Sequence Dependence of Critical Properties for 2-letter Chains

TL;DR

This study investigates how the sequence of monomers in 2-letter chains influences their critical phase separation properties using advanced Monte Carlo simulations, revealing sequence-dependent variations and implications for biomolecular and synthetic polymer design.

Contribution

It provides the first detailed analysis of sequence dependence on critical properties of 2-letter chains, with high-accuracy critical point data and insights into sequence effects.

Findings

Mixed blocks lower critical temperature and volume fraction.

Adding solvophilic segments decreases critical parameters.

Sequence variations cause significant differences in critical properties.

Abstract

Histogram-reweighting grand canonical Monte Carlo simulations are used to obtain the critical properties of lattice chains composed of solvophilic and solvophobic monomers. The model is a modification of one proposed by Larson \emph{et al.} [J. Chem. Phys. 83, 2411 (1985)], lowering the ``contrast'' between beads of different type to prevent aggregation into finite-size micelles that would mask true phase separation between bulk high- and low-density phases. Oligomeric chains of length between 5 and 24 beads are studied. Mixed-field finite-size scaling methods are used to obtain the critical properties with typical relative accuracies of better than $10^{-4}$ for the critical temperature and $10^{-3}$ for the critical volume fraction. Diblock chains are found to have lower critical temperatures and volume fractions relative to the corresponding homopolymers. Addition of solvophilic blocks of increasing length to a fixed-length solvophobic segment results in a decrease of both critical temperature and critical volume fraction, with an eventual slow asymptotic approach to the long-chain limiting behavior. Moving a single solvophobic or solvophilic bead along a chain leads to a minimum or maximum in the critical temperature, with no change in critical volume fraction. Chains of identical length and composition have a significant spread in their critical properties, depending on their precise sequence. The present study has implications on understanding biomolecular phase separation and for developing design rules for synthetic polymers with specific phase separation properties. It also provides data potentially useful for the further development of theoretical models for polymer and surfactant phase behavior.