In order to study the mechanisms limiting the topological chain confinement in polymer melts, we have performed neutron-spin-echo investigations of the single-chain dynamic-structure factor from polyethylene melts over a large range of chain lengths. While at high molecular weight the reptation model is corroborated, a systematic loosening of the confinement with decreasing chain length is found. The dynamic-structure factors are quantitatively described by the effect of contour-length fluctuations on the confining tube, establishing this mechanism on a molecular level in space and time.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1103/PhysRevLett.88.058301 | DOI Listing |
J Chem Phys
December 2024
Department of Physics, Kyungpook National University, Daegu, South Korea.
The freely jointed chain model with reversible hinges (rFJC) is the simplest theoretical model, which captures reversible transitions of the local bending stiffness along the polymer chain backbone (e.g., helix-coil-type of local conformational changes or changes due to the binding/unbinding of ligands).
View Article and Find Full Text PDFJ Chem Phys
May 2023
Department of Physics, University of Central Florida, Orlando, Florida 32816-2385, USA.
We study the universal aspects of polymer conformations and transverse fluctuations for a single swollen chain characterized by a contour length L and a persistence length ℓp in two dimensions (2D) and three dimensions (3D) in the bulk, as well as in the presence of excluded volume (EV) particles of different sizes occupying different area/volume fractions. In the absence of the EV particles, we extend the previously established universal scaling relations in 2D [Huang et al., J.
View Article and Find Full Text PDFJ Chem Phys
May 2023
Department of Chemical Engineering and Materials Science, University of Minnesota-Twin Cities, 421 Washington Ave. SE, Minneapolis, Minnesota 55455, USA.
We used Langevin dynamics simulations without hydrodynamic interactions to probe knot diffusion mechanisms and the time scales governing the evolution and the spontaneous untying of trefoil knots in nanochannel-confined DNA molecules in the extended de Gennes regime. The knot untying follows an "opening up process," wherein the initially tight knot continues growing and fluctuating in size as it moves toward the end of the DNA molecule before its annihilation at the chain end. The mean knot size increases significantly and sub-linearly with increasing chain contour length.
View Article and Find Full Text PDFJ Phys Condens Matter
March 2023
Department of Physics and Astronomy, Louisiana State University, Baton Rouge, LA, United States of America.
Dielectric spectroscopy is extremely powerful to study molecular dynamics, because of the very broad frequency range. Often multiple processes superimpose resulting in spectra that expand over several orders of magnitude, with some of the contributions partially hidden. For illustration, we selected two examples, (i) normal mode of high molar mass polymers partially hidden by conductivity and polarization and (ii) contour length fluctuations partially hidden by reptation using the well-studied polyisoprene melts as example.
View Article and Find Full Text PDFACS Macro Lett
January 2022
Micro/Bio/Nanofluidics Unit, Okinawa Institute of Science and Technology Graduate University, 1919-1 Tancha, Onna-son, Kunigami-gun, Okinawa 904-0495, Japan.
The entanglement dynamics and viscoelasticity of polyelectrolyte solutions remain active research topics. Previous studies have reported conflicting experimental results when compared to Dobrynin's scaling predictions derived from the Doi-Edwards (DE) tube model for entangled polymers. Herein, by combining classical bulk shear rheometry with diffusing wave spectroscopy (DWS) microrheometry, we investigate how the key viscoelastic parameters (the specific viscosity η, the plateau modulus , and the ratio of the reptation time to the Rouse time of an entanglement strand τ/τ) depend on the polymer concentration for semidilute entangled (SE) solutions containing poly(sodium styrenesulfonate) with high molecular weight.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!