Diffusive Trends in Concentrated Oppositely-Charged Polyelectrolyte Solutions and Onset of Glassy Dynamics

IF 5.1 Q1 POLYMER SCIENCE
Harrison Landfield, Muzhou Wang
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引用次数: 0

Abstract

We utilize single particle tracking studies to investigate the diffusion of polylysine through concentrated matrices of cationic polylysine and anionic polyglutamic acid with no added salts. These studies show that diffusivity has a strong apparently exponential dependence on concentration in crowded systems that does not appear to be a function of the charge sign. These trends are consistent in both single-phase systems prepared at concentrated conditions and polymer-rich coacervate phases formed from dilute phase-separating systems. The likely origin of this behavior is the onset of glassy dynamics spurred by a decrease in plasticization by water and the large excluded volume associated with charge-bearing species. This effect can be contextualized through free volume-based theories such as the Vrentas–Duda model. Overall, we obtain dynamic behavior that is distinctly different from behavior observed in more dilute systems and warrants further investigation.

Abstract Image

浓缩的对置电荷聚电解质溶液中的扩散趋势和玻璃态动力学的开始
我们利用单颗粒跟踪研究来探讨聚赖氨酸在阳离子聚赖氨酸和阴离子聚谷氨酸的浓缩基质中的扩散情况。这些研究表明,在拥挤的系统中,扩散率与浓度呈明显的指数关系,似乎与电荷符号无关。这些趋势在浓缩条件下制备的单相体系和稀相分离体系形成的富含聚合物的凝聚相中都是一致的。这种行为的起因可能是由于水的塑化作用减弱以及与含电荷物种相关的大排斥体积刺激了玻璃态动力学的发生。这种效应可以通过基于自由体积的理论(如弗伦塔斯-杜达模型)加以解释。总之,我们获得的动态行为与在更稀的体系中观察到的行为截然不同,值得进一步研究。
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来源期刊
CiteScore
10.40
自引率
3.40%
发文量
209
审稿时长
1 months
期刊介绍: ACS Macro Letters publishes research in all areas of contemporary soft matter science in which macromolecules play a key role, including nanotechnology, self-assembly, supramolecular chemistry, biomaterials, energy generation and storage, and renewable/sustainable materials. Submissions to ACS Macro Letters should justify clearly the rapid disclosure of the key elements of the study. The scope of the journal includes high-impact research of broad interest in all areas of polymer science and engineering, including cross-disciplinary research that interfaces with polymer science. With the launch of ACS Macro Letters, all Communications that were formerly published in Macromolecules and Biomacromolecules will be published as Letters in ACS Macro Letters.
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