Assembly of metal nanoparticles into nanogaps

The directed assembly of nanoparticles and nanoscale materials onto specific locations of a surface is one of the major challenges in nanotechnology. Here we present a simple and scalable method and model for the assembly of nanoparticles in between electrical leads. Gold nanoparticles, 20 nm in diameter, were assembled inside electrical gaps ranging from 15 to 150 nm with the use of positive ac dielectrophoresis. In this method, an alternating current is used to create a gradient of electrical field that attracts particles in between the two leads used to create the potential. Assembly is achieved when dielectrophoretic forces exceed thermal and electrostatic forces; the use of anchoring molecules, present in the gap, improves the final assembly stability. We demonstrate with both experiment and theory that nanoparticle assembly inside the gap is controlled by the applied voltage and the gap size. Experimental evidence and modeling suggest that a gap-size-dependent threshold voltage must be overcome before particle assembly is realized. Assembly results as a function of frequency and time are also presented. Assembly of fewer than 10 isolated particles in a gap is demonstrated. Preliminary electrical characterization reveals that stable conductance of the assembled particles can be achieved.     

Coalescence behaviour of amorphous and crystalline tantalum nanoparticles: a molecular dynamics study

Porous films of tantalum (Ta) and its oxides exhibit numerous properties suitable for high surface area applications, mainly in the semiconductor and bio-implant industries. Such films can be developed by Ta nanoparticle deposition using DC magnetron sputtering with gas aggregation. In order to engineer films of desirable properties, accurate control and in-depth understanding of the processes and parameters of nanoparticle growth, deposition and coalescence are crucial. Of utmost importance is to control the film’s porosity, since it determines many of the other physical properties. To this end, we performed a number of classical Molecular Dynamics simulations to study the coalescence of two or more Ta nanoparticles. Temperature, relative size and crystallographic orientation, defect content, degree of crystallinity and deposition rate effects were taken into account, and a mapping of the sintering processes was acquired. A broad range of possible interaction mechanisms were observed, from simple nanoparticle reorientation in order to achieve epitaxial configuration, to atomic adsorption, neck formation, twinning within the nanoparticles and full consolidation into a single, larger nanoparticle. The parameters studied are directly linked to experimental deposition parameters; therefore, fitting them accordingly can lead to growth of films with bespoke properties.     

Preparation and decoloration property of polystyrene-grafted palygorskite nanoparticles

The polymerization of styrene on inorganic palygorskite nanorods was carried out by reverse atom transfer radical polymerization (RATRP) in a completely controlled manner to form structurally well-defined PS-grafted hybrid nanocomposite. Well-defined PS chains were grown from the nanoparticle surfaces to yield individual particles composed of a palygorskite core and a well-defined outer PS layer. It has been found that the dispersibility of palygorskite particles in organic solvents is significantly improved by grafting polymers onto the surface of palygorskite particles. So the holding time of PS-palygorskite is prolonged in organic solvents. Active point of adsorption in palygorskite surface is adequately utilized. The polymer-grafted palygorskite nanoparticles possess excellent decoloration capacity in organic solvents.     

Size controlled synthesis of biocompatible gold nanoparticles and their activity in the oxidation of NADH

Size and shape controlled synthesis remains a major bottleneck in the research on nanoparticles even after the development of different methods for their preparation. By tuning the size and shape of a nanoparticle, the intrinsic properties of the nanoparticle can be controlled leading tremendous potential applications in different fields of science and technology. We describe a facile route for the one pot synthesis of gold nanoparticles in water using monosodium glutamate as the reducing and stabilizing agent in the absence of seed particles. The particle diameter can be easily controlled by varying the pH of the reaction medium. Nanoparticles were characterized using scanning electron microscopy, UV-vis absorption spectroscopy, cyclic voltammetry, and dynamic light scattering. Zeta potential measurements were made to compare the stability of the different nanoparticles. The results suggest that lower pH favours a nucleation rate giving rise to smaller particles and higher pH favours a growth rate leading to the formation of larger particles. The synthesized nanoparticles are found to be stable and biocompatible. The nanoparticles synthesized at high pH exhibited a good electrocatalytic activity towards oxidation of nicotinamide adenine dinucleotide (NADH).     

Formation of TiO2 nanoparticles by reactive-layer-assisted deposition and characterization by XPS and STM

Stoichiometric TiO2 nanoparticles (1-5 nm) were prepared by reactive-layer-assisted deposition (RLAD), in which Ti was initially deposited on a multilayer of H2O (or NO2) on a Au(111) substrate at approximately 90 K. The composition and atom-resolved structure of the nanoparticles were studied by XPS and STM. The approximately 5 nm TiO2 particles had either a rutile or anatase phase with various crystal facets. STS of the nanoparticles suggests size-dependent electronic structure. These well-defined nanoparticles can be used in molecular-level studies of the reactions and mechanisms of photocatalytic processes on TiO2 nanoparticle surfaces.     

Formation of silver nanoparticles by through thin film ablation

Well dispersed Ag nanoparticles have been formed by a process denoted Through Thin Film Ablation. The nanoparticles were deposited on room temperature substrates, had a most probable size of 1 nm, and were not agglomerated. The nanoparticle deposit produced by this process showed no evidence of the larger particles commonly observed from conventional pulsed laser ablation that uses a bulk target. Synthesis of nanoparticles by Through Thin Film Ablation should be possible for any material that can be made as a thin film target and may enable the unique properties of isolated, non-agglomerated nanoparticles to be exploited more fully.     

Synthesis and antibacterial properties of silver nanoparticles

Nanometer sized silver particles were synthesized by inert gas condensation and co-condensation techniques. Both techniques are based on the evaporation of a metal into an inert atmosphere with the subsequent cooling for the nucleation and growth of the nanoparticles. The antibacterial efficiency of the nanoparticles was investigated by introducing the particles into a media containing Escherichia coli. The antibacterial investigations were performed in solution and on petri dishes. The silver nanoparticles were found to exhibit antibacterial effects at low concentrations. The antibacterial properties were related to the total surface area of the nanoparticles. Smaller particles with a larger surface to volume ratio provided a more efficient means for antibacterial activity. The nanoparticles were found to be completely cytotoxic to E. coli for surface concentrations as low as 8 microg of Ag/cm2.     

Photo-induced growth of DNA-capped silver nanoparticles

We report the photo-induced nucleation and growth of silver nanoparticles in aqueous solution in the presence of DNA oligomers. An organic dye (Cy5) was used as a photosensitizer to initiate the nanoparticle growth upon illumination with 647 nm light. The formation of nanoparticles and growth kinetics were observed by extinction spectroscopy, dynamic light scattering, and transmission electron microscopy. Irradiation of the precursor solutions with light at the Cy5 absorption maximum triggered the instantaneous formation of spherical particles with a metallic core ~15 nm in diameter. Remarkably, the particles feature significantly larger effective hydrodynamic diameters (35 nm) in solution, indicative of a DNA ad-layer on the nanoparticle surface. Centrifugation experiments confirmed that DNA was inseparably associated with the nanoparticles and indicated that DNA oligomers adsorb onto the nanoparticle surface during growth, playing the role of a capping agent. The introduced method is a fast and facile way to prepare DNA-capped silver nanoparticles in a single growth step.     

Electrostatically stabilised nanoparticles: self-organization and electron-beam patterning

The self-organisation of citrate- and magnesium oleate-stabilised gold nanoparticles on SiO2/Si substrates was investigated. In drop deposition, nucleation of citrate-stabilised gold nanoparticles was observed at the rim of the droplet, symmetric or multibranched dendroid gold structures were found in the area between the rim and the central part of the droplet, depending on the drying temperature. Homogeneous submonolayer nanoparticle coverage was obtained by immersion of amineterminated SiO2/Si surfaces into a citrate-stabilised colloidal gold acidic solution. Drop deposition of magnesium oleate-stabilised gold nanoparticles onto the SiO2/Si surfaces resulted in the formation of uniformly close-packed nanoparticle arrays. Under electron beam irradiation, no apparent changes were found for monolayer films of citrate-stabilized particles, but sintering of the nanoparticles was observed in multilayer films. In contrast, coalescence of magnesium oleate-stabilised gold nanoparticle occurred in monolayer films after electron irradiation.     

Morphological control of laser-synthesized silicon nanoparticles

Size and crystallinity controlled silicon nanoparticles were prepared by a laser ablation, in situ annealing and mobility size-selection with a differential mobility analyzer (DMA). The shape and crystal structure of generated particles were observed by a transmission electron microscopy (TEM). Both densification of agglomerates and crystal growth of the particles were observed. The size of silicon primary particle was increased by the annealing, and the uniformity of the particle classified at 10 nm was improved as a result.     

Magnetic field switching of nanoparticles between orthogonal microfluidic channels

This paper reports on the manipulation of magnetic nanoparticles between microfluidic channels by the application of an external magnet. Two orthogonal channels were prepared using standard PDMS techniques with pressure-driven flow used to deliver the mobile phase. To study the ability to control magnetic nanoparticles within micrometer-sized channels, Fe2O3, MnFe2O4, and Au nanoparticle samples were compared. For the magnetic particles, transfer between flow streams is greatly increased by placing a permanent magnet beneath the intersection of the channels, but no change is observed for the nonmagnetic Au particles. More nanoparticles are magnetically transferred into the orthogonal channel as the solvent flow rate decreases. We demonstrate the ability to use this technique to perform multiple injections of plugs of magnetic particles by periodic application of a magnetic field.     

Silica coated noble metal nanoparticle hydrosols as supported catalyst precursors

Synthesis of well-defined nanoparticles has been intensively pursued not only for their fundamental scientific interest, but also for many technological applications. One important development of the nanomaterial is in the area of chemical catalysis. We have now developed a new aqueous-based method for the synthesis of silica encapsulated noble metal nanoparticles in controlled dimensions. Thus, colloid stable silica encapsulated approximately 5 nm platinum nanoparticle is synthesized by a multi-step method. The thickness of the silica coating could be controlled using a different amount of silica precursor. These particles supported on a high surface area alumina are also demonstrated to display a superior hydrogenation activity and stability against metal sintering after thermal activation.     

Molecularly self-assembled nucleic acid nanoparticles for targeted in vivo siRNA delivery

Nanoparticles are used for delivering therapeutics into cells. However, size, shape, surface chemistry and the presentation of targeting ligands on the surface of nanoparticles can affect circulation half-life and biodistribution, cell-specific internalization, excretion, toxicity and efficacy. A variety of materials have been explored for delivering small interfering RNAs (siRNAs)--a therapeutic agent that suppresses the expression of targeted genes. However, conventional delivery nanoparticles such as liposomes and polymeric systems are heterogeneous in size, composition and surface chemistry, and this can lead to suboptimal performance, a lack of tissue specificity and potential toxicity. Here, we show that self-assembled DNA tetrahedral nanoparticles with a well-defined size can deliver siRNAs into cells and silence target genes in tumours. Monodisperse nanoparticles are prepared through the self-assembly of complementary DNA strands. Because the DNA strands are easily programmable, the size of the nanoparticles and the spatial orientation and density of cancer-targeting ligands (such as peptides and folate) on the nanoparticle surface can be controlled precisely. We show that at least three folate molecules per nanoparticle are required for optimal delivery of the siRNAs into cells and, gene silencing occurs only when the ligands are in the appropriate spatial orientation. In vivo, these nanoparticles showed a longer blood circulation time (t(1/2) ≈ 24.2 min) than the parent siRNA (t(1/2) ≈ 6 min).     

Relative impacts of sintering and condensational obliteration on nanoparticle structure

During the nanoparticle growth, primary particles merge with one another due to sintering and condensational obliteration destructing the aggregate structure of nanoparticles. Because the property and behavior of the nanoparticles depend on the aggregate size and structure, it is crucial to understand the roles of sintering and condensational obliteration quantitatively. In this study, the relative impacts of sintering and condensational obliteration on nanoparticle structure were investigated using numerical simulations on generation of TiO2 nanoparticles at a wide range of temperature. The effect of condensational obliteration was shown to be significant at low temperature, whereas sintering was more important at high temperature. The simulation results demonstrated that both sintering and condensational obliteration must be taken into account in the model to predict the nanoparticle structure accurately.     

Fabrication of ZnO nanorods using metal nanoparticles as growth nuclei

ZnO nanorods were produced by pulsed laser deposition (PLD). Drops of nanoparticle colloid (gold or silver) were placed on silica substrates to form growth nuclei. All nanoparticles were monocrystalline, with well-defined crystal surfaces and a negative electrical charge. The ZnO nanorods were produced in an off-axis PLD configuration at oxygen pressure of 5 Pa. The growth of the nanorods started from the nanoparticles in different directions, as one nanoparticle could become a nucleus for more than one nanorod. The low substrate temperature used indicates the absence of a catalyst during the growth of the nanorods. The diameters of the fabricated 1-D ZnO nanostructures were in the range of 50-120 nm and their length was determined by the deposition time.     

Synthesis and sintering of biomimetic hydroxyapatite nanoparticles for biomedical applications

Synthesis of monodisperse nanoparticles with uniform morphology and narrow size distribution as achieved by nature is a challenge to materials scientists. Mimicking the process of biomineralization has led to the development of biomolecules mediated synthesis of nanoparticles that overcomes many of the problems associated with nanoparticle synthesis. Termed as biomimetics this paradigm shift in the philosophy of synthesis of materials is very advantageous for the design-based synthesis of nanoparticles. The effect of concentration of a protein named bovine serum albumin on particle size, morphology and degree of crystallinity of biomimetically synthesized hydroxyapatite particles, has been studied. Results establish 0.5% protein as the required concentration to produce 30–40 nm sized hydroxyapatite particles with an optimum degree of crystallinity as required for biomedical applications. These particles synthesized under certain stringent conditions are found to have stoichiometric calcium:phosphorus ratio of 1.67 and exhibit restricted grain growth during sintering.     

Mass production and size control of lipid-polymer hybrid nanoparticles through controlled microvortices

Lipid-polymer hybrid (LPH) nanoparticles can deliver a wide range of therapeutic compounds in a controlled manner. LPH nanoparticle syntheses using microfluidics improve the mixing process but are restricted by a low throughput. In this study, we present a pattern-tunable microvortex platform that allows mass production and size control of LPH nanoparticles with superior reproducibility and homogeneity. We demonstrate that by varying flow rates (i.e., Reynolds number (30-150)) we can control the nanoparticle size (30-170 nm) with high productivity (～3 g/hour) and low polydispersity (～0.1). Our approach may contribute to efficient development and optimization of a wide range of multicomponent nanoparticles for medical imaging and drug delivery.     

Controlling in vivo stability and biodistribution in electrostatically assembled nanoparticles for systemic delivery

This paper demonstrates the generation of systemically deliverable layer-by-layer (LbL) nanoparticles for cancer applications. LbL-based nanoparticles designed to navigate the body and deliver therapeutics in a programmable fashion are promising new and alternative systems for drug delivery, but there have been very few demonstrations of their systemic delivery in vivo due to a lack of knowledge in building LbL nanofilms that mimic traditional nanoparticle design to optimize delivery. The key to the successful application of these nanocarriers in vivo requires a systematic analysis of the influence of film architecture and adsorbed polyelectrolyte outer layer on their pharmacokinetics, which has thus far not been examined for this new approach to nanoparticle delivery. Herein, we have taken the first steps in stabilizing and controlling the systemic distribution of multilayer nanoparticles. Our findings highlight the unique character of LbL systems; the electrostatically assembled nanoparticles gain increased stability in vivo with larger numbers of deposited layers, and the final layer adsorbed generates a critical surface cascade, which dictates the surface chemistry and biological properties of the nanoparticle. This outer polyelectrolyte layer dramatically affects not only the degree of nonspecific particle uptake, but also the nanoparticle biodistribution. For hyaluronic acid (HA) outer layers, a long blood elimination half-life (～9 h) and low accumulation (～10-15% recovered fluorescence/g) in the liver were observed, illustrating that these systems can be designed to be highly appropriate for clinical translation.     

Perylene-labeled silica nanoparticles: synthesis and characterization of three novel silica nanoparticle species for live-cell imaging

The increasing exposure of humans to nanoscaled particles requires well-defined systems that enable the investigation of the toxicity of nanoparticles on the cellular level. To facilitate this, surface-labeled silica nanoparticles, nanoparticles with a labeled core and a silica shell, and a labeled nanoparticle network-all designed for live-cell imaging-are synthesized. The nanoparticles are functionalized with perylene derivatives. For this purpose, two different perylene species containing one or two reactive silica functionalities are prepared. The nanoparticles are studied by transmission electron microscopy, widefield and confocal fluorescence microscopy, as well as by fluorescence spectroscopy in combination with fluorescence anisotropy, in order to characterize the size and morphology of the nanoparticles and to prove the success and homogeneity of the labeling. Using spinning-disc confocal measurements, silica nanoparticles are demonstrated to be taken up by HeLa cells, and they are clearly detectable inside the cytoplasm of the cells.     

Study of sintering behavior of vapor forms of 1-octanethiol coated copper nanoparticles for application to ink-jet printing technology

Sub-50 nm copper nanoparticles coated with sub-5 nm 1-octanethiol layer for oxidation inhibition were examined to confirm the 1-octanethiol removal temperature as the sub-50 nm copper nanoparticles are sintered. As a result, 1-octanethiol Self-Assembled Multi-layers (SAMs) on sub-50 nm copper nanoparticles were successfully removed before sintering of copper nanoparticles so that a high density of copper line could be obtained. Finally, the line resistivity was measured and compared to verify the effect of sintering in different atmospheres. As a result, electrical resistivity of the copper pattern sintered in hydrogen atmosphere was measured at 6.96 x 10(-6) ohm-cm whereas that of the copper pattern sintered in mixed gas atmosphere was measured at 2.62 x 10(-5) ohm-cm. Thus, sintering of copper patterns was successfully done to show low electrical resistivity values. Moreover, removal of 1-octanethiol coating after sintering process was confirmed using X-ray photoelectron spectroscopy (XPS) analysis. By showing no sulfur content, XPS results indicate that 1-octanethiol is completely removed. Therefore, the vapor form of 1-octanethiol coating layers can be safely used as an oxidation inhibition layer for low temperature sintering processes and ink-jet applications.