Nanopatterning self-assembled nanoparticle superlattices by moulding microdroplets

Highly ordered arrays of nanoparticles exhibit many properties that are not found in their disordered counterparts. However, these nanoparticle superlattices usually form in a far-from-equilibrium dewetting process, which precludes the use of conventional patterning methods owing to a lack of control over the local dewetting dynamics. Here, we report a simple yet efficient approach for patterning such superlattices that involves moulding microdroplets containing the nanoparticles and spatially regulating their dewetting process. This approach can provide rational control over the local nucleation and growth of the nanoparticle superlattices. Using DNA-capped gold nanoparticles as a model system, we have patterned nanoparticle superlattices over large areas into a number of versatile structures with high degrees of internal order, including single-particle-width corrals, single-particle-thickness microdiscs and submicrometre-sized 'supra-crystals'. Remarkably, these features could be addressed by micropatterned electrode arrays, suggesting potential applications in bottom-up nanodevices.     

Synthetically programmable nanoparticle superlattices using a hollow three-dimensional spacer approach

Crystalline nanoparticle arrays and superlattices with well-defined geometries can be synthesized by using appropriate electrostatic, hydrogen-bonding or biological recognition interactions. Although superlattices with many distinct geometries can be produced using these approaches, the library of achievable lattices could be increased by developing a strategy that allows some of the nanoparticles within a binary lattice to be replaced with 'spacer' entities that are constructed to mimic the behaviour of the nanoparticles they replace, even though they do not contain an inorganic core. The inclusion of these spacer entities within a known binary superlattice would effectively delete one set of nanoparticles without affecting the positions of the other set. Here, we show how hollow DNA nanostructures can be used as 'three-dimensional spacers' within nanoparticle superlattices assembled through programmable DNA interactions. We show that this strategy can be used to form superlattices with five distinct symmetries, including one that has never before been observed in any crystalline material.     

Predicting chiral nanostructures, lattices and superlattices in complex multicomponent nanoparticle self-assembly

"Bottom up" type nanoparticle (NP) self-assembly is expected to provide facile routes to nanostructured materials for various, for example, energy related, applications. Despite progress in simulations and theories, structure prediction of self-assembled materials beyond simple model systems remains challenging. Here we utilize a field theory approach for predicting nanostructure of complex and multicomponent hybrid systems with multiple types of short- and long-range interactions. We propose design criteria for controlling a range of NP based nanomaterial structures. In good agreement with recent experiments, the theory predicts that ABC triblock terpolymer directed assemblies with ligand-stabilized NPs can lead to chiral NP network structures. Furthermore, we predict that long-range Coulomb interactions between NPs leading to simple NP lattices, when applied to NP/block copolymer (BCP) assemblies, induce NP superlattice formation within the phase separated BCP nanostructure, a strategy not yet realized experimentally. We expect such superlattices to be of increasing interest to communities involved in research on, for example, energy generation and storage, metamaterials, as well as microelectronics and information storage.     

Exciton-plasmon interactions in quantum dot-gold nanoparticle structures

We present a self-assembly method to construct CdSe/ZnS quantum dot-gold nanoparticle complexes. This method allows us to form complexes with relatively good control of the composition and structure that can be used for detailed study of the exciton-plasmon interactions. We determine the contribution of the polarization-dependent near-field enhancement, which may enhance the absorption by nearly two orders of magnitude and that of the exciton coupling to plasmon modes, which modifies the exciton decay rate.     

Magnetostatic interactions in planar ring-like nanoparticle structures

Numerical calculations of equilibrium state energies and local magnetic fields in planar ring-like nanoparticle structures were performed. The dipole–dipole, Zeeman and magnetic anisotropy interactions were included into the model. The result of their competition depends on the value of the external magnetic field, magnetic parameters of an individual nanoparticle, size and shape of the structures. Flux-closed vortexes, single domain, two-domain “onion”-like, “hedgehog”-like and more complex spin structures can be realized. The critical field, providing a sharp transition from the flux-closed vortex to the “onion”-like state, can be regulated by a variation of the particle magnetization and anisotropy constant, their easy directions, and particle space arrangement.     

Preparation of monodisperse Ni nanoparticles and their assembly into 3D nanoparticle superlattices

Monodisperse Ni nanoparticles with sizes varying from 4.8 to 11.3 nm are prepared via a one-pot reaction that involves the reduction of nickel(II) acetylacetonate in oleylamine in the presence of trioctylphosphine and 1,2-hexadecanediol. Reaction parameters such as temperature and the concentration of capping agent and metal precursor are critical for the adjustment of particle size. The decrease of crystallinity is observed for the samples with smaller particle sizes, which significantly affects the magnetic properties. Three-dimensional (3D) superlattices that are composed of Ni nanoparticles with different sizes are obtained on different substrates by a facile self-assembly process, and are characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM) and small-angle X-ray diffraction (SAXRD). The Ni nanoparticle superlattices formed on carbon-coated TEM copper grids exhibit a dominant hexagonal close-packed (hcp) symmetry, although local fcc packing is also occasionally observed. The formation of 3D nanoparticle superlattice structures on Si substrates is confirmed from the SAXRD measurements. The method revealed in this study for the preparation of 3D superlattices composed of Ni nanoparticles with tunable sizes offers the potential to explore their interesting collective properties for multiple applications.     

A gold nanoparticle platform for protein-protein interactions and drug discovery

Gold nanoparticles hold great promise for studying protein-protein interactions because of their intrinsic optical properties. Pink when in a homogeneous suspension, the solution turns blue-gray when particles are drawn close together, for example, when immobilized proteins specifically interact with each other. However, the nanoparticle stability, size, and method of protein attachment contribute to the unreliable outcome of current assays. To overcome these hurdles, we developed novel and reliable methods first to synthesize homogenous particles of optimal diameter and second to apply a heterologous NTA-Ni-SAM coating for controlled orientation and optimal presentation of histidine-tagged proteins. Both methods were proven to greatly enhance assay sensitivity and specificity by increasing the signal and minimizing the nonspecific binding. Our assay reproducibly detected known protein-protein interactions and unambiguously identified small molecules that inhibited them. We believe our gold nanoparticle bioassay is a versatile and trustworthy new platform for analyzing protein-protein interactions and high-throughput screening of small-molecule inhibitors.     

A colorimetric gold nanoparticle sensor to interrogate biomolecular interactions in real time on a surface

This paper presents a new label-free optical method to study biomolecular interactions in real time at the surface of an optically transparent substrate. The method relies on the change in the absorbance spectrum of a self-assembled monolayer of colloidal gold on glass, as a function of biomolecular binding to the surface of the immobilized colloids. Using this approach, we demonstrate proof of principle of a label-free optical biosensor to quantify biomolecular interactions in real time on a surface in a commercially available UV-visible spectrophotometer and of a colorimetric end-point assay using an optical scanner. The spectrophotometric sensor shows concentration-dependent binding and a detection limit of 16 nM for streptavidin. The sensor is easy to fabricate, is reproducible in its performance, has minimal technological requirements, namely, the availability of an UV-visible spectrophotometer or an optical scanner, and will enable high-throughput screening of biomolecular interactions in real time in an array-based format.     

Nuclear spin-lattice relaxation in superlattices

The nuclear spin-lattice relaxation rate in a superlattice subjected to a strong magnetic field H parallel to its axis is studied theoretically. The energy conservation law allows flip-flop spin-reversal processes due to the hyperfine interaction between the nuclear and electron spins only in some intervals of H. In particular, the width of the highest occupied superlattice subband /spl Delta/ must exceed the spin splitting of Landau levels, which results in the relaxation offset at some critical magnetic field H/sub 2/. At H相似文献   

Amorphous silicon-based superlattices

Synthesis and some interesting properties of amorphous silicon-based superlattices are reported. Both quantum-well type and doping modulated structures are studied. Quantum confinement, phonon folding and persistent photoconductivity are some of the fascinating effects which are described and their current interpretations discussed. Based on an invited paper presented at the Indo-USSR Symposium on Electronic Materials, held at the National Physical Laboratory, New Delhi, January 17–19, 1990.     

Stripe domains in nanomagnetic superlattices

Equations describing the equilibrium parameters of stripe domains in nanomagnetic multilayers have been obtained by means of an integral transformation of the magnetostatic energy expression. These equations are applied to the investigation of polydomain structures in Co/Pt multilayers.     

Critical Property of the Geometric Phase in the Dicke Model with the Dipole-dipole Interactions

We obtained the ground-state energy level and associated geometric phase in the Dicke model with the dipoledipole interactions analytically by the Holstein-Primakoff transformation and the boson expansion approach in the thermodynamic limit. The nonadiabatic geometric phase induced by the photon field was derived with the time-dependent unitary transformation. It is shown that dipole-dipole interactions have a deep influence on scaled behavior of the geometric phase at the critical point.     

Dipole-dipole interaction between molecules mediated by a chain of silver nanoparticles

We study the dipole-dipole coupling between two fluorescent molecules in the presence of a chain of metallic nanoparticles. We analyze the spectral behavior of the coupling strength and its dependence on the molecular orientation. Our results show that for certain resonant wavelengths the coupling strength between the molecules is greatly enhanced and is strongly polarization sensitive. We also demonstrate how metallic nanoparticles can be utilized in implementing a polarization-sensitive coupler.     

High thermal conductivity in short-period superlattices

The thermal conductivity of ideal short-period superlattices is computed using harmonic and anharmonic force constants derived from density-functional perturbation theory and by solving the Boltzmann transport equation in the single-mode relaxation time approximation, using silicon-germanium as a paradigmatic case. We show that in the limit of small superlattice period the computed thermal conductivity of the superlattice can exceed that of both the constituent materials. This is found to be due to a dramatic reduction in the scattering of acoustic phonons by optical phonons, leading to very long phonon lifetimes. By variation of the mass mismatch between the constituent materials in the superlattice, it is found that this enhancement in thermal conductivity can be engineered, providing avenues to achieve high thermal conductivities in nanostructured materials.     

Electron beam supercollimation in graphene superlattices

Although electrons and photons are intrinsically different, importing useful concepts in optics to electronics performing similar functions has been actively pursued over the last two decades. In particular, collimation of an electron beam is a long-standing goal. We show that ballistic propagation of an electron beam with virtual no spatial spreading or diffraction, without a waveguide or external magnetic field, can be achieved in graphene under an appropriate class of experimentally feasible one-dimensional external periodic potentials. The novel chiral quasi-one-dimensional metallic state that the charge carriers are in originates from a collapse of the intrinsic helical nature of the charge carriers in graphene owing to the superlattice potential. Beyond providing a new way to constructing chiral one-dimensional states in two dimensions, our findings should be useful in graphene-based electronic devices (e.g., for information processing) utilizing some of the highly developed concepts in optics.     

Construction and characterization of a gold nanoparticle wire assembled using Mg2+-dependent RNA-RNA interactions

Magnesium-ion-mediated RNA-RNA loop-receptor interactions, in conjunction with gold nanoparticles derivatized with DNA, have been used to make self-assembled nanowires. A wire located between lithographically fabricated nanoelectrodes is demonstrated that exhibits activated conduction by electron hopping at temperatures in the 150-300 K range. These techniques have the ability to link particles between devices and in the future may be used to assemble practical circuits.     

Beauty is skin deep: a surface monolayer perspective on nanoparticle interactions with cells and bio-macromolecules

Surface recognition of biosystems is a critical component in the development of novel biosensors and delivery vehicles, and for the therapeutic regulation of biological processes. Monolayer-protected nanoparticles present a highly versatile scaffold for selective interaction with bio-macromolecules and cells. Through the engineering of the monolayer surface, nanoparticles can be tailored for surface recognition of biomolecules and cells. This review highlights recent progress in nanoparticle-bio-macromolecule/cellular interactions, emphasizing the effect of the surface monolayer structure on the interactions with proteins, DNA, and cell surfaces. The extension of these tailored interactions to hybrid nanomaterials, biosensing platforms, and delivery vehicles is also discussed.