Linear and Ring Polymer Brushes: A Density Functional Theory Study

Егоров, С. А.

doi:10.1002/mats.202100065

Cited by 2 publications

(1 citation statement)

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“…[20,24] Interestingly, the presence of a confining substrate can amplify these and other topology effects. [25][26][27][28][29][30] Due to their reduced molecular dimensions, cyclic polymers can generate significantly denser polymer brushes when grafted on macroscopic surfaces and nanoparticles (NPs). Especially on NPs, this phenomenon provides increased colloidal stability and augmented hindrance toward unspecific interaction with serum proteins.…”

Section: Introductionmentioning

confidence: 99%

The Topology of Polymer Brushes Determines Their Nanoscale Hydration

Vagias

Nelson

Wang

et al. 2023

Macromol. Rapid Commun.

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Time-of-flight neutron reflectometry (ToF-NR) performed under different relative humidity conditions demonstrates that polymer brushes constituted by hydrophilic, cyclic macromolecules exhibit a more compact conformation with lower roughness as compared to linear brush analogues, due to the absence of dangling chain ends extending at the polymer-vapor interface. In addition, cyclic brushes feature a larger swelling ratio and an increased solvent uptake with respect to their linear counterparts as a consequence of the increased interchain steric repulsions. It is proposed that differences in swelling ratios between linear and cyclic brushes come from differences in osmotic pressure experienced by each brush topology. These differences stem from entropic constraints. The findings suggest that to correlate the equilibrium swelling ratios at different relative humidity for different topologies a new form of the Flory-like expression for equilibrium thicknesses of grafted brushes is needed.

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