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三硬脂酸甘油酯多晶型的非相干准弹性中子散射研究:烃链的动力学性质

Incoherent quasielastic neutron scattering study on the polymorphism of tristearin: dynamical properties of hydrocarbon chains.

作者信息

Takechi Chikayo, Kawaguchi Tatsuya, Kaneko Fumitoshi, Yamamuro Osamu, Akita Hiroyuki, Ono Machiko, Suzuki Masao

机构信息

Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.

出版信息

J Phys Chem B. 2007 Aug 23;111(33):9706-10. doi: 10.1021/jp070953k. Epub 2007 Jul 28.

DOI:10.1021/jp070953k
PMID:17661503
Abstract

Dynamical properties of acyl chains in the three polymorphic phases alpha, beta', and beta of tristearin [C(3)H(5)(OCOC(17)H(35))3] have been studied by means of incoherent quasielastic neutron scattering (IQNS) using selectively deuterated samples. The mean square displacement of hydrogen atoms, , was estimated from the scattering vector Q dependence of the elastic scattering component under the harmonic approximation. It was shown that the temperature dependence of was significantly different between the three phases. There was no marked difference in between these phases up to 193 K, and the value increased linearly with temperature. Although the beta phase remained linear up to 293 K, the alpha and beta' phases started to show a nonlinear increase around 200 K, suggesting an anharmonic nature of molecular motions. The alpha phase exhibited the most conspicuous temperature dependence. These characteristics were ascribable to the difference in the lateral packing of acyl chains. Compared with the beta phase which has a tightly packed T// subcell, the beta' and alpha phases have looser O perpendicular and H subcells, respectively. The molecular motion in the alpha phase was analyzed using the model of uniaxial rotational diffusion in a onefold cosine potential. It has been clarified that the rotational fluctuation about the chain axis in the alpha phase is rather restricted compared with that in the rotator phase of n-alkanes.

摘要

利用选择性氘代样品,通过非相干准弹性中子散射(IQNS)研究了三硬脂酸甘油酯[C(3)H(5)(OCOC(17)H(35))3]的α、β'和β三种多晶型相中酰基链的动力学性质。在简谐近似下,根据弹性散射分量对散射矢量Q的依赖性估算了氢原子的均方位移。结果表明,三种相之间的温度依赖性存在显著差异。在193K以下,这些相之间的没有明显差异,且值随温度线性增加。尽管β相在293K以下仍保持线性,但α相和β'相在200K左右开始呈现非线性增加,这表明分子运动具有非谐性。α相表现出最明显的温度依赖性。这些特性归因于酰基链侧向堆积的差异。与具有紧密堆积的T//亚晶胞的β相相比,β'相和α相分别具有较松散的O⊥和H亚晶胞。利用单轴旋转扩散在单重余弦势中的模型分析了α相中的分子运动。已经阐明,与正构烷烃的转子相相比,α相中围绕链轴的旋转涨落受到相当大的限制。

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