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ABSTRACT: The core-shell nanoparticle structure, which consists of an inner layer "guest" nanoparticle encapsulated inside another of a different material, is the simplest motif in two-component systems. In comparison to the conventional single-component systems, complex systems pose both challenges and opportunities. In this Account, we describe our recent progresses in using core-shell motif for exploring new and sophisticated nanostructures. Our discussion is focused on the mechanistic details, in order to facilitate rational design in future studies. We believe that systematic development of synthetic capability, particularly in complex and multifunctional systems, is of great importance for future applications. A key issue in obtaining core-shell nanostructures is minimizing the core-shell interfacial tension. Typically, one can coat the core with a ligand for better interaction with the shell. By selecting suitable ligands, we have developed general encapsulation methods in three systems. A variety of nanoparticles and nanowires were encapsulated using either amphiphilic block copolymer (polystyrene-block-poly(acrylic acid)), conductive polymer (polyaniline, polypyrrole, or polythiophene), or silica as the shell material. Obvious uses of shells are to stabilize colloidal objects, retain their surface ligands, prevent particle aggregation, or preserve the assembled superstructures. These simple capabilities are essential in our synthesis of surface-enhanced Raman scattering nanoprobes, in assigning the solution state of nanostructures before drying, and in developing purification methods for nano-objects. When it is applied in situ during nanocrystal growth or nanoparticle assembly, the intermediates trapped by shell encapsulation can offer great insights into the mechanistic details. On the other hand, having a shell as a second component provides a window for exploring the core-shell synergistic effects. Hybrid core-shell nanocrystals have interesting effects, for example, in causing the untwisting of nanowires to give double helices. In addition, partial polymer shells can bias nanocrystal growth towards one direction or promote the random growth of Au dendritic structures; contracting polymer shells can compress the embedded nanofilaments (Au nanowires or carbon nanotubes), forcing them to coil into rings. Also, by exploiting the sphere-to-cylinder conversion of block copolymer micelles, the Au nanoparticles pre-embedded in the polymer micelles can be assembled into long chains. Lastly, shells are also very useful for mechanistic studies. We have demonstrated such applications in studying the controlled aggregation of nanoparticles, in probing the diffusion kinetics of model drug molecules from nanocarriers to nanoacceptors, and in measuring the ionic diffusion through polyaniline shells.
Accounts of Chemical Research 04/2013; · 21.64 Impact Factor
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ABSTRACT: Hydrophobic carbon nanotubes (CNTs) and hydrophilic nanofilaments such as oxidized CNTs, Pd nanowires (NWs), and MnO2 NWs, are transformed from wires to rings by a general methodology. We show that both oil-in-water and water-in-oil emulsions, so long as their droplet size is sufficiently small, can exert significant force to the entrapped nanostructures causing their deformation. This effect can be easily achieved by simply mixing a few solutions in correct ratios. Even pre-formed oil droplets can take in CNTs from the aqueous solution converting them into rings, indicating the important role of thermodynamics: The question here is not if the droplets can exert sufficient force to bend the nanofilaments, because their random vibration may be already doing it. As long as the difference in solvation energy is large enough for a nanofilament, it would "want" to move away from the bulk solution and fit inside tiny droplets, even at the cost of induced strain energy. That said, the specific interactions between a droplet and a filament is also of importance. For example, when an oil droplet rapidly shrinks in size, it can compress the entrapped CNTs in multiple stages into structures with higher curvatures (thus higher strain) than that of a circular ring, which has minimal induced strain inside a spherical droplet.
Journal of the American Chemical Society 12/2012; · 9.91 Impact Factor
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ABSTRACT: One-dimensional assembly of gold nanoparticlesis achieved by a sphere-to-cylinder transformation of polymer shells. A large amount of monomers remains after the assembly, which is characteristic of the chain-growth "polymerization". Single-line chains can be converted to double-line chains, thus substantiating the unique role of the polymer shell.
Angewandte Chemie International Edition 07/2012; 51(32):8021-5. · 13.45 Impact Factor
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ABSTRACT: The chain-growth "polymerization" of gold nanoparticles involves their initial encapsulation by polystyrene-block-poly(acrylic acid) and the self-assembly of the resulting "monomers" into long chains of up to 300 nanoparticles. In their Communication (DOI: 10.1002/anie.201203088), H. Chen et al. state that the nanoparticle assembly is highly selective and gives chains with uniform width and interparticle spacing. The background of the picture shows the skyline of Singapore.
Angewandte Chemie International Edition 07/2012; · 13.45 Impact Factor
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ABSTRACT: New methods to self-assemble polystyrene-block-poly(acrylic acid) (PSPAA) on silica via electrostatic interaction and to deposit silica on PSPAA shells are developed. The mutual encapsulation of silica and PSPAA allows versatile syntheses of well-controlled nanohybrids.
Small 03/2012; 8(12):1857-62. · 8.35 Impact Factor
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ABSTRACT: We show that the microstructures of polycrystalline ice can serve as a confining template for one-dimensional assembly of colloidal nanoparticles. Upon simply freezing an aqueous colloid, the nanoparticles are excluded from ice grains and form chains in the ice veins. The nanoparticle chains are transferable and can be strengthened by polymer encapsulation. After coating with polyaniline shells, simple sedimentation is used to remove large aggregates, enriching single-line chains of 40 nm gold nanoparticles with a total length of several micrometers. When gold nanorods were used, they formed one-dimensional aggregates with specific end-to-end conformation, indicating the confining effects of the nanoscale ice veins at the final stage of freezing. The unbranched and ultralong plasmonic chains are of importance for future study of plasmonic coupling and development of plasmonic waveguides.
ACS Nano 09/2011; 5(10):8426-33. · 10.77 Impact Factor
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ABSTRACT: We show that bundles of carbon nanotubes can be coiled into ring structures by controlling the contraction of their polymer shells. With the robust carbon nanotubes, we demonstrate their reversible transformation between circular and compressed rings in a colloid.
Journal of the American Chemical Society 06/2011; 133(25):9654-7. · 9.91 Impact Factor
