Intra-Globular Structures in Multiblock Copolymer Chains from a Monte Carlo Simulation

TL;DR

This study uses Monte Carlo simulations to explore the diverse intra-globular structures of multiblock copolymer chains in nonselective solvents, revealing phase behavior and potential experimental correlations.

Contribution

It introduces a detailed Monte Carlo simulation approach to characterize intra-globular structures and phase diagrams of multiblock copolymers with various architectures.

Findings

Multiple intra-globular structures identified, including diclusters, triclusters, and n-clusters.

Phase diagrams mapped in the temperature-compatibility space.

Structure factor calculations relate simulation results to scattering experiments.

Abstract

Multiblock copolymer chains in implicit nonselective solvents are studied by Monte Carlo method which employs a parallel tempering algorithm. Chains consisting of 120 $A$ and 120 $B$ monomers, arranged in three distinct microarchitectures: $(10-10)_{12}$, $(6-6)_{20}$, and $(3-3)_{40}$, collapse to globular states upon cooling, as expected. By varying both the reduced temperature $T^*$ and compatibility between monomers $\omega$, numerous intra-globular structures are obtained: diclusters (handshake, spiral, torus with a core, etc.), triclusters, and $n$-clusters with $n>3$ (lamellar and other), which are reminiscent of the block copolymer nanophases for spherically confined geometries. Phase diagrams for various chains in the $(T^*, \omega)$-space are mapped. The structure factor $S(k)$, for a selected microarchitecture and $\omega$, is calculated. Since $S(k)$ can be measured in scattering experiments, it can be used to relate simulation results to an experiment. Self-assembly in those systems is interpreted in term of competition between minimization of the interfacial area separating different types of monomers and minimization of contacts between chain and solvent. Finally, the relevance of this model to the protein folding is addressed.