Synthesis and Characterization of MgCr2S4 Thiospinel as a Potential Magnesium Cathode.

Magnesium-ion batteries are a promising energy storage technology because of their higher theoretical energy density and lower cost of raw materials. Among the major challenges has been the identification of cathode materials that demonstrate capacities and voltages similar to lithium-ion systems. Thiospinels represent an attractive choice for new Mg-ion cathode materials owing to their interconnected diffusion pathways and demonstrated high cation mobility in numerous systems. Reported magnesium thiospinels, however, contain redox inactive metals such as scandium or indium, or have low voltages, such as MgTi2S4. This article describes the direct synthesis and structural and electrochemical characterization of MgCr2S4, a new thiospinel containing the redox active metal chromium and discusses its physical properties and potential as a magnesium battery cathode. However, as chromium(III) is quite stable against oxidation in sulfides, removing magnesium from the material remains a significant challenge. Early attempts at both chemical and electrochemical demagnesiation are discussed.

Heterogeneous nucleation and shape transformation of multicomponent metallic nanostructures.

To be able to control the functions of engineered multicomponent nanomaterials, a detailed understanding of heterogeneous nucleation at the nanoscale is essential. Here, by using in situ synchrotron X-ray scattering, we show that in the heterogeneous nucleation and growth of Au on Pt or Pt-alloy seeds the heteroepitaxial growth of the Au shell exerts high stress (∼2 GPa) on the seed by forming a core/shell structure in the early stage of the reaction. The development of lattice strain and subsequent strain relaxation, which we show using atomic-resolution transmission electron microscopy to occur through the slip of {111} layers, induces morphological changes from a core/shell to a dumbbell structure, and governs the nucleation and growth kinetics. We also propose a thermodynamic model for the nucleation and growth of dumbbell metallic heteronanostructures.

Atomic Origins of Monoclinic-Tetragonal (Rutile) Phase Transition in Doped VO2 Nanowires.

There has been long-standing interest in tuning the metal-insulator phase transition in vanadium dioxide (VO2) via the addition of chemical dopants. However, the underlying mechanisms by which doping elements regulate the phase transition in VO2 are poorly understood. Taking advantage of aberration-corrected scanning transmission electron microscopy, we reveal the atomistic origins by which tungsten (W) dopants influence the phase transition in single crystalline WxV1-xO2 nanowires. Our atomically resolved strain maps clearly show the localized strain normal to the (122̅) lattice planes of the low W-doped monoclinic structure (insulator). These strain maps demonstrate how anisotropic localized stress created by dopants in the monoclinic structure accelerates the phase transition and lead to relaxation of structure in tetragonal form. In contrast, the strain distribution in the high W-doped VO2 structure is relatively uniform as a result of transition to tetragonal (metallic) phase. The directional strain gradients are furthermore corroborated by density functional theory calculations that show the energetic consequences of distortions to the local structure. These findings pave the roadmap for lattice-stress engineering of the MIT behavior in strongly correlated materials for specific applications such as ultrafast electronic switches and electro-optical sensors.

Reversible modulation of orbital occupations via an interface-induced polar state in metallic manganites.

The breaking of orbital degeneracy on a transition metal cation and the resulting unequal electronic occupations of these orbitals provide a powerful lever over electron density and spin ordering in metal oxides. Here, we use ab initio calculations to show that reversibly modulating the orbital populations on Mn atoms can be achieved at ferroelectric/manganite interfaces by the presence of ferroelectric polarization on the nanoscale. The change in orbital occupation can be as large as 10%, greatly exceeding that of bulk manganites. This reversible orbital splitting is in large part controlled by the propagation of ferroelectric polar displacements into the interfacial region, a structural motif absent in the bulk and unique to the interface. We use epitaxial thin film growth and scanning transmission electron microscopy to verify this key interfacial polar distortion and discuss the potential of reversible control of orbital polarization via nanoscale ferroelectrics.

Deep ultraviolet emitting polarization induced nanowire light emitting diodes with AlxGa1-xN active regions.

In this report, we demonstrate band gap tuning of the active region emission wavelength from 365 nm to 250 nm in light emitting diodes fashioned from catalyst-free III-nitride nanowires. Optical characteristics of the nanowire heterostructures and fabricated devices are studied via electroluminescence (EL) and photoluminescence spectroscopy over a wide range of active region compositions. It is observed that for typical nanowire plasma assisted molecular beam epitaxy growth conditions, tuning of emission to wavelengths shorter than 300 nm is hampered by the presence of an optically active defect level. We show that by increasing the AlGaN nanowire growth temperatures this defect emission can be suppressed. These findings are applied to growth of the active region of a nanowire light emitting diode, resulting in a polarization-induced nanowire light emitting diode with peak EL at 250 nm.

A new silicon drift detector for high spatial resolution STEM-XEDS: performance and applications.

A newly designed, 100 mm2, silicon drift detector has been installed on an aberration-corrected scanning transmission electron microscope equipped with an ultra-high resolution pole piece, without requiring column modifications. With its unique, windowless design, the detector's active region is in close proximity to the sample, resulting in a dramatic increase in count rate, while demonstrating an increased sensitivity to low energy X-rays and a muted tilt dependence. Numerous examples of X-ray energy dispersive spectrometry are presented on relevant materials such as Al x Ga1-x N nanowires, perovskite oxides, and polycrystalline CdTe thin films, across both varying length scales and accelerating voltages.

Mixed polarity in polarization-induced p-n junction nanowire light-emitting diodes.

Polarization-induced nanowire light emitting diodes (PINLEDs) are fabricated by grading the Al composition along the c-direction of AlGaN nanowires grown on Si substrates by plasma-assisted molecular beam epitaxy (PAMBE). Polarization-induced charge develops with a sign that depends on the direction of the Al composition gradient with respect to the [0001] direction. By grading from GaN to AlN then back to GaN, a polarization-induced p-n junction is formed. The orientation of the p-type and n-type sections depends on the material polarity of the nanowire (i.e., Ga-face or N-face). Ga-face material results in an n-type base and a p-type top, while N-face results in the opposite. The present work examines the polarity of catalyst-free nanowires using multiple methods: scanning transmission electron microscopy (STEM), selective etching, conductive atomic force microscopy (C-AFM), and electroluminescence (EL) spectroscopy. Selective etching and STEM measurements taken in annular bright field (ABF) mode demonstrate that the preferred orientation for catalyst-free nanowires grown by PAMBE is N-face, with roughly 10% showing Ga-face orientation. C-AFM and EL spectroscopy allow electrical and optical differentiation of the material polarity in PINLEDs since the forward bias direction depends on the p-n junction orientation and therefore on nanowire polarity. Specifically, C-AFM reveals that the direction of forward bias for individual nanowire LEDs changes with the polarity, as expected, due to reversal of the sign of the polarization-induced charge. Electroluminescence measurements of mixed polarity PINLEDs wired in parallel show ambipolar emission due to the mixture of p-n and n-p oriented PINLEDs. These results show that, if catalyst-free III-nitride nanowires are to be used to form polarization-doped heterostructures, then it is imperative to understand their mixed polarity and to design devices using these nanowires accordingly.

HbA1c, blood glucose monitoring and insulin therapy.

BACKGROUND: Safe adjustment of insulin therapy requires review of both long-term and short-term glycaemic control, HbA1c and blood glucose monitoring (BGM), respectively. OBJECTIVE: To summarise the information that HbA1c and BGM provide about glycaemic control and to outline how to use these measures to guide insulin therapy. DISCUSSION: There are three components to the 24-hour blood glucose profile: 1. the flat baseline set by the fasting blood glucose 2. often a daytime increment in this baseline 3. the prandial blood glucose increase. Insulin therapy aims to sequentially control each component to achieve a desired level of glycaemic control (usually HbA1c <7%). Clinical use of the two glycaemic measures requires that BGM results are not highly variable (which complicates safe insulin adjustment) and that both BGM and HbA1c results are reliable. If these conditions are met and there is a discrepancy between the BGM profile and the average blood glucose expected from the measured HbA1c, there may be periods of undetected hyper- or hypoglycaemia over the 24-hour period, which require changes in insulin therapy.

Contaminants in stream sediments from seven United States metropolitan areas: part I: distribution in relation to urbanization.

Organic contaminants and trace elements were measured in bed sediments collected from streams in seven metropolitan study areas across the United States to assess concentrations in relation to urbanization. Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorine pesticides, the pyrethroid insecticide bifenthrin, and several trace elements were significantly related to urbanization across study areas. Most contaminants (except bifenthrin, chromium, nickel) were significantly related to the total organic carbon (TOC) content of the sediments. Regression models explained 45-80 % of the variability in individual contaminant concentrations using degree of urbanization, sediment-TOC, and study-area indicator variables (which represent the combined influence of unknown factors, such as chemical use or release, that are not captured by available explanatory variables). The significance of one or more study-area indicator variables in all models indicates marked differences in contaminant levels among some study areas, even after accounting for the nationally modeled effects of urbanization and sediment-TOC. Mean probable effect concentration quotients (PECQs) were significantly related to urbanization. Trace elements were the major contributors to mean PECQs at undeveloped sites, whereas organic contaminants, especially bifenthrin, were the major contributors at highly urban sites. Pyrethroids, where detected, accounted for the largest share of the mean PECQ. Part 2 of this series (Kemble et al. 2012) evaluates sediment toxicity to amphipods and midge in relation to sediment chemistry.

Polarization-induced pn diodes in wide-band-gap nanowires with ultraviolet electroluminescence.

Almost all electronic devices utilize a pn junction formed by random doping of donor and acceptor impurity atoms. We developed a fundamentally new type of pn junction not formed by impurity-doping, but rather by grading the composition of a semiconductor nanowire resulting in alternating p and n conducting regions due to polarization charge. By linearly grading AlGaN nanowires from 0% to 100% and back to 0% Al, we show the formation of a polarization-induced pn junction even in the absence of any impurity doping. Since electrons and holes are injected from AlN barriers into quantum disk active regions, graded nanowires allow deep ultraviolet LEDs across the AlGaN band-gap range with electroluminescence observed from 3.4 to 5 eV. Polarization-induced p-type conductivity in nanowires is shown to be possible even without supplemental acceptor doping, demonstrating the advantage of polarization engineering in nanowires compared with planar films and providing a strategy for improving conductivity in wide-band-gap semiconductors. As polarization charge is uniform within each unit cell, polarization-induced conductivity without impurity doping provides a solution to the problem of conductivity uniformity in nanowires and nanoelectronics and opens a new field of polarization engineering in nanostructures that may be applied to other polar semiconductors.

Three-dimensional GaN/AlN nanowire heterostructures by separating nucleation and growth processes.

Bottom-up nanostructure assembly has been a central theme of materials synthesis over the past few decades. Semiconductor quantum dots and nanowires provide additional degrees of freedom for charge confinement, strain engineering, and surface sensitivity-properties that are useful to a wide range of solid state optical and electronic technologies. A central challenge is to understand and manipulate nanostructure assembly to reproducibly generate emergent structures with the desired properties. However, progress is hampered due to the interdependence of nucleation and growth phenomena. Here we show that by dynamically adjusting the growth kinetics, it is possible to separate the nucleation and growth processes in spontaneously formed GaN nanowires using a two-step molecular beam epitaxy technique. First, a growth phase diagram for these nanowires is systematically developed, which allows for control of nanowire density over three orders of magnitude. Next, we show that by first nucleating nanowires at a low temperature and then growing them at a higher temperature, height and density can be independently selected while maintaining the target density over long growth times. GaN nanowires prepared using this two-step procedure are overgrown with three-dimensionally layered and topologically complex heterostructures of (GaN/AlN). By adjusting the growth temperature in the second growth step either vertical or coaxial nanowire superlattices can be formed. These results indicate that a two-step method allows access to a variety of kinetics at which nanowire nucleation and adatom mobility are adjustable.

HbA1c and monitoring glycaemia.

This article forms part of our 'Tests and results' series for 2012, which aims to provide information about common tests that general practitioners order regularly. It considers areas such as indications, what to tell the patient, what the test can and cannot tell you, and interpretation of results.

Thyroid therapy - tips and traps.

CASE STUDY: Thea, aged 63 years, presents for review after a small inferior myocardial infarction (MI) 3 months previously.

Oral glucose tolerance testing.

The oral glucose tolerance test (OGTT) is currently the gold standard for the diagnosis of diabetes. The recommended preparation for and administration of the OGTT are important to ensure that test results are not affected. Interpretation is based on venous plasma glucose results before and 2 hours after a 75 g oral glucose load.

Groundwater discharges as a source of phytoestrogens and other agriculturally derived contaminants to streams.

Groundwater discharge zones in streams are important habitats for aquatic organisms. The use of discharge zones for thermal refuge and spawning by fish and other biota renders them susceptible to potential focused discharge of groundwater contamination. Currently, there is a paucity of information about discharge zones as a potential exposure pathway of chemicals to stream ecosystems. Using thermal mapping technologies to locate groundwater discharges, shallow groundwater and surface water from three rivers in the Chesapeake Bay Watershed, USA were analyzed for phytoestrogens, pesticides and their degradates, steroid hormones, sterols and bisphenol A. A Bayesian censored regression model was used to compare groundwater and surface water chemical concentrations. The most frequently detected chemicals in both ground and surface water were the phytoestrogens genistein (79%) and formononetin (55%), the herbicides metolachlor (50%) and atrazine (74%), and the sterol cholesterol (88%). There was evidence suggesting groundwater discharge zones could be a unique exposure pathway of chemicals to surface water systems, in our case, metolachlor sulfonic acid (posterior mean concentration = 150 ng/L in groundwater and 4.6 ng/L in surface water). Our study also demonstrated heterogeneity of chemical concentration in groundwater discharge zones within a stream for the phytoestrogen formononetin, the herbicides metolachlor and atrazine, and cholesterol. Results support the hypothesis that discharge zones are an important source of exposure of phytoestrogens and herbicides to aquatic organisms. To manage critical resources within the Chesapeake Bay Watershed, more work is needed to characterize exposure in discharge zones more broadly across time and space.

Pesticides and their degradates in groundwater reflect past use and current management strategies, Long Island, New York, USA.

Long Island, New York, has a mix of urban/suburban to agricultural/horticultural land use and nearly 3 million residents that rely on a sole-source aquifer for drinking water. The analysis of shallow groundwater (<40 m below land surface) collected from 54 monitoring wells across Long Island detected 53 pesticides or pesticide degradates. Maximum concentrations for individual pesticides or pesticide degradates ranged from 3 to 368,000 ng/L. The highest concentrations and most frequent pesticide detections occurred in samples collected from the pesticide management (PM) network, set in an agricultural/horticultural area in eastern Long Island with coordinated pesticide management by state and local agencies. The other two networks (Suffolk and Nassau/Queens) were set in suburban and urban areas, respectively, and had less frequent detections and lower pesticide concentrations than the PM network. Pesticide detections and concentration patterns (herbicide, insecticide, or fungicide) differed among the three networks revealing broad differences in land use. The predominance of fungicides metalaxyl, 1H-1,2,4-triazole (propiconazole/myclobutanil degradate), and 4-hydroxychlorothalonil (HCTL, chlorothalonil degradate) in samples from the PM network reflects their intensive use in agricultural settings. Total fungicide concentrations in the PM network ranged from <10 to >300,000 ng/L. The widespread detection of imidacloprid and triazine herbicides, simazine and atrazine, reveal a mixture of current and past use pesticides across the Long Island region. Low concentrations (<200 ng/L) of the triazines in the Suffolk and Nassau/Queens networks may reflect a change in land use and application. Acetanilide herbicides and aldicarb have been discontinued for 20 and 40 years, respectively, yet the concentrations of their degradates were among the highest observed in this study. Acetanilide (total concentrations up to 10,000 ng/L) and aldicarb degradates (up to 270 ng/L) are present in the PM network at much lower concentrations than previous Long Island studies and reflect changes in agricultural practices and pesticide management.

Environmental and anthropogenic drivers of contaminants in agricultural watersheds with implications for land management.

If not managed properly, modern agricultural practices can alter surface and groundwater quality and drinking water resources resulting in potential negative effects on aquatic and terrestrial ecosystems. Exposure to agriculturally derived contaminant mixtures has the potential to alter habitat quality and negatively affect fish and other aquatic organisms. Implementation of conservation practices focused on improving water quality continues to increase particularly in agricultural landscapes throughout the United States. The goal of this study was to determine the consequences of land management actions on the primary drivers of contaminant mixtures in five agricultural watersheds in the Chesapeake Bay, the largest watershed of the Atlantic Seaboard in North America where fish health issues have been documented for two decades. Surface water was collected and analyzed for 301 organic contaminants to determine the benefits of implemented best management practices (BMPs) designed to reduce nutrients and sediment to streams in also reducing contaminants in surface waters. Of the contaminants measured, herbicides (atrazine, metolachlor), phytoestrogens (formononetin, genistein, equol), cholesterol and total estrogenicity (indicator of estrogenic response) were detected frequently enough to statistically compare to seasonal flow effects, landscape variables and BMP intensity. Contaminant concentrations were often positively correlated with seasonal stream flow, although the magnitude of this effect varied by contaminant across seasons and sites. Land-use and other less utilized landscape variables including biosolids, manure and pesticide application and percent phytoestrogen producing crops were inversely related with site-average contaminant concentrations. Increased BMP intensity was negatively related to contaminant concentrations indicating potential co-benefits of BMPs for contaminant reduction in the studied watersheds. The information gained from this study will help prioritize ecologically relevant contaminant mixtures for monitoring and contributes to understanding the benefits of BMPs on improving surface water quality to better manage living resources in agricultural landscapes inside and outside the Chesapeake Bay watershed.

Long-term follow-up of women with gestational diabetes mellitus: the South Australian Gestational Diabetes Mellitus Recall Register.

BACKGROUND: Women who have had gestational diabetes mellitus (GDM) are at increased risk of developing type 2 diabetes. Early detection and management of type 2 diabetes are important for reducing associated complications and costs. AIMS: To evaluate an existing register for long-term follow-up of women who have been diagnosed with GDM. METHODS: Recruitment to the GDM Recall Register began at the diabetes centres of two hospitals in South Australia from July 2002, and was expanded to include a third hospital from September 2005. Women enrolled on the Register are sent an annual letter reminding them that they are at increased risk of developing type 2 diabetes and encouraging them to get their blood glucose checked. An update form is also included for women to complete and return to the Register. RESULTS: As at 30 June 2009, 817 women were enrolled on the Register. Of women diagnosed with GDM at the participating hospital sites, recruitment to the Register was 68.4% in 2002 and 64.4% in 2007. Of the 429 women who had been sent their first reminder letter, 46.4% had returned the update form. Of these, 56.3% had undergone a glucose test for diabetes. Two women reported developing type 2 diabetes. CONCLUSIONS: Expansion of the GDM Recall Register is likely to result in increased opportunities for early detection of diabetes for this high-risk group in South Australia, therefore allowing earlier intervention and treatment to prevent or reduce serious, costly diabetes-related complications.

Oral hypoglycaemics - a review of the evidence.

BACKGROUND: The range of oral hypoglycaemic agents (OHAs) has increased from one insulin sensitiser (metformin) and one class of insulin secretagogues (sulphonylureas) with the addition of further class of insulin secretagogues (glitinides), a further class of insulin sensitisers (glitazones) and two new classes: an alpha glycosidase inhibitor and glucagon-like peptide agents. Recent data has influenced the recommended sequence and usage of OHAs and glycaemic targets. OBJECTIVE: This article reviews the recent evidence in type 2 diabetes about the pros and cons of oral hypoglycaemic agents and the benefits and costs of intensive glycaemic control. It suggests a stepwise approach to glycaemic control with OHAs according to the evidence base currently available. DISCUSSION: Before 2008, the recommended glycaemic management was healthy lifestyle, metformin and sulphonylurea if tolerated, then rosiglitazone or insulin. Pioglitazone could be used with insulin therapy but not as triple therapy. In 2007 and 2008 data about glitazones demonstrated a potential increased risk of myocardial infarction with rosiglitazone and increased risk of heart failure, peripheral fractures and macular oedema with both pioglitazone and rosiglitazone. In 2009 a new class of hypoglycaemic agents, glucagon-like peptide 1 agents, became available. Three trials published in 2009 failed to show a statistically significant reduction in cardiovascular events with intensive glycaemic management compared to conventional management. The current recommended target for HbA1c is <7% but higher or lower targets may be appropriate for individual patients.

Bacterial quality of groundwater downgradient of onsite wastewater disposal systems and the influence on eastern Long Island's embayments.

Onsite wastewater disposal systems (OWDS) can introduce bacterial and chemical contaminants, via groundwater, into aquifers and adjacent waterways. We evaluated the concentration of fecal indicator bacteria (FIB) and antibiotic resistant bacteria (ARB) in the shallow groundwater of Eastern Long Island, New York, downgradient of OWDS using cultivation approaches and analysis of 16 S rRNA genes. While FIB and ARB were detected in 80% and 67% of groundwater samples, respectively, concentrations were low, suggesting that, at least at the time of sampling, groundwater was not a large-scale source of fecal bacterial contamination to adjacent embayments. ARB isolates did not include common fecal associated genera and the concentration of FIB and ARB did not correlate well with the concentration of pharmaceutical contaminants, suggesting that bacterial contaminants were poorly linked to OWDS discharge. Concentrations of FIB in the studied embayments were significantly greater in nearshore compared to mid-channel environments, suggesting that land-based sources are likely to be the major contributors of bacterial contamination.