Abstract
Chemical and topographic surface patterning of inorganic polymer-functionalized nanoparticles (NPs) and their self-assembly in nanostructures with controllable architectures enable the design of new NP-based materials. Capping of NPs with inorganic polymer ligands, such as metallopolymers, can lead to new synergetic properties of individual NPs or their assemblies, and enhance NP processing in functional materials. Here, for gold NPs functionalized with polyferrocenylsilane, two distinct triggers are used to induce attraction between the polymer ligands and achieve NP self-assembly or topographic surface patterning of individual polymer-capped NPs. Control of polymer-solvent interactions is achieved by either changing the solvent composition or by the electrooxidation of polyferrocenylsilane ligands. These results expand the range of polymer ligands used for NP assembly and patterning, and can be used to explore new self-assembly modalities. The utilization of electrochemical polymer oxidation stimuli at easily accessible potentials broadens the range of stimuli leading to NP self-assembly and patterning.
Highlights
Polymer-functionalized nanoparticles (NPs) have a broad range of applications, including colloidal stabilization,[1] chemical and biological sensing,[2] imaging,[3] and medical diagnostics and therapeutics.[4]
We explored the SA and surface patterning (SP) approaches for NPs capped with a metallopolymer ligand which combines the properties of metals with the desirable ease of polymer processing.[15]
The latter was prepared in two steps which involved i) termination of living anionic PFDMS with a chloro(vinyl)silane followed by ii) attachment of the thiol group via a photochemically mediated thiol-ene “Click” reaction
Summary
Polymer-functionalized nanoparticles (NPs) have a broad range of applications, including colloidal stabilization,[1] chemical and biological sensing,[2] imaging,[3] and medical diagnostics and therapeutics.[4]. [6] Self-assembly enables the organization of NPs into nanostructures with increasingly complex architectures, which exhibit new collective optical, magnetic or electronic properties[7] due to the coupling of properties of individual NPs. Patterning of NPs with chemically and/or topographically distinct surface regions renders directionality in their interactions and self-assembly and can be used to explore new SA modes, generate colloidal surfactants[5] and produce templates for the synthesis of multicomponent, hybrid NPs. [6] Self-assembly enables the organization of NPs into nanostructures with increasingly complex architectures, which exhibit new collective optical, magnetic or electronic properties[7] due to the coupling of properties of individual NPs Both SA and SP can be realized for NPs capped with end-tethered polymer chains by tuning the relationship between the polymer conformational entropy and the enthalpy of its interactions with a solvent.[8] When a polymer-functionalized NP is transferred from a good to a poor solvent, polymer ligands collapse and associate with each other to reduce the free energy of the system. At a sufficiently high NP concentration, a reduction in solvent quality leads to the association of polymer ligands on proximal NPs and the formation of interparticle physical bonds, thereby producing self-assembled nanostructures.[6,9,10] Tuning the molecular weight and the grafting density of the polymer ligands, as well as the quality of the solvent enables control over interparticle spacing in the nanostructures, the characteristics that is important in chemical and biological sensing.[11,12]
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