Rationally Designing the Supramolecular Interfaces of Nanoparticle Superlattices with Multivalent Polymers.

In supramolecular materials, multiple weak binding groups can act as a single collective unit when confined to a localized volume, thereby producing strong but dynamic bonds between material building blocks. This principle of multivalency provides a versatile means of controlling material assembly, as both the number and the type of supramolecular moieties become design handles to modulate the strength of intermolecular interactions. However, in materials with building blocks significantly larger than individual supramolecular moieties (e.

Improving nanoparticle superlattice stability with deformable polymer gels.

The self-assembly of colloidal nanoparticles into ordered superlattices typically uses dynamic interactions to govern particle crystallization, as these non-permanent bonds prevent the formation of kinetically trapped, disordered aggregates. However, while the use of reversible bonding is critical in the formation of highly ordered particle arrangements, dynamic interactions also inherently make the structures more prone to disassembly or disruption when subjected to different environmental stimuli. Thus, there is typically a trade-off between the ability to initially form an ordered colloidal material and the ability of that material to retain its order under different conditions.

Polymer Grafted Nanoparticle Composites with Enhanced Thermal and Mechanical Properties.

The distribution of filler particles within a polymer matrix nanocomposite has a profound influence on the properties and processability of the material. While filler aggregation and percolation can significantly enhance particular functionalities such as thermal and electrical conductivity, the formation of larger filler clusters and networks can also impair mechanical properties like strength and toughness and can also increase the difficulty of processing. Here, a strategy is presented for the preparation of functional composites that enhance thermal conductivity over polymer alone, without negatively affecting mechanical performance or processability.

Crosslinking of Pressure-Sensitive Adhesives with Polymer-Grafted Nanoparticles.

Nanocomposite filler particles provide multiple routes to mechanically reinforce pressure-sensitive adhesives (PSAs), as their large surface area to volume ratios provide a means of effectively crosslinking multiple polymer chains. A major advancement could therefore be enabled by the design of a particle architecture that forms multiple physical and chemical interactions with the surrounding polymer matrix, while simultaneously ensuring particle dispersion and preventing particle aggregation. Understanding how such multivalent interactions between a nanoparticle crosslinking point and the PSA polymer affect material mechanical performance would provide both useful scientific knowledge on the mechanical structure-property relationships in polymer composites, as well as a new route to synthesizing useful PSA materials.

Design and Synthesis of Quick Setting Nonswelling Hydrogels via Brush Polymers.

Brush polymers have emerged as components of novel materials that show huge potential in multiple disciplines and applications, including self-assembling photonic crystals, drug delivery vectors, biomimetic lubricants, and ultrasoft elastomers. However, an understanding of how this unique topology can affect the properties of highly solvated materials like hydrogels remain under investigated. Here, it is investigated how the high functionality and large overall size of brush polymers enhances the gelation kinetics of low polymer weight percent gels, enabling 100-fold faster gelation rates and 15-fold higher stiffness values than gels crosslinked by traditional star polymers of the same composition and polymer chain length.

Dynamic Manipulation of DNA-Programmed Crystals Embedded in a Polyelectrolyte Hydrogel.

DNA is a powerful tool for programming the three-dimensional organization of nanomaterials, where the specificity of nucleotide base-pairing can enable precise, complex, and dynamically addressable structures like colloidal crystals. However, because these DNA-programmed materials are often only stable in solution, their organization can be easily disrupted by changes to its local environment. Methods to stabilize these materials have been developed, but often come at the expense of altering or permanently fixing the materials' structures, removing many of the benefits of using DNA interactions to program assembly.

Multistimuli Responsive Nanocomposite Tectons for Pathway Dependent Self-Assembly and Acceleration of Covalent Bond Formation.

Nanocomposite tectons (NCTs) are a recently developed building block for polymer-nanoparticle composite synthesis, consisting of nanoparticle cores functionalized with dense monolayers of polymer chains that terminate in supramolecular recognition groups capable of linking NCTs into hierarchical structures. In principle, the use of molecular binding to guide particle assembly allows NCTs to be highly modular in design, with independent control over the composition of the particle core and polymer brush. However, a major challenge to realize an array of compositionally and structurally varied NCT-based materials is the development of different supramolecular bonding interactions to control NCT assembly, as well as an understanding of how the organization of multiple supramolecular groups around a nanoparticle scaffold affects their collective binding interactions.