Malardier-Jugroot Cecile, Head-Gordon Teresa
Department of Bioengineering, University of California, Berkeley, CA 94720, USA.
Phys Chem Chem Phys. 2007 Apr 28;9(16):1962-71. doi: 10.1039/b616997j. Epub 2007 Feb 6.
We report quasi-elastic neutron scattering experiments at two resolutions that probe timescales of picoseconds to nanoseconds for the hydration dynamics of water, confined in a concentrated solution of N-acetyl-leucine-methylamide (NALMA) peptides in water over a temperature range of 248 K to 288 K. The two QENS resolutions used allow for a clean separation of two observable translational components, and ultimately two very different relaxation processes, that become evident when analyzed under a combination of the jump diffusion model and the relaxation cage model. The first translational motion is a localized beta-relaxation process of the bound surface water, and exhibits an Arrhenius temperature dependence and a large activation energy of approximately 8 kcal mol(-1). The second non-Arrhenius translational component is a dynamical signature of the alpha-relaxation of more fluid water, exhibiting a glass transition temperature of approximately 116 K when fit to the Volger Fulcher Tamman functional form. These peptide solutions provide a novel experimental system for examining confinement in order to understand the dynamical transition in bulk supercooled water by removing the unwanted interface of the confining material on water dynamics.
我们报告了在两种分辨率下进行的准弹性中子散射实验,这些实验探测了水的水合动力学中皮秒到纳秒时间尺度的情况,水被限制在N - 乙酰 - 亮氨酸 - 甲酰胺(NALMA)肽在水中的浓溶液中,温度范围为248 K至288 K。所使用的两种准弹性中子散射分辨率能够清晰地分离出两个可观测的平移分量,最终分离出两个截然不同的弛豫过程,当在跳跃扩散模型和弛豫笼模型的组合下进行分析时,这些过程变得明显。第一个平移运动是结合在表面的水的局部β弛豫过程,表现出阿仑尼乌斯温度依赖性和大约8千卡摩尔⁻¹的大活化能。第二个非阿仑尼乌斯平移分量是更多流动性水的α弛豫的动力学特征,当拟合到Volger Fulcher Tamman函数形式时,表现出约116 K的玻璃化转变温度。这些肽溶液提供了一个用于研究受限情况的新型实验系统,以便通过去除限制材料对水动力学的不必要界面来理解大量过冷水的动力学转变。