Aug 2026· Macromolecules· 0 citations· 73 references
Abstract
Time-dependent aging phenomena in polymer adsorption at solid–liquid interfaces from dilute solutions were discovered over three decades ago. However, how the properties of a single polymer chain evolve over macroscopic timescales remains poorly understood. Here, we conducted a long-term experimental study on polyethylene glycol (PEG) chains adsorbed from ultradilute solutions by complementarily using single-molecule fluorescence tracking, liquid-environment atomic force microscopy, and sum-frequency generation vibrational spectroscopy. We observe distinctly nonequilibrium and aging dynamics in individual adsorbed polymer chains. Immediately after adsorption, the polymer conformations exhibit a coexistence of states with both low and high segment–surface contact, which display significantly different desorption timescales. The observed time-dependent aging phenomenon can be attributed to the probabilistic formation of distinct conformations upon adsorption, rather than from postadsorption rearrangements. This behavior is well rationalized by a nonergodic continuous-time random walk model. This suggests that ergodicity breaking underlies the nonequilibrium polymer dynamics at solid–liquid interfaces under ultradilute conditions.
Melt memory in semicrystalline polymers is the remarkable ability of polymer chains to retain structural information from a prior crystalline state after being heated above the melting temperature. This phenomenon can induce extraordinary self-nucleation and strongly influence crystallization kinetics and final materia...
A. de Nicola, A. Müller, Dario Cavallo et al.· Journal of the American Chem...· 0 citations
Helical segments in polymer chains are often transient, finite, and dynamically evolving, yet their origin and stability remain incompletely understood. Here, we develop a minimal coarse-grained statistical-mechanical theory that explains how such "living helices" emerge in fluctuating polymer systems. Using a three-st...
Biman Bagchi· Journal of Chemical Physics· 0 citations
Understanding the interfacial structure of multi-site polymer adsorption is critical for the rational design of functional nanomaterials. However, the distribution of chains attached via one, two, or more anchor points has remained inaccessible to experiments and conventional simulations. Experiments typically measure...
Surface-liquid slip is critical in nanofluidic and confined biological systems, where interfacial effects dominate. Slip is typically described by a Markovian Navier friction coefficient, which fails to capture nonstationary friction dynamics. Here, a recent generalization of the Navier friction coefficient for subnano...
S. Carlson, Benjamin J. A. Héry, Louis Lehmann et al.· Journal of Physical Chemistr...· 0 citations
Polymer adsorption at solid/liquid interfaces plays a crucial role in many applications, yet the molecular pathway of adsorption remains difficult to resolve experimentally. Here, we investigated the adsorption of poly(methyl methacrylate) (PMMA) and polystyrene (PS) from solution onto silica using in situ, real-time s...
Tatsuki Abe, Tieyi Lu, John S. Andre et al.· Langmuir· 0 citations
We investigate the kinetics of bubble coarsening in a single-component Lennard-Jones fluid using large-scale molecular dynamics simulations. A homogeneous high-temperature system is quenched below the vapor-liquid critical temperature to induce nucleation and growth of vapor bubbles within a dense liquid matrix. The st...
P. A, Bhaskar Sen Gupta· Journal of Chemical Physics· 0 citations
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