Self-Assembly of Inorganic Nanoparticle Vesicles and Tubules Driven by Tethered Linear Block Copolymers

Abstract

Controllable self-assembly of nanoscale building blocks into larger specific structures provides an effective route for the fabrication of new materials with unique optical, electronic, and magnetic properties. The ability of nanoparticles (NPs) to self-assemble like molecules is opening new research frontiers in nanoscience and nanotechnology. We present a new class of amphiphilic "colloidal molecules" (ACMs) composed of inorganic NPs tethered with amphiphilic linear block copolymers (BCPs). Driven by the conformational changes of tethered BCP chains, such ACMs can self-assemble into well-defined vesicular and tubular nanostructures comprising a monolayer shell of hexagonally packed NPs in selective solvents. The morphologies and geometries of these assemblies can be controlled by the size of NPs and molecular weight of BCPs. Our approach also allows us to control the interparticle distance, thus fine-tuning the plasmonic properties of the assemblies of metal NPs. This strategy provides a general means to design new building blocks for assembling novel functional materials and devices.

Hairy nanoparticle assemblies as one-component functional polymer nanocomposites: opportunities and challenges

“…This design allows for much more controlled structure formation (Fig. 3): BCP-tethered HNPs have been used by multiple researchers to create complex structures such as tubules and vesicles with walls built out of HNPs, [52] as well as lamellae and "segmented worms." [53] Jayaraman and Schweizer used a modified version of the polymer reference interaction site model to investigate structure formation for particles with very low graft densities; 1, 2, 4, and 6 polymers per particle.…”

Self-Assembly of Shaped Nanoparticles into Free-Standing 2D and 3D Superlattices

“…The surface of NRs was functionalized with thiol-terminated polystyrene (PS) through a ligand exchange approach (see Scheme S2, Supporting Information). [37][38][39] Thiol-terminated PS with M w ranging from 5 to 50k Da was used in this work. A solution of PS-tethered NRs and P4VP 60k (PDP) 1.0 supramolecules (the subscript 60k represents the M w of P4VP) in chloroform was slowly evaporated to remove solvent to form a thin fi lm.…”

“…[ 53 ] Au NPs with size of 15 nm were synthesized by the previously reported citrate reduction method. [ 39 ] Synthesis of Au NRs : Au NRs were synthesized following the published protocols. [ 54 ] The seed solution of gold NRs was pre- NRs were purifi ed using twice 30 min long centrifugation cycles at 10 000-12 000 rpm.…”

Synthetic cellularity based on non-lipid micro-compartments and protocell models

“…Assembly is driven by a decrease in total free energy associated with placement of the particles specifically at the liquid/liquid interface [13], and produces stabilized water or oil droplets that are dispersed in an oil or water continuous phase, respectively. Since the seminal paper by Weitz et al in 2002 [14 ], a wide range of colloidosomes have been prepared using inorganic particles, such as silica [15 ,16], clays [17], CaCO 3 [18], graphene oxide [19], TiO 2 [20], Fe 3 O 4 [21], cerium oxide [22], gold particles [23], metal organic frameworks [24] and polyoxometalateorganic hybrid particles [25]. In most cases, the colloidosomes are several tens of micrometres in diameter, and consist of a monolayer of closely packed particles in the form of a continuous, enclosed membrane.…”