Macromolecular self-assembly is essential in life and interfacial science. A macromolecule consisting of chemically distinct components tends to self-assemble in a selective solvent to minimize the exposure of the solvophobic segments to the medium while the solvophilic segments adopt extended conformations. While micelles composed of linear block copolymers represent classic examples of such solution assembly, recent interest focuses on the self-assembly of complex macromolecules with nonlinear architectures, such as star, graft, and bottlebrush. Such macromolecules include several to hundreds of polymer chains covalently tied to a core and a backbone. The pre-programmed, non-exchangeable chain arrangement makes a huge difference in their self-assembly. The field has witnessed tremendous advances in synthetic methodologies to construct the desired architectures, leading to discoveries of exotic self-assembly behavior. Thanks to the rapid evolution of computing power, computer simulation has also been an emerging and complementary approach for understanding the association mechanism and further predicting the self-assembling morphologies. However, simulating the self-assembly of architected macromolecules has posed a challenge as a huge number of objects should be included in the simulations. Comparing experimental results with simulations is not always straightforward, as synthetic routes to well-defined model systems with systematically controlled structural parameters are not often available. In this manuscript, we propose to bridge a gap between experiments and simulations in self-assembly of architected macromolecules. We focus on the key articles in this area reporting experimental evidence and simulation details and also cover recent examples in the literature. We start with discussing simulation methodologies applicable to investigate solution self-assembly across multiple levels of chemical resolution from all-atom to particle dynamics. Then, we delve into topological design, synthesis, and simulation of nonlinear macromolecules, including dendritic/star, network, and graft/bottlebrush polymers, to understand the architectural effect on the self-assembly behavior. We expand our discourse to embrace recent advances toward realizing more complex systems. For example, self-assembly in the presence of strong Coulombic interactions, such as in the case of polyelectrolytes, geometric constraints, and other components in solutions, exemplified by inorganic fillers, are introduced. Finally, the challenges and perspectives are discussed in the final section of the manuscript.

Bottlebrush polymers (BBPs) are a type of comb-like macromolecule with densely grafted polymeric sidechains attached to the polymer backbones, and many intriguing properties and applications have been demonstrated due to their unique architecture. Moreover, a ring-opening metathesis polymerization (ROMP) technique using Grubbs catalysts allows a precise control of various structural parameters in BBPs, such as the sidechain length, backbone length, and sidechain microstructures. This review mainly highlights recent advances of BBPs prepared by ROMP, from synthesis efforts to properties and applications.

We developed a methodology, inspired by the folding of proteins, for the precision synthesis of hairy polymer nanoparticles. High-molar mass and narrowly dispersed graft copolymers were synthesized by graft-through ring opening metathesis polymerization, to incorporate a designated number of side chains and dimerizable cinnamic acid groups. Intrachain photodimerization collapsed the backbone and arrested it into a compact globular conformation, resulting in hairy nanoparticles topologically equivalent to a core cross-linked star polymer. The single-chain collapse process translates the molecular information written on the 1D graft copolymer into the 3D globular polymer nanoparticle, like protein folding. Unprecedented control over structural parameters was achieved, including the length, number, and composition of the side chains as well as cross-linking density. Different side chains formed distinct subdomains in the sterically congested nanoparticle state and further self-assembled into micellar aggregates in a selective solvent. Both experimental observations and computational simulations indicated that preorganization of the side chains in the block sequence produces subdomains which primarily follow the backbone length scale, while random sequences showed side chain-dependent scaling. Polymer nanoparticles with discrete multiple subdomains were produced by folding of the ternary block graft copolymers. Drastic differences in the self-assembly behavior of ABC- and ACB-sequenced nanoparticles indicate that the spatial organization of subdomains can be achieved by sequence control.