Polymer-Tethered Nanoparticles: From Surface Engineering to Directional Self-Assembly.

Current interest in nanoparticle ensembles is motivated by their collective synergetic properties that are distinct from or better than those of individual nanoparticles and their bulk counterparts. These new advanced optical, electronic, magnetic, and catalytic properties can find applications in advanced nanomaterials and functional devices, if control is achieved over nanoparticle organization. Self-assembly offers a cost-efficient approach to produce ensembles of nanoparticles with well-defined and predictable structures. Nanoparticles functionalized with polymer molecules are promising building blocks for self-assembled nanostructures, due to the comparable dimensions of macromolecules and nanoparticles, the ability to synthesize polymers with various compositions, degrees of polymerization, and structures, and the ability of polymers to self-assemble in their own right. Moreover, polymer ligands can endow additional functionalities to nanoparticle assemblies, thus broadening the range of their applications.In this Account, we describe recent progress of our research groups in the development of new strategies for the self-assembly of nanoparticles tethered to macromolecules. At the beginning of our journey, we developed a new approach to patchy nanoparticles and their self-assembly. In a thermodynamically driven strategy, we used poor solvency conditions to induce homopolymer surface segregation in pinned micelles (patches). Patchy nanoparticles underwent self-assembly in a well-defined and controlled manner. Following this work, we overcame the limitation of low yield of the generation of patchy nanoparticles, by using block copolymer ligands. For block copolymer-capped nanoparticles, patch formation and self-assembly were "staged" by using distinct stimuli for each process. We expanded this work to the generation of patchy nanoparticles via dynamic exchange of block copolymer molecules between the nanoparticle surface and micelles in the solution. The scope of our work was further extended to a series of strategies that utilized the change in the configuration of block copolymer ligands during nanoparticle interactions. To this end, we explored the amphiphilicity of block copolymer-tethered nanoparticles and complementary interactions between reactive block copolymer ligands. Both approaches enabled exquisite control over directional and self-limiting self-assembly of complex hierarchical nanostructures. Next, we focused on the self-assembly of chiral nanostructures. To enable this goal, we attached chiral molecules to the surface of nanoparticles and organized these hybrid building blocks in ensembles with excellent chiroptical properties. In summary, our work enables surface engineering of polymer-capped nanoparticles and their controllable and predictable self-assembly. Future research in the field of nanoparticle self-assembly will include the development of effective characterization techniques, the synthesis of new functional polymers, and the development of environmentally responsive self-assembly of polymer-capped nanoparticles for the fabrication of nanomaterials with tailored functionalities.

Electrostatic Adsorption Behaviors of Charged Polymer-Tethered Nanoparticles on Oppositely Charged Surfaces.

Polymer-grafted hairy nanoparticles (HNPs) that combine the unique properties of inorganic nanoparticles (NPs) and polymers are attractive building blocks for the layer-by-layer assembly of functional hybrid materials, but the adsorption behaviors of HNPs on substrates remain unclear. This article describes a systematic study on the adsorption behaviors of charged polymer-grafted HNPs on oppositely charged substrates in different solvent media via a combination of experiments and simulations. It is shown in simulations that the adsorption process of HNPs is associated with the release of counterions around charged polymers on HNPs, thus resulting in a higher energy barrier of NP adsorption than bare NPs without charged polymer tethers. This energy barrier decreases with decreasing the dielectricity of solvents or ionization degree of grafted polymers or increasing ionic strength of the solution. Furthermore, the theoretical prediction is confirmed in experiments by using a model system of poly(acrylic acid)-grafted silica NPs and poly(diallyldimethylammonium chloride)-modified wafers. The work provides guidance for the electrostatic assembly of HNPs into functional hybrid composites with applications in membranes, optical devices, and biomedicines.