100th Anniversary of Macromolecular Science Viewpoint: Opportunities in the Physics of Sequence-Defined Polymers

Abstract

Polymer science has been driven by ever-increasing molecular complexity, as polymer synthesis expands an alreadyvast palette of chemical and architectural parameter space. Copolymers represent a key example, where simple homopolymers have given rise to random, alternating, gradient, and block copolymers. Polymer physics has provided the insight needed to explore this monomer sequence parameter space. The future of polymer science, however, must contend with further increases in monomer precision, as this class of macromolecules moves ever closer to the sequence-monodisperse polymers that are the workhorses of biology. The advent of sequence-defined polymers gives rise to opportunities for material design, with increasing levels of chemical information being incorporated into long-chain molecules; however, this also raises questions that polymer physics must address. What properties uniquely emerge from sequence-definition? Is this circumstance dependent? How do we define and think about sequence dispersity? How do we think about a hierarchy of sequence effects? Are more sophisticated characterization methods, as well as theoretical and computational tools needed to understand this class of macromolecules? The answers to these questions touch on many difficult scientific challenges, setting the stage for a rich future for sequence-defined polymers in polymer physics.

Recent progress in the science of complex coacervation

“…4 Understanding and mimicking these systems has thus become an active area of research, due not only to the impliciations in biophysics, but in a more fundamental aspiration to control polymer structure and function via monomer sequence. 252…”

Recent Advances in the Synthesis and Application of Polymer Compartments for Catalysis

“…Sequence-defined polymers have emerged over the last couple of years, where monomers are positioned along the polymer chain with single monomer precision [ 71 ]. Both concepts, sequence-defined polymers and single chain polymer nanoparticles, follow a related aim, i.e., to mimic the ability of proteins to fold into defined 3D nanostructures providing polymer materials with unique physical properties [ 72 ]. Introducing catalytic moieties into sequence-defined polymers could bring us even closer to protein and enzyme mimetic catalysts.…”

Spatiotemporal Formation Kinetics of Polyelectrolyte Complex Micelles with Millisecond Resolution

“…Furthermore, the formation kinetics may be strongly dependent on the chemical nature of the polymer constituents themselves. Charged heteropolymers and sequence-defined macromolecules give rise to distinct hierarchical assemblies at equilibrium, 43 depending on the local interactions and sequence variation of the primary structure. By extension, the dynamics of PEC micelle formation, chain exchange, and equilibration are also likely highly influenced by how oppositely-charged polyelectrolytes associate at the molecular level.…”