Automated Parameterization of Coarse-Grained Polyethylenimine Under Martini Framework

Abstract

As a versatile polymer in many applications, synthesized polyethylenimine (PEI) is polydisperse with diverse branched structures that attain pH-dependent protonation states. Understanding the structure-function relationship of PEI is necessary for enhancing its efficacy in various applications. Coarse-grained (CG) simulations can be performed at length- and timescales directly comparable with experimental data while maintaining the molecular perspective. However, manually developing CG forcefields for complex PEI structures is time-consuming and prone to human errors. This article presents a fully automated algorithm that can coarse-grain any branched architecture of PEI from its all-atom (AA) simulation trajectories and topology. The algorithm is demonstrated by coarse-graining a branched 2 kDa PEI, which can replicate the AA diffusion coefficient, radius of gyration, and end-to-end distance of the longest linear chain. Commercially available 25 kDa and 2 kDa Millipore-Sigma PEIs are used for experimental validation. Specifically, branched PEI architectures are proposed, coarse-grained using the automated algorithm, and then simulated at different mass concentrations. The CG-PEIs can reproduce existing experimental data on PEI’s diffusion coefficient and Stokes-Einstein radius at infinite dilution, as well as its intrinsic viscosity. This suggests a strategy where probable chemical structures of synthetic PEIs can be inferred computationally using the developed algorithm. The coarse-graining methodology presented here can also be extended to other polymers.