Robust hybrid nanostructures comprising gold and thiol-functionalized polymer nanoparticles: facile preparation, diverse morphologies and unique properties

Abstract

Nanohybrids are generated via covalent integration of Au nanoparticles (NPs) with thiolfunctionalized crosslinked polymer NPs. The polymer NPs have been readily prepared by the controlled intramolecular crosslinking of long-chain highly branched polymers through the thiol-ene reaction in dilute solution, and the thiol groups on polymer NPs can be introduced and tailored by alternating the cross linkers with various thiol functionalities, which facilitates the further fabricatation of nanohybrids with different loadings of Au NPs. The structures and optical properties of these nanostructures are characterized by elemental analysis, IR, NMR, XPS, XRD, and UV-vis measurements. The morphologies of nanostructures are investigated via dynamic light scattering, atom force microscopy, transmission electron microscopy, and cryogenic transmission electron microscopy. The results reveal that the crosslinked polymer NPs have an average diameter of 45 nm, and Au NPs in the nanohybrids are isolated and distributed throughout the surface of the polymer NPs. When varying the concentrations, the hybrid nanostructures display diverse morphologies going through nanosphere, chainlike assembly and nanorod, accompanied with unique optical properties. Additionally, this type of hybrid nanostructure has high stability and recoverability in catalysis, and shows excellent efficiency for the reduction of nitro compounds.

Survey of Plasmonic Nanoparticles: From Synthesis to Application

“…The high affinity of gold toward thiols was also utilized by Xie et al for the synthesis of spherical clusters. At first, a highly branched amphiphilic polymer bearing acrylate groups was synthesized.…”

Thermosensitive mixed shell polymeric micelles decorated with gold nanoparticles at the outmost surface: tunable surface plasmon resonance and enhanced catalytic properties with excellent colloidal stability

“…Especially, in the cases of polymeric NPs based on polymeric micelles, the self-assembly of block polymers offers versatile possibilities to fabricate nano-assemblies with rich morphologies and internal architectures. 17,[27][28][29][30] On the other hand, installing polymeric NPs with metal NPs can impart novel functional properties upon the otherwise inert polymeric materials to realize functional integration. [15][16][17][18][19][20][21] On one hand, polymeric NPs have been wisely recruited as templates either for the formation of metal NPs, [22][23][24][25][26] or for the three dimensional arrangement of preformed metal NPs.…”

“…17,[27][28][29][30] On the other hand, installing polymeric NPs with metal NPs can impart novel functional properties upon the otherwise inert polymeric materials to realize functional integration. 25,29,40 Furthermore, it is possible to control the interparticle distances of metal NPs loaded at the outmost surface, which are well known to be related to the electronic and magnetic properties of the nanoparticles. [31][32][33][34][35][36][37] In hybrid NPs consisting of metal and polymeric NPs, the metal NPs can either be loaded into the core, 36,38,39 homogenously distributed inside whole particles, 23,26 or located on the peripheral surface of the polymeric particles.…”

“…18,41,42 With such goals in mind, stimuli responsive polymeric components such as thermo-responsive poly(N-isopropylacrylamide) (PNIPAM), and pH sensitive poly(vinylpyridine) (PVP), have been used as the anchors for the metal NPs. 29 If the size of the polymeric template is set, increasing the density of metal NPs means decreasing the interparticle distance. Accordingly, the spatial position of the loaded metal NPs can also be netuned, resulting in tunable surface plasmon resonance (SPR), surface enhanced Raman scattering (SERS) or catalytic behavior.…”

Dumbbells, Trikes and Quads: Organic–Inorganic Hybrid Nanoarchitectures Based on “Clicked” Gold Nanoparticles

“…The detection of proteins has been achieved by using functional Au NPs, which create large assemblies resulting in an optical response . Au NPs were also assembled by click chemistry to form photo responsive networks, liquid crystals, oligomers, chains, combined networks of metal nanoparticles and robust nanostructures of different shapes of Au NPs . Furthermore the assembly of Au NPs via click chemistry on functionalized metal and polymer surfaces was performed …”