All-Atom Molecular Dynamics Simulations of Grafted Poly(N,N-dimethylaminoethyl methacrylate) Brushes

Author(s)

Simon Tippner, David Hernández-Castillo, Felix H. Schacher, Leticia González

Abstract

Modeling polymer brushes is essential for understanding their complex behavior at surfaces and interfaces, enabling the design of materials with tunable properties. We present a computational protocol to model polymer brushes composed of grafted, brush-like chains of the charged polymer poly(N,N-dimethylaminoethyl methacrylate) (p(DMAEMA)) using an all-atom representation that captures detailed molecular interactions and structural properties. The approach is flexible and non-grid-based and allows for randomized strand configurations and the incorporation of periodic boundary conditions, enabling the construction of asymmetric polymer brush setups. An atactic p(DMAEMA) configuration is demonstrated as an example, though the protocol can be readily adapted to construct other brush-like polymer systems with varying tacticities or compositions, depending on the pH environment. Furthermore, this can be extended to stimuli-responsive materials, which generate conformation or charge upon changes in pH value or other external triggers. Molecular dynamics simulations are then employed to gain insights into the conformational behavior of the grafted p(DMAEMA) brushes and their surrounding aqueous environment, as well as their response to temperature, protonation, and variations in grafting densities, in terms of the solvent-accessible surface area, radius of gyration, and radial distribution functions. This versatile protocol provides a robust tool for simulating and analyzing the properties of diverse polyelectrolyte polymer brush systems and also as composite materials.

Organisation(s)

Department of Theoretical Chemistry, Research Platform Accelerating Photoreaction Discovery

External organisation(s)

Vienna Doctoral School in Chemistry (DoSChem), Friedrich-Schiller-Universität Jena

Journal

Journal of Physical Chemistry B

Volume

129

Pages

2105-2114

No. of pages

10

ISSN

1520-6106

DOI

https://doi.org/10.1021/acs.jpcb.4c07928

Publication date

02-2025

Peer reviewed

Yes

Austrian Fields of Science 2012

104017 Physical chemistry, 104022 Theoretical chemistry

ASJC Scopus subject areas

Physical and Theoretical Chemistry, Surfaces, Coatings and Films, Materials Chemistry

Portal url

https://ucrisportal.univie.ac.at/en/publications/da822069-282d-4e54-a8e4-f43f5693667d