44221 Dortmund, Germany.

出版信息

J Chem Phys. 2022 May 21;156(19):194506. doi: 10.1063/5.0088290.

Abstract

Glyceline, a green solvent considered for various electrochemical applications, represents a multi-component glass former. Viewed from this perspective, the choline cation and the hydrogen bond donor glycerol, the two major constituents forming this deep eutectic solvent, were studied using nuclear magnetic resonance in a selective manner by means of suitably deuteron-labeled isotopologues. Carried out from far above to far below the glass transition temperature, measurements and analyses of the spin-lattice and spin-spin relaxation times reveal that the reorientational dynamics of the components, i.e., of glycerol as well as of chain deuterated choline chloride are slightly different. Possible implications of this finding regarding the hydrogen-bonding pattern in glyceline are discussed. Furthermore, the deuterated methyl groups in choline chloride are exploited as sensitive probes of glyceline's supercooled and glassy states. Apart from spin relaxometry, a detailed line shape analysis of the CD spectra yields valuable insights into the broad intermolecular and intramolecular energy barrier distributions present in this binary mixture.

摘要

甘醇,一种被认为适用于各种电化学应用的绿色溶剂,是一种多组分玻璃形成剂。从这个角度来看,胆碱阳离子和氢供体甘油是形成这种深共晶溶剂的两个主要成分,通过使用适当的氘标记同位素,以选择性的方式使用核磁共振进行了研究。从远高于玻璃化转变温度到远低于玻璃化转变温度进行的自旋晶格和自旋-自旋弛豫时间的测量和分析表明,各组分的重取向动力学,即甘油以及链氘化氯化胆碱的重取向动力学略有不同。关于甘醇中的氢键模式,讨论了这一发现的可能意义。此外,氯化胆碱中的氘代甲基基团可用作甘醇过冷和玻璃态的灵敏探针。除了自旋弛豫测量法外,对 CD 光谱的详细线形分析还提供了有关该二元混合物中存在的广泛的分子间和分子内能量势垒分布的有价值的见解。

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