Discreteness and dispersity in the design of polymeric materials

Abstract

Nature produces macromolecules with discrete molar mass and precise composition, both of which are essential for ensuring structural control, distinctive properties, and specific functions. However, in some cases, bioderived components are heterogeneous in size, and this plays a crucial role in defining their physicochemical characteristics. In a similar way, polymer scientists have been striving to develop robust synthetic protocols to access macromolecules with homogeneous composition and discrete molar mass. Simultaneously, significant advances in controlled polymerization techniques have enabled the precise regulation of chain length heterogeneity, or dispersity (Đ), across a wide range of values. Achieving perfectly monodisperse polymers is not only a remarkable synthetic achievement but also provides fundamental building blocks for new classes of polymeric materials. These materials could be either free of defects or exhibit properties that are precisely tunable in a quantized manner. On the other hand, obtaining polymer samples with controlled dispersity provides an additional tuning parameter for the physicochemical properties of a variety of materials formulations. By leveraging macromolecular discreteness and fine-tuning polymer dispersity, we have expanded the toolbox for designing advanced “soft” materials. Block copolymers with discrete segment lengths or controlled dispersity can be used to create novel nanostructured materials. Stimuli-responsive polymeric systems can be engineered to precisely adjust their physical transitions while maintaining a constant chemical composition. In addition, tailoring polymer dispersity during the fabrication of gels and brush coatings enhances the ability to fine-tune their physicochemical properties, further broadening their potential applications.