Nanoparticle-regulated phase behavior of ordered block copolymers

This document is the accepted manuscript version of a published article. Published by The Royal Society of Chemistry in the journal "Soft Matter" issue 8, DOI: 10.1039/b805540hAlthough block copolymer motifs have received considerable attention as supramolecular templates for inorganic nanoparticles, experimental observations of a nanostructured diblock copolymer containing inorganic nanoparticles—supported by theoretical trends predicted from a hybrid self-consistent field/density functional theory—confirm that nanoparticle size and selectivity can likewise stabilize the copolymer nanostructure by increasing its order– disorder transition temperature.Research Council of Norway under the NANOMAT Program Los Alamos National Laboratory || Contract No. DE-AC52-06NA25396 NSERC of Canada GEM Fellowship and a NOBCChE Procter and Gamble Fellowship

Nanoparticle Network Formation in Nanostructured and Disordered Block Copolymer Matrices

Incorporation of nanoparticles composed of surface-functionalized fumed silica (FS) or native colloidal silica (CS) into a nanostructured block copolymer yields hybrid nanocomposites whose mechanical properties can be tuned by nanoparticle concentration and surface chemistry. In this work, dynamic rheology is used to probe the frequency and thermal responses of nanocomposites composed of a symmetric poly(styrene-b-methyl methacrylate) (SM) diblock copolymer and varying in nanoparticle concentration and surface functionality. At sufficiently high loading levels, FS nanoparticle aggregates establish a load-bearing colloidal network within the copolymer matrix. Transmission electron microscopy images reveal the morphological characteristics of the nanocomposites under these conditions

Dynamic Assembly of Ultrasoft Colloidal Networks Enables Cell Invasion Within Restrictive Fibrillar Polymers

In regenerative medicine, natural protein-based polymers offer enhanced endogenous bioactivity and potential for seamless integration with tissue, yet form weak hydrogels that lack the physical robustness required for surgical manipulation, making them difficult to apply in practice. The use of higher concentrations of protein, exogenous cross-linkers, and blending synthetic polymers has all been applied to form more mechanically robust networks. Each relies on generating a smaller network mesh size, which increases the elastic modulus and robustness, but critically inhibits cell spreading and migration, hampering tissue regeneration. Here we report two unique observations; first, that colloidal suspensions, at sufficiently high volume fraction (ϕ), dynamically assemble into a fully percolated 3D network within high-concentration protein polymers. Second, cells appear capable of leveraging these unique domains for highly efficient cell migration throughout the composite construct. In contrast to porogens, the particles in our system remain embedded within the bulk polymer, creating a network of particle-filled tunnels. Whereas this would normally physically restrict cell motility, when the particulate network is created using ultralow cross-linked microgels, the colloidal suspension displays viscous behavior on the same timescale as cell spreading and migration and thus enables efficient cell infiltration of the construct through the colloidal-filled tunnels