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通过布里渊非弹性紫外散射研究海藻糖-水溶液中结构弛豫时间的浓度-温度依赖性

Concentration-temperature dependencies of structural relaxation time in trehalose-water solutions by brillouin inelastic UV scattering.

作者信息

Di Fonzo S, Masciovecchio C, Bencivenga F, Gessini A, Fioretto D, Comez L, Morresi A, Gallina M E, De Giacomo O, Cesàro A

机构信息

Sincrotrone Trieste, Strada Statale 14 km 163.5, Area Science Park, I-34012 Trieste, Italy.

出版信息

J Phys Chem A. 2007 Dec 13;111(49):12577-83. doi: 10.1021/jp075982+. Epub 2007 Nov 13.

Abstract

A Brillouin scattering investigation has been carried out on trehalose-water solutions in a wide range of concentrations (0<phi<0.74) in the ultraviolet regime. A complete set of data as a function of temperature (-10 degrees C<or=T<or=100 degrees C) has been obtained for each concentration. The T-phi evolution of the system has been analyzed in terms of energy position and line width of inelastic peaks. These results have been used to derive the structural relaxation time, tau, of the system. This was found to be in the tens of picoseconds time scale, and its T dependence can be described with an activation (Arrhenius) law. Most importantly, a significant slowing down of the relaxation dynamics has been observed as trehalose concentration was increased. At low phi, the activation energy of the relaxation has been found to be consistent with literature data for pure water and comparable with intermolecular hydrogen bond (HB) energy. This evidence strongly supports the hypothesis that the main microscopic mechanism responsible for the relaxation process in trehalose solutions lies in the continuous rearrangement of the HB network. Finally, the results are discussed in terms of the evolution of the system upon increasing trehalose concentration, in order to provide a complete description of the viscoelastic stiffening in real biological conditions.

摘要

在紫外区域对不同浓度(0<φ<0.74)的海藻糖-水溶液进行了布里渊散射研究。对于每种浓度,都获得了一组完整的随温度变化(-10℃≤T≤100℃)的数据。根据非弹性峰的能量位置和线宽对系统的T-φ演化进行了分析。这些结果被用于推导系统的结构弛豫时间τ。发现其处于几十皮秒的时间尺度,其对T的依赖性可用活化(阿仑尼乌斯)定律来描述。最重要的是,随着海藻糖浓度的增加,观察到弛豫动力学显著减慢。在低φ时,发现弛豫的活化能与纯水的文献数据一致,且与分子间氢键(HB)能量相当。这一证据有力地支持了这样的假设,即海藻糖溶液中弛豫过程的主要微观机制在于HB网络的持续重排。最后,根据海藻糖浓度增加时系统的演化对结果进行了讨论,以便对实际生物条件下的粘弹性硬化提供完整描述。

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