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A recently developed density functional theory (DFT) for tethered bead-spring chains is used to investigate colloidal forces for the good solvent case. A planar surface of tethered chains is opposed to a bare, hard wall and the force exerted on the bare wall is calculated by way of the contact density. Previously, the case of large wall separation was investigated. The density profiles of the unperturbed chains, in that case, were found to be neither stepfunctions nor parabolas and were shown to accurately predict computer simulation results. In the present paper, the surface forces that result from the distortion of these density profiles at finite wall separation is studied. The resulting force function is analyzed for varying surface coverages, wall separations, and chain lengths. The results are found to be in near quantitative agreement with the scaling predictions of Alexander [S. Alexander, J. Phys. (Paris) 38, 983 (1977)] when the layer thickness is "correctly" defined. Finally, a hybrid Alexander-DFT theory is suggested for the analysis of experimental results.
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http://dx.doi.org/10.1063/1.1884113 | DOI Listing |
PLoS One
August 2025
Department of Physics and Astronomy, University of Texas Rio Grande Valley, Edinburg, Texas, United States of America.
DNA flow-stretching is a widely employed, powerful technique for investigating the mechanisms of DNA-binding proteins involved in compacting and organizing chromosomal DNA. We combine single-molecule DNA flow-stretching experiments with Brownian dynamics simulations to study the effect of the crowding agent polyethylene glycol (PEG) in these experiments. PEG interacts with DNA by an excluded volume effect, resulting in compaction of single, free DNA molecules in PEG solutions.
View Article and Find Full Text PDFSoft Matter
July 2025
Sandia National Laboratories, Albuquerque, New Mexico, 87185, USA.
Tailoring the topology of associative polymers offers a means to control macromolecular responses that in turn enables the design of new responsive soft materials. The current study probes the conformation and response of ring associative polymers in comparison with their entangled linear analogues using molecular dynamics simulations of a coarse-grained bead-spring model. The uniqueness of ring polymers lies in their topology where the chains have no free ends, resulting in considerably faster dynamics compared to their linear analogs, whereas the associative groups drive assembly that constrains the polymer motion.
View Article and Find Full Text PDFSoft Matter
July 2025
School of Chemical Engineering, The University of Queensland, Brisbane 4072, Australia.
The mechanical response and structure of cellulose hydrogel composites (CHCs) are modelled as cellulose microfibrils using a bead-spring coarse-graining approach. Our results demonstrate that varying the adhesive contact energy between the flexible chains, as well as the number of contacts and structural anisotropy, significantly impacts the mechanical response of the network structure under tensile forces. Specifically, decreasing the contact energy and increasing its range is sufficient to increase the network's extensibility while decreasing its overall modulus.
View Article and Find Full Text PDFMolecules
April 2025
School of Chemistry & Physics, University of KwaZulu-Natal, Pietermaritzburg, Private Bag X01, Scottsville 3209, South Africa.
We performed extensive molecular dynamics simulations using a bead-spring model to investigate the interfacial behavior of blends of linear and cyclic polymer chains confined between two planar, attractive substrates. The model system was studied over a range of chain lengths spanning an order of magnitude in the number of beads for varying blend compositions and for two different levels of substrate affinity. For short chains, we observed the preferential adsorption of linear chains at the substrate interface when they are the majority component (10% cyclic chains) as well as at equimolar composition.
View Article and Find Full Text PDFDNA flow-stretching is a widely employed, powerful technique for investigating the mechanisms of DNA-binding proteins involved in compacting and organizing chromosomal DNA. We combine single-molecule DNA flow-stretching experiments with Brownian dynamics simulations to study the effect of the crowding agent polyethylene glycol (PEG) in these experiments. PEG interacts with DNA by an excluded volume effect, resulting in compaction of single, free DNA molecules in PEG solutions.
View Article and Find Full Text PDF