Sequential Lonsdaleite to Diamond Formation in Ureilite Meteorites via In Situ Chemical Fluid/Vapor Deposition.

Ureilite meteorites are arguably our only large suite of samples from the mantle of a dwarf planet and typically contain greater abundances of diamond than any known rock. Some also contain lonsdaleite, which may be harder than diamond. Here, we use electron microscopy to map the relative distribution of coexisting lonsdaleite, diamond, and graphite in ureilites. These maps show that lonsdaleite tends to occur as polycrystalline grains, sometimes with distinctive fold morphologies, partially replaced by diamond + graphite in rims and cross-cutting veins. These observations provide strong evidence for how the carbon phases formed in ureilites, which, despite much conjecture and seemingly conflicting observations, has not been resolved. We suggest that lonsdaleite formed by pseudomorphic replacement of primary graphite shapes, facilitated by a supercritical C-H-O-S fluid during rapid decompression and cooling. Diamond + graphite formed after lonsdaleite via ongoing reaction with C-H-O-S gas. This graphite > lonsdaleite > diamond + graphite formation process is akin to industrial chemical vapor deposition but operates at higher pressure (∼1-100 bar) and provides a pathway toward manufacture of shaped lonsdaleite for industrial application. It also provides a unique model for ureilites that can reconcile all conflicting observations relating to diamond formation.

Room-Temperature Magnetic Phase Transition in an Electrically Tuned van der Waals Ferromagnet.

Finding tunable van der Waals (vdW) ferromagnets that operate at above room temperature is an important research focus in physics and materials science. Most vdW magnets are only intrinsically magnetic far below room temperature and magnetism with square-shaped hysteresis at room temperature has yet to be observed. Here, we report magnetism in a quasi-2D magnet Cr_{1.2}Te_{2} observed at room temperature (290 K). This magnetism was tuned via a protonic gate with an electron doping concentration up to 3.8×10^{21} cm^{-3}. We observed nonmonotonic evolutions in both coercivity and anomalous Hall resistivity. Under increased electron doping, the coercivities and anomalous Hall effects (AHEs) vanished, indicating a doping-induced magnetic phase transition. This occurred up to room temperature. DFT calculations showed the formation of an antiferromagnetic (AFM) phase caused by the intercalation of protons which induced significant electron doping in the Cr_{1.2}Te_{2}. The tunability of the magnetic properties and phase in room temperature magnetic vdW Cr_{1.2}Te_{2} is a significant step towards practical spintronic devices.

Hexagonal metal oxide monolayers derived from the metal-gas interface.

Two-dimensional (2D) crystals are promising materials for developing future nano-enabled technologies1-6. The cleavage of weak, interlayer van der Waals bonds in layered bulk crystals enables the production of high-quality 2D, atomically thin monolayers7-10. Nonetheless, as earth-abundant compounds, metal oxides are rarely accessible as pure and fully stoichiometric monolayers owing to their ion-stabilized 'lamellar' bulk structure11-14. Here, we report the discovery of a layered planar hexagonal phase of oxides from elements across the transition metals, post-transition metals, lanthanides and metalloids, derived from strictly controlled oxidation at the metal-gas interface. The highly crystalline monolayers, without the support of ionic dopants or vacancies, can easily be mechanically exfoliated by stamping them onto substrates. Monolayer and few-layered hexagonal TiO2 are characterized as examples, showing p-type semiconducting properties with hole mobilities of up to 950 cm2 V-1 s-1 at room temperature. The strategy can be readily extended to a variety of elements, possibly expanding the exploration of metal oxides in the 2D quantum regime.

Cobalt-Directed Assembly of Antibodies onto Metal-Phenolic Networks for Enhanced Particle Targeting.

The orientation-specific immobilization of antibodies onto nanoparticles, to preserve antibody-antigen recognition, is a key challenge in developing targeted nanomedicines. Herein, we report the targeting ability of metal-phenolic network (MPN)-coated gold nanoparticles with surface-physisorbed antibodies against respective antigens. The MPN coatings were self-assembled from metal ions (FeIII, CoII, CuII, NiII, or ZnII) cross-linked with tannic acid. Upon physisorption of antibodies, all particle systems exhibited enhanced association with target antigens, with CoII systems demonstrating more than 2-fold greater association. These systems contained more metal atoms distributed in a way to specifically interact with antibodies, which were investigated by molecular dynamics simulations. A model antibody fragment crystallizable (Fc) region in solution with CoII-tannic acid complexes revealed that the solvent-exposed CoII can directly coordinate to the histidine-rich portion of the Fc region. This one-pot interaction suggests anchoring of the antibody Fc region to the MPN on nanoparticles, allowing for enhanced targeting.

Retrospective evaluation of perioperative and short term clinical outcomes in appendicular long bone skeleton fractures repaired via the string of pearls (SOP) locking plate system.

BACKGROUND: Internal plate fixation and, more recently, locking plate fixation are commonly used in the repair of fractures in small animal surgery. This retrospective study reviewed the use of the String of Pearls locking plate system in the fixation/repair of appendicular long bone skeleton fractures in 31 small animal veterinary patients (33 fractures). RESULTS: Major complications necessitating revision surgery occurred in 7/33 (21%), with implant failure as the inciting cause in all cases. Variables corresponding to an unsuccessful outcome were evaluated, and a correlation was found with plates placed in a bridging manner (placed without rigid anatomic reconstruction, p = 0.02) and length of follow-up (p = 0.01). CONCLUSIONS: The SOP plating system can be used in the repair of appendicular longbone skeletal fractures, however, the authors propose that adjunct fixation, such as intramedullary pin, double plating, or external coaptation would likely improve results and should be considered imperative in cases in which anatomic reconstruction is either not desirable or achievable.

Effect of a Swelling Agent on the Performance of Ni/Porous Silica Catalyst for CH4-CO2 Reforming.

Hierarchical porous materials are of great interest in various industrial applications because of their potential to overcome the mass transport limitations typically encountered for single-mode porous materials. This report describes the synthesis of a hierarchical trimodal porous silica-based material using a 7.5 molar ratio of a relatively inexpensive nonionic surfactant template, triblock copolymer P123, EO20PO70EO20. The pore size distribution curve shows the presence of three types of pores with average diameters of ∼8, 25, and 89 nm. Electron microscope images confirm the existence of smaller ordered mesopores (first mode), larger ordered mesopores (second mode), and macropores (third mode). Ni nanoparticles dispersed on this trimodal porous silica produce a material that exhibited excellent catalytic performance for the CO2 reforming of CH4. This research provides new insights that will facilitate the development of trimodal porous silica (TMS) materials for a variety of applications. The results demonstrated that the presence of large pores (second and third mode pores) in TMS material increased the number of accessible active Ni sites, which led to the high activity observed for Ni/TMS catalyst.

Modular molecules: site-selective metal substitution, photoreduction, and chirality in polyoxometalate hybrids.

The first members of a promising new family of hybrid amino acid-polyoxometalates have emerged from a search for modular functional molecules. Incorporation of glycine (Gly) or norleucine (Nle) ligands into an yttrium-tungstoarsenate structural backbone, followed by crystallization with p-methylbenzylammonium (p-MeBzNH3(+)) cations, affords (p-MeBzNH3)6K2(GlyH)[As(III)4(Y(III)W(VI)3)W(VI)44Y(III)4O159(Gly)8(H2O)14]⋅47 H2O (1) and enantiomorphs (p-MeBzNH3)15(NleH)3[As(III)4(Mo(V)2Mo(VI)2)W(VI)44Y(III)4O160(Nle)9(H2O)11][As(III)4(Mo(VI)2W(VI)2)W(VI)44Y(III)4O160(Nle)9(H2O)11] (generically designated 2: L-Nle, 2 a; D-Nle, 2 b). An intensive structural, spectroscopic, electrochemical, magnetochemical and theoretical investigation has allowed the elucidation of site-selective metal substitution and photoreduction of the tetranuclear core of the hybrid polyanions. In the solid state, markedly different crystal packing is evident for the compounds, which indicates the role of noncovalent interactions involving the amino acid ligands. In solution, mass spectrometric and small-angle X-ray scattering studies confirm maintenance of the structure of the polyanions of 2, while circular dichroism demonstrates that the chirality is also maintained. The combination of all of these features in a single modular family emphasizes the potential of such hybrid polyoxometalates to provide nanoscale molecular materials with tunable properties.

Interaction of hydrogen with ZnO nanopowders--evidence of hydroxyl group formation.

There have been many investigations to reveal the nature of the hydrogen gas and ZnO nanopowder interaction at elevated temperatures, while at present no conclusive description of such an interaction has been confidently reported. In this work, we demonstrate that a hydroxyl group is formed during this interaction, depending on size and relative crystallinity of nanopowders. Our in situ Raman spectroscopy investigations show that the interaction directly affects the intensity of the Raman signal at 483 cm(-1), relative to the peak at 519 cm(-1). Ex situ x-ray diffraction (XRD) and infrared spectroscopy also show extra peaks at 44° and 1618 cm(-1), respectively, after hydrogenation. These peaks were all identified as surface hydroxyl groups, which can be related to the formation of water on the ZnO nanopowder surfaces.

ZIF-C for targeted RNA interference and CRISPR/Cas9 based gene editing in prostate cancer.

Gene therapy is highly suited for prostate cancer (PC). Metal-organic-frameworks (MOFs) are potential gene delivery systems. Target-specific cytoplasmic and nuclear knockdown in host gene expression using ZIF-C is shown for the first time through RNAi and CRISPR/Cas9 based gene editing in PC cells. A green tea phytochemical coating enhances intracellular delivery.

Iridescence and hydrophobicity have no clear delineation that explains flower petal micro-surface.

Plant organs including flowers and leaves typically have a variety of different micro-structures present on the epidermal surface. These structures can produce measurable optical effects with viewing angle including shifts in peak reflectance and intensity; however, these different structures can also modulate hydrophobic properties of the surfaces. For some species optical effects have been proposed to act as signals to enhance pollination interactions, whilst the ability to efficiently shed water provides physiological advantages to plants in terms of gas exchange and reducing infections. Currently, little is known about epidermal surface structure of flowering plants in the Southern Hemisphere, and how micro-surface may be related with either hydrophobicity or visual signalling. We measured four Australian native species and two naturalised species using a combination of techniques including SEM imaging, spectral sampling with a goniometer and contact angle measurements. Spectral data were evaluated in relation to published psychophysics results for important pollinators and reveal that potential visual changes, where present, were unlikely to be perceived by relevant pollinators. Nevertheless, hydrophobicity also did not simply explain petal surfaces as similar structures could in some cases result in very different levels of water repellency.

Preparation of Au nanoparticles on a magnetically responsive support via pyrolysis of a Prussian blue composite.

A strategy is described for the direct preparation of Au nanoparticles (AuNPs) on a Fe-based support, coated with porous carbon (PC), via pyrolysis of an AuCN functionalised Prussian Blue (PB) metal organic framework (MOF). The composite starting material was prepared with an even distribution of AuCN on the surface via galvanic exchange of PB with a gold salt in solution. The resulting structures after pyrolysis were shown to be active Au-based nanomaterials for model applications including catalysis (4-nitrophenol reduction) and electroanalysis (arsenic (III) detection), suggesting broad application where Au nanoparticles are required at a liquid-solid interface. The Fe based support was seen to consist of Fe, Fe3C and Fe4C phases, and the carbon coating increased the stability and improved the conductivity of the materials. The temperature of pyrolysis was seen to affect the activity of the supported nanoparticles, with an increased Au surface area obtained at the higher pyrolysis temperature (650 °C) tested. A general strategy is thus confirmed for preparation of noble metal nanoparticles evenly distributed on a magnetic support, allowing easy separation of catalysts from products in heterogeneous applications.

Co3O4 needles on Au honeycomb as a non-invasive electrochemical biosensor for glucose in saliva.

While glucose monitoring technology is widely available, the continued prevalence of diabetes around the world coupled with its debilitating effects continues to grow. The significant limitations which exist in the current technology, instils the need for materials capable of non-invasive glucose detection. In this study a unique non-enzymatic electrochemical glucose sensor was developed, utilising a gold honeycomb-like framework upon which sharp Co3O4 needles are anchored. This composite nanomaterial demonstrates excellent sensing performance in glucose concentrations ranging between 20 µM and 4 mM, exceeding the range required for non-invasive glucose sensing. In conjunction with this high sensitivity (2.014 mA mM-1·cm-2), the material possesses excellent selectivity towards glucose for commonly interfering physiological species such as uric acid and ascorbic acid. Glucose detection in synthetic saliva was then performed showing excellent capability in the low concentration range (20 µM-1 mM) for non-invasive sensing performance. Further tests showed good selectivity of the sensor in physiological contaminants commonly found in saliva such as cortisol and dopamine. This development provides excellent scope to create next-generation non-invasive diabetes monitoring platforms, with excellent performance when detecting low glucose concentrations in complex solutions such as saliva.

Zinc Titanate Nanoarrays with Superior Optoelectrochemical Properties for Chemical Sensing.

In this report, the gas sensing performance of zinc titanate (ZnTiO3) nanoarrays (NAs) synthesized by coating hydrothermally formed zinc oxide (ZnO) NAs with TiO2 using low-temperature chemical vapor deposition is presented. By controlling the annealing temperature, diffusion of ZnO into TiO2 forms a mixed oxide of ZnTiO3 NAs. The uniformity and the electrical properties of ZnTiO3 NAs made them ideal for light-activated acetone gas sensing applications for which such materials are not well studied. The acetone sensing performance of the ZnTiO3 NAs is tested by biasing the sensor with voltages from 0.1 to 9 V dc in an amperometric mode. An increase in the applied bias was found to increase the sensitivity of the device toward acetone under photoinduced and nonphotoinduced (dark) conditions. When illuminated with 365 nm UV light, the sensitivity was observed to increase by 3.4 times toward 12.5 ppm acetone at 350 °C with an applied bias of 9 V, as compared to dark conditions. The sensor was also observed to have significantly reduced the adsorption time, desorption time, and limit of detection (LoD) when excited by the light source. For example, LoD of the sensor in the dark and under UV light at 350 °C with a 9 V bias is found to be 80 and 10 ppb, respectively. The described approach also enabled acetone sensing at an operating temperature down to 45 °C with a repeatability of >99% and a LoD of 90 ppb when operated under light, thus indicating that the ZnTiO3 NAs are a promising material for low concentration acetone gas sensing applications.

Antisymmetric magnetoresistance in van der Waals Fe3GeTe2/graphite/Fe3GeTe2 trilayer heterostructures.

With no requirements for lattice matching, van der Waals (vdW) ferromagnetic materials are rapidly establishing themselves as effective building blocks for next-generation spintronic devices. We report a hitherto rarely seen antisymmetric magnetoresistance (MR) effect in vdW heterostructured Fe3GeTe2 (FGT)/graphite/FGT devices. Unlike conventional giant MR (GMR), which is characterized by two resistance states, the MR in these vdW heterostructures features distinct high-, intermediate-, and low-resistance states. This unique characteristic is suggestive of underlying physical mechanisms that differ from those observed before. After theoretical calculations, the three-resistance behavior was attributed to a spin momentum locking induced spin-polarized current at the graphite/FGT interface. Our work reveals that ferromagnetic heterostructures assembled from vdW materials can exhibit substantially different properties to those exhibited by similar heterostructures grown in vacuum. Hence, it highlights the potential for new physics and new spintronic applications to be discovered using vdW heterostructures.

Hard magnetic properties in nanoflake van der Waals Fe3GeTe2.

Two-dimensional van der Waals materials have demonstrated fascinating optical and electrical characteristics. However, reports on magnetic properties and spintronic applications of van der Waals materials are scarce by comparison. Here, we report anomalous Hall effect measurements on single crystalline metallic Fe3GeTe2 nanoflakes with different thicknesses. These nanoflakes exhibit a single hard magnetic phase with a near square-shaped magnetic loop, large coercivity (up to 550 mT at 2 K), a Curie temperature near 200 K and strong perpendicular magnetic anisotropy. Using criticality analysis, the coupling length between van der Waals atomic layers in Fe3GeTe2 is estimated to be ~5 van der Waals layers. Furthermore, the hard magnetic behaviour of Fe3GeTe2 can be well described by a proposed model. The magnetic properties of Fe3GeTe2 highlight its potential for integration into van der Waals magnetic heterostructures, paving the way for spintronic research and applications based on these devices.

Effect of Surface Chemistry on the Fluorescence of Detonation Nanodiamonds.

Detonation nanodiamonds (DNDs) have unique physical and chemical properties that make them invaluable in many applications. However, DNDs are generally assumed to show weak fluorescence, if any, unless chemically modified with organic molecules. We demonstrate that detonation nanodiamonds exhibit significant and excitation-wavelength-dependent fluorescence from the visible to the near-infrared spectral region above 800 nm, even without the engraftment of organic molecules to their surfaces. We show that this fluorescence depends on the surface functionality of the DND particles. The investigated functionalized DNDs, produced from the same purified DND as well as the as-received polyfunctional starting material, are hydrogen, hydroxyl, carboxyl, ethylenediamine, and octadecylamine-terminated. All DNDs are investigated in solution and on a silicon wafer substrate and compared to fluorescent high-pressure high-temperature nanodiamonds. The brightest fluorescence is observed from octadecylamine-functionalized particles and is more than 100 times brighter than the least fluorescent particles, carboxylated DNDs. The majority of photons emitted by all particle types likely originates from non-diamond carbon. However, we locally find bright and photostable fluorescence from nitrogen-vacancy centers in diamond in hydrogenated, hydroxylated, and carboxylated detonation nanodiamonds. Our results contribute to understanding the effects of surface chemistry on the fluorescence of DNDs and enable the exploration of the fluorescent properties of DNDs for applications in theranostics as nontoxic fluorescent labels, sensors, nanoscale tracers, and many others where chemically stable and brightly fluorescent nanoparticles with tailorable surface chemistry are needed.

Exfoliation Solvent Dependent Plasmon Resonances in Two-Dimensional Sub-Stoichiometric Molybdenum Oxide Nanoflakes.

Few-layer two-dimensional (2D) molybdenum oxide nanoflakes are exfoliated using a grinding assisted liquid phase sonication exfoliation method. The sonication process is carried out in five different mixtures of water with both aprotic and protic solvents. We found that surface energy and solubility of mixtures play important roles in changing the thickness, lateral dimension, and synthetic yield of the nanoflakes. We demonstrate an increase in proton intercalation in 2D nanoflakes upon simulated solar light exposure. This results in substoichiometric flakes and a subsequent enhancement in free electron concentrations, producing plasmon resonances. Two plasmon resonance peaks associated with the thickness and the lateral dimension axes are observable in the samples, in which the plasmonic peak positions could be tuned by the choice of the solvent in exfoliating 2D molybdenum oxide. The extinction coefficients of the plasmonic absorption bands of 2D molybdenum oxide nanoflakes in all samples are found to be high (ε > 10(9) L mol(-1) cm(-1)). It is expected that the tunable plasmon resonances of 2D molybdenum oxide nanoflakes presented in this work can be used in future electronic, optical, and sensing devices.

Substoichiometric two-dimensional molybdenum oxide flakes: a plasmonic gas sensing platform.

Two-dimensional (2D) molybdenum oxides at their various stoichiometries are promising candidates for generating plasmon resonances in visible light range. Herein, we demonstrate plasmonic 2D molybdenum oxide flakes for gas sensing applications, in which hydrogen (H2) is selected as a model gas. The 2D molybdenum oxide flakes are obtained using a grinding-assisted liquid exfoliation method and exposed to simulated sunlight to acquire its substoichiometric quasi-metallic form. After the exposure to H2 gas molecules, the quasi-metallic molybdenum oxide flakes are partially transformed into semiconducting states, thus gradually losing their plasmonic properties. The novel 2D plasmonic sensing platform is tested using different concentrations of H2 gas at various operating temperatures to comprehensively assess its sensing performance. The presented 2D plasmonic system offers great opportunities for future sensing and optical applications.

Electrochromic properties of TiO2 nanotubes coated with electrodeposited MoO3.

Despite a favourable morphology, anodized and ordered TiO2 nanotubes are incapable of showing electrochromic properties in comparison to many other metal oxide counterparts. To tackle this issue, MoO3 of ~5 to 15 nm thickness was electrodeposited onto TiO2 nanotube arrays. A homogenous MoO3 coating was obtained and the crystal phase of the electrodeposited coating was determined to be α-MoO3. The electronic and optical augmentations of the MoO3 coated TiO2 platforms were evaluated through electrochromic measurements. The MoO3/TiO2 system showed a 4-fold increase in optical density over bare TiO2 when the thickness of the MoO3 coating was optimised. The enhancement was ascribed to (a) the α-MoO3 coating reducing the bandgap of the composite material, which shifted the band edge of the TiO2 platform, and subsequently increased the charge carrier transfer of the overall system and (b) the layered morphology of α-MoO3 that increased the intercalation probability and also provided direct pathways for charge carrier transfer.

Aqueous phase synthesis of copper nanoparticles: a link between heavy metal resistance and nanoparticle synthesis ability in bacterial systems.

We demonstrate aqueous phase biosynthesis of phase-pure metallic copper nanoparticles (CuNPs) using a silver resistant bacterium Morganella morganii. This is particularly important considering that there has been no report that demonstrates biosynthesis and stabilization of pure copper nanoparticles in the aqueous phase. Electrochemical analysis of bacterial cells exposed to Cu(2+) ions provides new insights into the mechanistic aspect of Cu(2+) ion reduction within the bacterial cell and indicates a strong link between the silver and copper resistance machinery of bacteria in the context of metal ion reduction. The outcomes of this study take us a step closer towards designing rational strategies for biosynthesis of different metal nanoparticles using microorganisms.