Mesoporous Metal Sponges Produced by Explosive Decomposition.

The formation of mesoporous gold sponges by explosive decomposition of 'knallgold' (also known as 'fulminating' gold) is studied. Proof-of-principle experiments are conducted and then the phenomena are further investigated using 'toy physics' molecular dynamics simulations. The simulations invoked various ratios of a volatile Lennard-Jones element G and a noble metal element N. In both experiment and simulation the morphology of the resulting sponge is found to depend on the stoichiometry of the starting material. As the mole fraction of G (χG) is increased from 0.5 to close to 1.0 in the simulations, the morphology of the sponges changes from closed to open, with a corresponding increase in the average mean curvature from 0 to +0.12 inverse Lennard-Jones length (L) units. The average Gaussian curvature of the simulated sponges is always negative, with the minimum value of 0.05 L-2 being found for χG≈0.65. In broad agreement with experiment, sponge formation in the simulations is bounded by stoichiometry; no sponges form if χG is <0.52, for χG between 0.52 and 0.70 the sponge is characterized by vermicular cavities whereas classic bicontinuous fibrous sponges form for 0.70<χG<0.85 and, finally, discrete particles result if χG>0.85.

Thermal Effect during Laser-Induced Plasmonic Heating of Polyelectrolyte-Coated Gold Nanorods in Well Plates.

We examined the generation and transfer of heat when laser irradiation is applied to water containing a suspension of gold nanorods coated with different polyelectrolytes. The ubiquitous well plate was used as the geometry for these studies. The predictions of a finite element model were compared to experimental measurements. It is found that relatively high fluences must be applied in order to generate biologically relevant changes in temperature. This is due to the significant lateral heat transfer from the sides of the well, which strongly limits the temperature that can be achieved. A 650 mW continuous-wave (CW) laser, with a wavelength that is similar to the longitudinal plasmon resonance peak of the gold nanorods, can deliver heat with an overall efficiency of up to 3%. This is double the efficiency achievable without the nanorods. An increase in temperature of up to 15 °C can be achieved, which is suitable for the induction of cell death by hyperthermia. The nature of the polymer coating on the surface of the gold nanorods is found to have a small effect.

The fate of organic species upon sintering of thiol-stabilised gold nanoparticles under different atmospheric conditions.

Understanding and controlling the sintering behavior of gold nanoparticles is important for applications such as printed electronics, catalysis and sensing that utilise these materials. Here we examine the processes by which thiol-protected gold nanoparticles thermally sinter under a variety of atmospheres. We find that upon sintering, the surface-bound thiyl ligands exclusively form the corresponding disulfide species when released from the gold surface. Experiments conducted using air, hydrogen, nitrogen, or argon atmospheres revealed no significant differences between the temperatures of the sintering event nor on the composition of released organic species. When conducted under high vacuum, the sintering event occurred at lower temperatures compared to ambient pressures in cases where the resulting disulfide had relatively high volatility (dibutyl disulfide). Hexadecylthiol-stabilized particles exhibited no significant differences in the temperatures of the sintering event under ambient pressures compared to high vacuum conditions. We attribute this to the relatively low volatility of the resultant dihexadecyl disulfide product.

Comparison of Single- and Mixed-Sized Gold Nanoparticles on Lateral Flow Assay for Albumin Detection.

The sensitivity and reproducibility of the lateral flow assay can be influenced by multiple factors, such as the size of gold nanoparticles (GNPs) employed. Here, we evaluated the analytical performance of single-sized and mixed-sized GNPs using a simple lateral flow assay (LFA) platform. This platform was used as a model assay to diagnose albumin levels and demonstrate the analytical performance of single-sized and mixed-sized GNPs in LFA tests. Two sizes of GNPs@anti-bovine serum albumin (BSA) conjugate proteins were mixed at different ratios. The unique optical properties of the GNPs induced a distinguishing color-shedding effect on the single- and mixed-sized GNPs@anti-BSA conjugates interacting with the target analyte BSA spotted on the test line. The use of mixed-sized GNPs@anti-BSA conjugates enhanced signal relative to the 20 nm GNPs, and provided superior stability compared with solely employing the large GNPs (50 nm). The proposed platform in this study could provide an efficient BSA detection mechanism that can be utilized as a model biomarker for confronting chronic kidney disease.

Single and multiple detections of foodborne pathogens by gold nanoparticle assays.

A late detection of pathogenic microorganisms in food and drinking water has a high potential to cause adverse health impacts in those who have ingested the pathogens. For this reason there is intense interest in developing precise, rapid and sensitive assays that can detect multiple foodborne pathogens. Such assays would be valuable components in the campaign to minimize foodborne illness. Here, we discuss the emerging types of assays based on gold nanoparticles (GNPs) for rapidly diagnosing single or multiple foodborne pathogen infections. Colorimetric and lateral flow assays based on GNPs may be read by the human eye. Refractometric sensors based on a shift in the position of a plasmon resonance absorption peak can be read by the new generation of inexpensive optical spectrometers. Surface-enhanced Raman spectroscopy and the quartz microbalance require slightly more sophisticated equipment but can be very sensitive. A wide range of electrochemical techniques are also under development. Given the range of options provided by GNPs, we confidently expect that some, or all, of these technologies will eventually enter routine use for detecting pathogens in food. This article is categorized under: Diagnostic Tools > Biosensing.

The Quest for Zero Loss: Unconventional Materials for Plasmonics.

There has been an ongoing quest to optimize the materials used to build plasmonic devices: first the elements were investigated, then alloys and intermetallic compounds, later semiconductors were considered, and, most recently, there has been interest in using more exotic materials such as topological insulators and conducting oxides. The quality of the plasmon resonances in these materials is closely correlated with their structure and properties. In general gold and silver are the most commonly specified materials for these applications but they do have weaknesses. Here, it is shown how, in specific circumstances, the selection of certain other materials might be more useful. Candidate alternatives include Tix N, VO2 , Al, Cu, Al-doped ZnO, and Cu-Al alloys. The relative merits of these choices and the many pitfalls and subtle problems that arise are discussed, and a frank perspective on the field is provided.

Heat transfer from nanoparticles for targeted destruction of infectious organisms.

Whereas the application of optically or magnetically heated nanoparticles to destroy tumours is now well established, the extension of this concept to target pathogens has barely begun. Here we examine the challenge of targeting pathogens by this means and, in particular, explore the issues of power density and heat transfer. Depending on the rate of heating, either hyperthermia or thermoablation may occur. This division of the field is fundamental and implies very different sources of excitation and heat transfer for the two modes, and different strategies for their clinical application. Heating by isolated nanoparticles and by agglomerates of nanoparticles is compared: hyperthermia is much more readily achieved with agglomerates and for large target volumes, a factor which favours magnetic excitation and moderate power densities. In contrast, destruction of planktonic pathogens is best achieved by localised thermoablation and very high power density, a scenario that is best delivered by pulsed optical excitation.

Gold nanoparticles improve metabolic profile of mice fed a high-fat diet.

BACKGROUND: Obesity is a high risk for multiple metabolic disorders due to excessive influx of energy, glucose and lipid, often from a western based diet. Low-grade inflammation plays a key role in the progression of such metabolic disorders. The anti-inflammatory property of gold compounds has been used in treating rheumatoid arthritis in the clinic. Previously we found that pure gold nanoparticles (AuNPs, 21 nm) also possess anti-inflammatory effects on the retroperitoneal fat tissue following intraperitoneal injection, by downregulating tumor necrosis factor (TNF) α. However, whether such an effect can change the risk of metabolic disorders in the obese has not been well studied. The study employed C57BL/6 mice fed a pellet high fat diet (HFD, 43% as fat) that were treated daily with AuNPs [low (HFD-LAu) or high (HFD-HAu) dose] via intraperitoneal injection for 9 weeks. In the in vitro study, RAW264.7 macrophages and 3T3-L1 adipocytes were cultured with low and high concentrations of AuNPs alone or together. RESULTS: The HFD-fed mice showed a significant increase in fat mass, glucose intolerance, dyslipidemia, and liver steatosis. The HFD-LAu group showed an 8% reduction in body weight, ameliorated hyperlipidemia, and normal glucose tolerance; while the HFD-HAu group had a 5% reduction in body weight with significant improvement in their glucose intolerance and hyperlipidemia. The underlying mechanism may be attributed to a reduction in adipose and hepatic local proinflammatory cytokine production, e.g. TNFα. In vitro studies of co-cultured murine RAW264.7 macrophage and 3T3-L1 adipocytes supported this proposed mechanism. CONCLUSION: AuNPs demonstrate a promising profile for potential management of obesity related glucose and lipid disorders and are useful as a research tool for the study of biological mechanisms.

From Lead(II) Dithiocarbamate Precursors to a Fast Response PbS Positive Temperature Coefficient Thermistor.

PbS submicron crystals were formed by thermolysis of two different lead dithiocarbamate complexes. These precursors were readily synthesized and fully characterized, and in situ synchrotron powder diffraction experiments were performed to characterize their decomposition. The structure and purity of resultant PbS was examined using scanning electron and transmission electron microscopies, powder X-ray diffraction, and infrared spectroscopy. Submicron crystalline PbS was used to create a new PbS thermistor with excellent sensitivity and an ultrarapid thermal response time.

Photomechanical photochromism in a cetyltrimethylammonium isopolytungstate.

The photochromic properties of a hybrid compound comprised of the surfactant cation cetyltrimethylammonium [(C16H33)N(CH3)3]+ (CTA+) and the isopolytungstate anion [H2W12O40]6- is investigated. The compound, which has the nominal formula (CTA)7[H2W12O40]Cl·2H2O, changes from white to blue when exposed to UV radiation. The sample returns to the bleached state if stored in the dark-ambient. Application of XPS indicates that the coloring species are WV and WIV. The CTA+ component is found by XPS and FTIR to undergo progressive and irreversible oxidation during this cycle. Examination of FTIR suggests that the changes occur at multiple sites across the amphiphile. Surprisingly, the photochromic cycle is correlated with changes in the X-ray diffraction pattern, indicating partially reversible changes in the ordering of the Keggin ions and their spacing. In particular, application of the UV radiation causes the progressive accumulation of strain in the [001] direction. This is due to permanent oxidative changes in the CTA+ accumulating from cycle to cycle, resulting in an increase in interlamellar-distance due to less interdigitation of the chains. This provides a controllable photomechanical response.

Optical properties and oxidation of α-phase Ag-Al thin films.

We investigate a series of Ag-Al thin films containing up to 12 at% Al with the purpose of discovering whether these alloys would be a better choice for nanophotonic applications than pure Ag. Variable angle spectroscopic ellipsometry, AFM, x-ray diffraction and density functional theory are applied to explore and characterize the materials. Electromagnetic simulations of optical properties are used to place the results into a theoretical framework. We find that the increase in electron-to-atom ratio associated with the Al additions changes the optical properties: additions of the order of 1-2 at% Al are beneficial as they are associated with favorable changes in the dielectric function, but for greater additions of Al there is a flattening of the absorption edge and an increase in optical loss. In addition, contents of more than about 2 at% Al are associated with the onset of time-dependent intergranular oxidation, which causes a pronounced dip in the reflectance spectrum at about 2.3-2.4 eV (∼500-540 nm).

Multipolar and dark-mode plasmon resonances on drilled silver nano-triangles.

Dark-mode plasmon resonances can be excited by positioning a suitable nano-antenna above a nanostructure to couple a planar incident wave-front into a virtual point source. We explore this phenomenon using a prototypical nanostructure consisting of a silver nanotriangle into which a hole has been drilled and a rod-like nano-antenna of variable aspect ratio. Using numerical simulations, we establish the behavior of the basic drilled nanotriangle under plane wave illumination and electron beam irradiation to provide a baseline, and then add the nano-antenna to investigate the stimulation of additional dark-mode plasmon resonances. The introduction of a suitably tuned nano-antenna provides a new and general means of exciting dark-mode resonances using plane wave light. The resulting system exhibits a very rich variety of radiant and sub-radiant resonance modes.

Seed-induced growth of flower-like Au-Ni-ZnO metal-semiconductor hybrid nanocrystals for photocatalytic applications.

The combination of metal and semiconductor components in nanoscale to form a hybrid nanocrystal provides an important approach for achieving advanced functional materials with special optical, magnetic and photocatalytic functionalities. Here, a facile solution method is reported for the synthesis of Au-Ni-ZnO metal-semiconductor hybrid nanocrystals with a flower-like morphology and multifunctional properties. This synthetic strategy uses noble and magnetic metal Au@Ni nanocrystal seeds formed in situ to induce the heteroepitaxial growth of semiconducting ZnO nanopyramids onto the surface of metal cores. Evidence of epitaxial growth of ZnO{0001} facets on Ni {111} facets is observed on the heterojunction, even though there is a large lattice mismatch between the semiconducting and magnetic components. Adjustment of the amount of Au and Ni precursors can control the size and composition of the metal core, and consequently modify the surface plasmon resonance (SPR) and magnetic properties. Room-temperature superparamagnetic properties can be achieved by tuning the size of Ni core. The as-prepared Au-Ni-ZnO nanocrystals are strongly photocatalytic and can be separated and re-cycled by virtue of their magnetic properties. The simultaneous combination of plasmonic, semiconducting and magnetic components within a single hybrid nanocrystal furnishes it multifunctionalities that may find wide potential applications.

Optical readout of the intracellular environment using nanoparticle transducers.

There is rapid growth in the use of multi-functional nanoparticles as transducers to probe the intracellular environment. New designs of nanoparticles can provide quantitative information at sub-cellular resolution on parameters such as pH, temperature and concentration of nicotinamide adenine dinucleotide (NADH) or selected metal ions. This new work builds on the existing practice of using nanoparticles and fluorescent dyes to provide enhanced microscopic images of cells, but goes beyond it by adding new functionalities and analytical capabilities. In this review, we discuss the recent literature on the development of such nanoparticles for simultaneous biosensing and imaging. We explore and examine the different measurements that will be possible, and analyze the likely accuracy and resolution that could be achieved.

Effect of precursor stoichiometry on the morphology of nanoporous platinum sponges.

Nanoscale sponges formed by de-alloying suitable metallic alloys have a wide variety of potential applications due to their enhanced catalytic, optical, and electrochemical properties. In general, these materials have a bi-continuous, vermicular morphology of pores and ligaments with a fibrous appearance; however, other morphologies are sometimes reported. Here, we investigate how stoichiometry and process parameters control the characteristics of sponges formed from thin film precursors of AlxPt. Materials deposited at elevated temperatures and with mole fraction of Al between 0.65 and 0.90 produce the classic isotropic fibrous sponges with a morphology that varies systematically with precursor stoichiometry; however, de-alloying of material deposited at room temperature produced unusual isotropic foamy sponges. The evidence suggests that formation of a conventional fibrous sponge requires an equilibrated precursor whereas foamy morphologies will result if the precursor is metastable. Modeling was used to investigate the range of possible morphologies. As stoichiometry changed in the model system, the average mean and Gaussian curvature of the sponges systematically changed, too. The evolution of these shapes passed through certain special morphologies; for example, modelled structures with 0.80 Al had a zero average Gaussian curvature and might represent a structural optimum for some applications. These observations provide a means to control sponge morphology at the nanoscale.

Charging of gold/metal oxide/gold nanocapacitors in a scanning electron microscope.

Triangular parallel-plate nanocapacitors were fabricated by a combination of microsphere lithography and physical vapor deposition. The devices were comprised of a 20 nm layer of dielectric material sandwiched between two 20 nm layers of gold. Dielectric materials with a range of relative permittivities were investigated. Charging of the capacitors was probed in a scanning electron microscope (SEM) by monitoring the change in brightness of the images of the devices as a function of time. The time constants, RC, associated with the charging of the capacitors, were extracted from the SEM grayscale data. The resulting average RC values were 248 ± 27 s for SiO2, 70 ± 8 s for Al2O3, 113 ± 80 s for ZnO and 125 ± 13 s for HfO2. These values are consistent with the anticipated RC values based on the resistivities and permittivities of the materials used in the devices and importantly, were measured without the need to attach any wires or leads.

Nanomedical research in Australia and New Zealand.

Although Australia and New Zealand have a combined population of less than 30 million, they have an active and interlinked community of nanomedical researchers. This report provides a synopsis and update on this network with a view to identifying the main topics of interest and their likely future trajectories. In addition, our report may also serve to alert others to opportunities for joint projects. Australian and New Zealand researchers are engaged in most of the possible nanomedical topics, but the majority of interest is focused on drug and nucleic acid delivery using nanoparticles or nanoporous constructs. There are, however, smaller programs directed at hyperthermal therapy and radiotherapy, various kinds of diagnostic tests and regenerative technologies.

Zinc hydroxide sulphate and its transformation to crystalline zinc oxide.

The thermal transformation of zinc hydroxide sulphate hydrate to zinc oxide has been examined using synchrotron X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, and surface area measurements. By collecting X-ray diffraction data in situ, we found that the dehydration of zinc hydroxide sulphate pentahydrate proceeded in discrete steps to form anhydrous zinc hydroxide sulphate. This compound then decomposed to a mixture of zinc oxide and a compound tentatively identified as Zn3(OH)2(SO4)2 at ~235 °C. At ~360 °C, the final dehydroxylation occurred with the formation of zinc oxy-sulphate, Zn3O(SO4)2, which then decomposed to ZnO at about ~800 °C. Interruption of the dehydration process can be used to synthesize the intermediate compounds.

In vivo study of spherical gold nanoparticles: inflammatory effects and distribution in mice.

OBJECTIVES: Gold nanoparticles (AuNPs) of 21 nm have been previously well characterized in vitro for their capacity to target macrophages via active uptake. However, the short-term impact of such AuNPs on physiological systems, in particular resident macrophages located in fat tissue in vivo, is largely unknown. This project investigated the distribution, organ toxicity and changes in inflammatory cytokines within the adipose tissue after mice were exposed to AuNPs. METHODS: Male C57BL/6 mice were injected intraperitoneally (IP) with a single dose of AuNPs (7.85 µg AuNPs/g). Body weight and energy intake were recorded daily. Tissues were collected at 1 h, 24 h and 72 h post-injection to test for organ toxicity. AuNP distribution was examined using electron microscopy. Proinflammatory cytokine expression and macrophage number within the abdominal fat pad were determined using real-time PCR. RESULTS: At 72 hours post AuNP injection, daily energy intake and body weight were found to be similar between Control and AuNP treated mice. However, fat mass was significantly smaller in AuNP-treated mice. Following IP injection, AuNPs rapidly accumulated within the abdominal fat tissue and some were seen in the liver. A reduction in TNFα and IL-6 mRNA levels in the fat were observed from 1 h to 72 h post AuNP injection, with no observable changes in macrophage number. There was no detectable toxicity to vital organs (liver and kidney). CONCLUSION: Our 21 nm spherical AuNPs caused no measurable organ or cell toxicity in mice, but were correlated with significant fat loss and inhibition of inflammatory effects. With the growing incidence of obesity and obesity-related diseases, our findings offer a new avenue for the potential development of gold nanoparticles as a therapeutic agent in the treatment of such disorders.

Multimode resonances in silver nanocuboids.

A rich variety of dipolar and higher order plasmon resonances have been predicted for nanoscale cubes and parallopipeds of silver, in contrast to the simple dipolar modes found on silver nanospheres or nanorods. However, in general, these multimode resonances are not readily detected in experimental colloidal ensembles, due primarily to the usual variation of size and shape of the particles obscuring or blending the individual extinction peaks. Recently, methods have been found to prepare silver parallopipeds with unprecedented shape control by nucleating the silver onto a tightly controlled suspension of gold nanorods (Okuno, Y.; Nishioka, K.; Kiya, A.; Nakashima, N.; Ishibashi, A.; Niidome, Y. Uniform and Controllable Preparation of Au-Ag Core-Shell Nanorods Using Anisotropic Silver Shell Formation on Gold Nanorods. Nanoscale 2010, 2, 1489-1493). The optical extinction spectra of suspensions of such monodisperse particles are found to contain multiple extinction peaks, which we show here to be due to the multimode resonances predicted by theoretical studies. Control of the radius of the nanoparticle edges is found to be an effective way to turn some of these modes on or off. These nanoparticles provide a flexible platform for the excitation, manipulation, and exploration of higher order plasmon resonances.