A Tunable, Particle-Based Model for the Diverse Conformations Exhibited by Chiral Homopolymers

• Published in: Macromolecules 2022-08, Vol.55 (15), p.6321-6331
• Main Authors: Buchanan, Natalie, Provenzano, Joules, Padmanabhan, Poornima
• Format: Article
• Language: English
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/acs.macromol.2c00613

Chiral block copolymers capable of hierarchical self-assembly can also exhibit chirality transferthe transfer of chirality at the monomer or conformational scale to the self-assembly. Prior studies focused on experimental and theoretical methods that are unable to fully decouple the thermodynamic origins of chirality transfer and necessitate the development of particle-based models that can be used to quantify intrachain, interchain, and entropic contributions. With this goal in mind, in this work, we developed a parametrized coarse-grained model of a chiral homopolymer and extensively characterized the resulting conformations. Specifically, the energetic parameter in the angular and dihedral potentials, the angular set point, and the dihedral set point are systematically varied to produce a wide range of conformations from a random coil to a nearly ideal helix. The average helicity, pitch, persistence length, and end-to-end distance are measured, and correlations between the model parameters and resulting conformations are obtained. Using available experimental data on model polypeptoid-based chiral polymers, we back out the required parameters that produce similar pitch and persistence length ratios reported in the experiments. The conformations for the experimentally matched chains appear to be somewhat flexible, exhibiting some helical turns. Our model is versatile and can be used to perform molecular dynamics simulations of chiral block copolymers and even sequence-specific polypeptides to study their self-assembly and to gain thermodynamic insights.