{"title":"Diffusive Trends in Concentrated Oppositely-Charged Polyelectrolyte Solutions and Onset of Glassy Dynamics","authors":"Harrison Landfield, Muzhou Wang","doi":"10.1021/acsmacrolett.4c00378","DOIUrl":null,"url":null,"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.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.1000,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Macro Letters","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acsmacrolett.4c00378","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
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.
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.