Dynamics of crystals in metastable liquids with applications to the growth of polypeptide hormones

Dmitri V. Alexandrov, Alexander A. Ivanov, Irina V. Alexandrova, Eugenya V. Makoveeva
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Abstract

This study is concerned with the dynamics of a polydisperse ensemble of crystals in a single-component metastable solution/melt. A new theory based on the kinetic and balance equations is developed for the description of initial and intermediate stages of bulk crystallization. Such phenomena as unsteady growth rates of individual crystals with fluctuations, diffusion of the crystal-size distribution function in the space of particle radii, the Gibbs–Thomson and atomic kinetics effects, various crystal nucleation mechanisms are taken into account. The analytical solution is constructed in a parametric form with the modified time being the decision variable. Namely, the metastability degree, particle-radius distribution function, crystallization time, total number of crystals and their mean size are found as the functions of decision variable. The analytical solutions show that the metastability degree decreases with time as a result of liquid desupersaturation/desupercooling. As this takes place, the particle-radius distribution function moves to greater particle radii, becomes wider and lower with increasing the crystallization time. The theory is tested against experiments on the growth of such polypeptide hormones as porcine and bovine insulins. We show that the theory is in good agreement with the experimental data.

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晶体在易变质液体中的动力学及其在多肽激素生长中的应用
本研究涉及单组分可蜕变溶液/熔体中多分散晶体集合体的动力学。在动力学和平衡方程的基础上开发了一种新的理论,用于描述块状结晶的初始和中间阶段。该理论考虑了具有波动的单个晶体的不稳定增长率、晶体尺寸分布函数在粒子半径空间中的扩散、吉布斯-汤姆森效应和原子动力学效应、各种晶体成核机制等现象。分析解是以参数形式构建的,修正时间是决定变量。即,将蜕变度、粒子半径分布函数、结晶时间、晶体总数及其平均尺寸作为决策变量的函数。分析结果表明,由于液体去饱和/去过冷,转移度会随着时间的推移而降低。随着结晶时间的延长,颗粒半径分布函数会向更大的颗粒半径移动,变得更宽且更低。该理论通过猪和牛胰岛素等多肽激素的生长实验进行了检验。结果表明,该理论与实验数据十分吻合。
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