Comparing solvophobic and multivalent induced collapse in polyelectrolyte brushes

Jackson, Nicholas E.; Brettmann, Blair K.; Vishwanath, Venkatram; Tirrell, Matthew; de Pablo, Juan J.

doi:10.1021/acsmacrolett.6b00837

Comparing solvophobic and multivalent induced collapse in polyelectrolyte brushes

Journal Article · Fri Feb 03 00:00:00 EST 2017 · ACS Macro Letters

DOI:https://doi.org/10.1021/acsmacrolett.6b00837· OSTI ID:1351285

Jackson, Nicholas E. ^[1]; ^[2]; Vishwanath, Venkatram ^[3]; Tirrell, Matthew ^[1]; ^[1]

The Univ. of Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
The Univ. of Chicago, Chicago, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)

Here, coarse-grained molecular dynamics enhanced by free-energy sampling methods is used to examine the roles of solvophobicity and multivalent salts on polyelectrolyte brush collapse. Specifically, we demonstrate that while ostensibly similar, solvophobic collapsed brushes and multivalent-ion collapsed brushes exhibit distinct mechanistic and structural features. Notably, multivalent-induced heterogeneous brush collapse is observed under good solvent polymer backbone conditions, demonstrating that the mechanism of multivalent collapse is not contingent upon a solvophobic backbone. Umbrella sampling of the potential of mean-force (PMF) between two individual brush strands confirms this analysis, revealing starkly different PMFs under solvophobic and multivalent conditions, suggesting the role of multivalent “bridging” as the discriminating feature in trivalent collapse. Structurally, multivalent ions show a propensity for nucleating order within collapsed brushes, whereas poor-solvent collapsed brushes are more disordered; this difference is traced to the existence of a metastable PMF minimum for poor solvent conditions, and a global PMF minimum for trivalent systems, under experimentally relevant conditions.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1351285

Journal Information:: ACS Macro Letters, Journal Name: ACS Macro Letters Journal Issue: 2 Vol. 6; ISSN 2161-1653

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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From Octopus to Dendrite - Semiflexible Polyelectrolyte Brush Condensates in Trivalent Counterion Solution Liu, Lei; Hyeon, Changbong arXiv https://doi.org/10.48550/arxiv.1803.00167	text	January 2018

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