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.g., polymer or nanoparticle scaffolds), the degree of multivalency is difficult to predict or control, as sufficiently large scaffolds inherently preclude separated supramolecular moieties from interacting. Because molecular models commonly used to examine supramolecular interactions are intrinsically unable to examine any trends or emergent behaviors that arise due to nanoscale scaffold geometry, our understanding of the thermodynamics of these massively multivalent systems remains limited. Here we address this challenge via the coassembly of polymer-grafted nanoparticles and multivalent polymers, systematically examining how multivalent scaffold size, shape, and spacing affect their collective thermodynamics. Investigating the interplay of polymer structure and supramolecular group stoichiometry reveals complicated but rationally describable trends that demonstrate how the supramolecular scaffold design can modulate the strength of multivalent interactions. This approach to self-assembled supramolecular materials thus allows for the manipulation of polymer-nanoparticle composites with controlled thermal stability, nanoparticle organization, and tailored meso- to microscopic structures. The sophisticated control of multivalent thermodynamics through precise modulation of the nanoscale scaffold geometry represents a significant advance in the ability to rationally design complex hierarchically structured materials via self-assembly.

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. Here, we present a method for embedding colloidal nanoparticle superlattices into a polymer gel matrix. This encapsulation strategy physically prevents the nanoparticles from dissociating upon heating, drying, or the introduction of chemicals that would normally disrupt the lattice. However, the use of a gel as the embedding medium still permits further modification of the colloidal nanoparticle lattice by introducing stimuli that deform the gel network (as this deformation in turn alters the nanoparticle lattice structure in a predictable manner). Moreover, encapsulation of the lattice within a gel permits further stabilization into fully solid materials by removing the solvent from the gel or by replacing the solvent with a liquid monomer that can be photopolymerized. This embedding method therefore makes it possible to incorporate ordered colloidal arrays into a polymer matrix as either dynamic or static structures, expanding their potential for use in responsive materials.

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. Thermal cross-linking of self-suspended polymer grafted nanoparticles is used to prepare highly filled (>50 vol %) macroscopic nanocomposites with homogeneously dispersed, non-percolating alumina particles in an organic matrix. The initial composites use low glass transition temperature polymer grafts and thus are flexible and easily shaped by thermoforming methods. However, after thermal aging, the resulting materials display high stiffness (>10 GPa) and enhanced thermal conductivity (>100% increase) and also possess mechanical strength similar to commodity plastics. Moreover, the covalent bonding between matrix and filler allows for the significant elevation of thermal conductivity despite the extensive interfacial area in the nanocomposite. The thermal aging of polymer grafted nanoparticles is therefore a promising method for producing easily processable, mechanically sturdy, and macroscopic nanocomposites with improved thermal conductivity.

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. This work demonstrates that brush polymer topology provides a useful means to control gelation kinetics without the need to manipulate polymer composition or crosslinking chemistry. The unique architecture of brush polymers also results in restrained or even nonswelling behavior at different temperatures, regardless of the polymer concentration. Brush polymers therefore are an interesting tool for examining how high-functionality polymer building blocks can affect structure-property relationships and chemical kinetics in hydrogel materials, and also provide a useful rapidly-setting hydrogel platform with tunable properties and great potential for multiple material applications.

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. Thus, these methods limit the application of DNA-assembled structures as dynamic and programmable material components. Here, a method is presented to resolve these drawbacks for DNA-grafted nanoparticles, also known as Programmable Atom Equivalents (PAEs), by embedding assembled lattices within a hydrogel matrix. The preformed lattices are exposed to polymerizable residues that electrostatically bind to the charged backbone of the DNA ligands and form a continuous, permeating gel network that stabilizes the colloidal crystals upon introduction of a radical initiator. After embedding PAEs in a hydrogel, deformation of the macroscopic matrix results in concomitant deformation of the PAE lattices, allowing superlattice structural changes to be induced by chemical methods (such as changing solute concentration to alter swelling pressure) or by application of mechanical strain. Changes to the structure of the PAE lattices are reversible and repeatable over multiple cycles and can be either isotropic (such as by swelling) or anisotropic (such as by mechanical deformation). This method of embedding nanoparticle crystals inside of a flexible and environmentally responsive hydrogel is therefore a useful tool in extending the utility of PAEs and other micro- and nanostructures assembled with DNA.

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. Here, we present a suite of rationally designed NCT systems, where multiple types of supramolecular interactions (hydrogen bonding, metal complexation, and dynamic covalent bond formation) are used to tune NCT assembly as a function of multiple external stimuli including temperature, small molecules, pH, and light. Furthermore, the incorporation of multiple orthogonal supramolecular chemistries in a single NCT system makes it possible to dictate the morphologies of the assembled NCTs in a pathway-dependent fashion. Finally, multistimuli responsive NCTs enable the modification of composite properties by postassembly functionalization, where NCTs linked by covalent bonds with significantly enhanced stability are obtained in a fast and efficient manner. The designs presented here therefore provide major advancement for the field of composite synthesis by establishing a framework for synthesizing hierarchically ordered composites capable of complicated assembly behaviors.