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七种二糖中糖苷键流动性的介电研究。

Dielectric studies on mobility of the glycosidic linkage in seven disaccharides.

作者信息

Kaminski K, Kaminska E, Wlodarczyk P, Pawlus S, Kimla D, Kasprzycka A, Paluch M, Ziolo J, Szeja W, Ngai K L

机构信息

Institute of Physics, Silesian Univ., ul. Uniwersytecka 4, 40-007 Katowice, Poland.

出版信息

J Phys Chem B. 2008 Oct 9;112(40):12816-23. doi: 10.1021/jp804240a. Epub 2008 Sep 13.

Abstract

Isobaric dielectric relaxation measurements were performed on seven chosen disaccharides. For five of them, i.e., sucrose, maltose, trehalose, lactulose, and leucrose, we were able to observe the temperature evolution of the structural relaxation process. In the case of the other disaccharides studied (lactose and cellobiose), it was impossible to obtain such information because of the large contribution of the dc conductivity and polarization of the capacitor plates to the imaginary and real part of the complex permittivity, respectively. On the other hand, in the glassy state, two secondary relaxations have been identified in the dielectric spectra of all investigated carbohydrates. The faster one (gamma) is a common characteristic feature of the entire sugar family (mono-, di-, oligo-, and polysaccharide). The molecular origin of this process is still not unambiguously identified but is expected to involve intramolecular degrees of freedom as inferred from insensitivity of its relaxation time to pressure found in some monosaccharides (fructose and ribose). The slower one (labeled beta) was recently identified to be intermolecular in origin (i.e., a Johari-Goldstein (JG) beta-relaxation), involving twisting motion of the monosugar rings around the glycosidic bond. The activation energies and dielectric strengths for the beta-relaxation determined herein provide us valuable information about the flexibility of the glycosidic bond and the mobility of this particular linkage in the disaccharides studied. In turn, this information is essential for the control of the diffusivity of drugs or water entrapped in the sugar matrix.

摘要

对七种选定的二糖进行了等压介电弛豫测量。对于其中五种,即蔗糖、麦芽糖、海藻糖、乳果糖和异麦芽糖,我们能够观察到结构弛豫过程的温度演变。对于所研究的其他二糖(乳糖和纤维二糖),由于直流电导率和电容器极板极化分别对复介电常数的虚部和实部有很大贡献,因此无法获得此类信息。另一方面,在玻璃态下,在所有研究的碳水化合物的介电谱中都识别出了两种次级弛豫。较快的一种(γ)是整个糖类家族(单糖、二糖、寡糖和多糖)的共同特征。这个过程的分子起源仍未明确确定,但根据一些单糖(果糖和核糖)中其弛豫时间对压力不敏感推断,预计涉及分子内自由度。较慢的一种(标记为β)最近被确定为分子间起源(即乔哈里 - 戈尔茨坦(JG)β弛豫),涉及单糖环围绕糖苷键的扭转运动。本文确定的β弛豫的活化能和介电强度为我们提供了有关糖苷键灵活性以及所研究二糖中这种特定键合流动性的有价值信息。反过来,这些信息对于控制被困在糖基质中的药物或水的扩散率至关重要。

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