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了解凝聚相和凝胶相的性质:两亲性抗坏血酸衍生物的 2H 和 13C NMR 研究。

Understanding the properties of the coagel and gel phases: a 2H and 13C NMR study of amphiphilic ascorbic acid derivatives.

机构信息

Department of Chemistry and Industrial Chemistry, University of Pisa, via Risorgimento 35, 56126 Pisa, Italy.

出版信息

J Phys Chem B. 2010 Dec 9;114(48):15872-8. doi: 10.1021/jp107324e. Epub 2010 Nov 15.

Abstract

The coagel and gel phases formed by the d and l diastereoisomers of ascorbyl-dodecanoate (ASC12) in deuterated water were studied through solid-state NMR techniques. In particular, the dynamic properties of water and surfactant chains were investigated by (2)H and (13)C NMR static spectra, respectively. Two fractions of water with very different dynamics were found in the coagel phases, one solidlike and one liquidlike, assigned to water strongly bound to the surfactant polar heads and bulk water, respectively. Only one kind of "intermediate" water was instead detected in the gel phase suggesting that the merging of the two types of water in the interlayers between the surfactant lamellae occurs at the coagel-to-gel transition. Moreover, the surfactant chains, very rigid in the coagel phase, give rise to fast trans-gauche interconformational jumps in the gel phase, where almost isotropic reorientations of the whole aggregates also occur. A different dynamic behavior was found for the two diastereoisomers in particular for what concerns the surfactant molecules in the gel phase and the water molecules in the coagel presumably ascribable to different inter- and intramolecular interactions that involve the polar heads.

摘要

通过固态 NMR 技术研究了抗坏血酸十二烷酯(ASC12)的 d 和 l 非对映异构体在氘化水中形成的凝聚相和凝胶相。特别是,通过 (2)H 和 (13)C NMR 静态光谱分别研究了水和表面活性剂链的动态特性。在凝聚相中有两种动态非常不同的水分数,一种固体状和一种液体状,分别分配给与表面活性剂极性头强结合的水和体相水。在凝胶相中仅检测到一种“中间”水,这表明在两个表面活性剂层片之间的层间水的两种类型的合并发生在从凝聚相向凝胶相的转变中。此外,在凝胶相中,表面活性剂链非常僵硬,导致快速的反式- gauche 构象转变,其中整个聚集物也发生几乎各向同性的重新取向。对于两种非对映异构体,发现了不同的动态行为,特别是对于凝胶相中表面活性剂分子和凝聚相中水分子,这可能归因于涉及极性头的不同的分子间和分子内相互作用。

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