Computer Study of the Association Behavior of Gradient Copolymers: Analysis of Simulation Results Based on a New Algorithm for Recognition and Classification of Aggregates

Abstract

We present a computer study of the association behavior of copolymer chains with a gradient part and soluble tail of variable length. As a simulation method we use dynamic Monte Carlo simulation on a simple cubic lattice with pair interaction parameters. The solvent quality and selectivity is modeled by the variation of pair interaction parameters between nearest neighbors on the lattice. The role of the length of soluble part in the self‐assembly and its effect on the structure of aggregates was the main goal of this work. The size and structure of aggregates were analyzed using an improved topological classification method which has been developed and tested in the present study. The structure and association numbers of aggregates were compared with those of linear diblock copolymers.

Poly(2-oxazoline)-Based Amphiphilic Gradient Copolymers as Nanocarriers for Losartan: Insights into Drug–Polymer Interactions

“…Specifically, some of the solvophilic units may be integrated in the core while some solvophobic units may be distributed in the corona. Thus, GCs usually possess greater solubility than the corresponding BCs [18,20,21], slower micellization process [22] and a lower value of the aggregation number [19,23], reflecting a smaller size according to DLS [24].…”

Collapse transitions in thermosensitive multi-block copolymers: A Monte Carlo study

“…Towards this end, computer simulations have recently made substantial strides 4,19,20,21,22,23,24,25,26,27,28,29,30,31 focusing on solutions of linear multiblock copolymers of the (A n B n ) m type, where n is the degree of polymerization of each block and m is the number of blocks. Systematic explorations within the large parameter space established quantitative relations on how copolymer architecture and intermolecular interactions determine the macroscopic phase behavior and the related chain conformations changes.…”

Understanding and controlling the structure of thin polymer films used in photolithography

“…Extensive studies of the association behaviour of gradient copolymers in selective solvents have been reported over the past few years [98,99,105,164,204,[219][220][221][222][223][224][225][226]. A significant finding was that gradient copolymers have higher solubility than the corresponding diblock copolymers leading to significantly higher values of the CMC [173,222,227].…”

“…A significant finding was that gradient copolymers have higher solubility than the corresponding diblock copolymers leading to significantly higher values of the CMC [173,222,227]. Monte Carlo (MC) simulations have been employed to study the self-assembly of gradient copolymers, which differs with respect to the steepness of the gradient of the local composition along the chain [225]. It was demonstrated that the association behaviour does not depend solely on the net composition of the copolymers, but also on the sequence of monomer units [228].…”

“…It was demonstrated that the association behaviour does not depend solely on the net composition of the copolymers, but also on the sequence of monomer units [228]. In contrast to the diblock copolymers, which form welldefined spherical micelles in selective solvents, gradient copolymers often associate into aggregates with ill-defined shapes and a wide size distribution [108,225]. Using SCF theory, Shull [82] predicted that gradient copolymers should exhibit a substantially higher CMC than those of block copolymers of similar molecular weight and composition, and this was later experimentally confirmed by Torkelson and co-workers [173] for St/MMA copolymers.…”