Fluorinated Metal-Organic Coatings with Selective Wettability.

Surface chemistry is a major factor that determines the wettability of materials, and devising broadly applicable coating strategies that afford tunable and selective surface properties required for next-generation materials remains a challenge. Herein, we report fluorinated metal-organic coatings that display water-wetting and oil-repelling characteristics, a wetting phenomenon different from responsive wetting induced by external stimuli. We demonstrate this selective wettability with a library of metal-organic coatings using catechol-based coordination and silanization (both fluorinated and fluorine-free), enabling sensing through interfacial reconfigurations in both gaseous and liquid environments, and establish a correlation between the coating wettability and polarity of the liquids. This selective wetting performance is substrate-independent, spontaneous, durable, and reversible and occurs over a range of polar and nonpolar liquids (60 studied). These results provide insight into advanced liquid-solid interactions and a pathway toward tuning interfacial affinities and realizing robust, selective superwettability according to the surrounding conditions.

Metallomics Study in Plants Exposed to Arsenic, Mercury, Selenium and Sulphur.

This chapter is focussing on the interaction of arsenic, mercury and selenium with plans. Aspects of biotransformations are discussed, before the analytical methodologies are listed and critically appraised in the second part. A holistic view is given, starting from the soil environment and continuing to the plant roots and the translocations into the upper part of the plants. Under different soil conditions, different kinds of elemental species are identified, which have an impact on how the elemental species are taken up by the plant. The uptake mechanisms of these elemental species are explained and compared before the biotransformation reactions of all elemental species in the plant root; their transport into the vacuoles and translocation to the leaves and grains are discussed. Here in particular the interaction with sulphur-rich phytochelatins is described for all three elemental species. Since the sulphur chemistry is so important for the uptake, bioaccumulation and translocation of the metals and metalloids, a subchapter about sulphur chemistry in plants has been added. All aspects of biotransformation dealt with in this chapter is finally rounded up by a thorough description of the analytical methodology given with a focus on the use of HPLC-ICPMS/ESI-MS for both quantitative and molecular analysis.

Sex-biased inbreeding effects on reproductive success and home range size of the critically endangered black rhinoceros.

A central premise of conservation biology is that small populations suffer reduced viability through loss of genetic diversity and inbreeding. However, there is little evidence that variation in inbreeding impacts individual reproductive success within remnant populations of threatened taxa, largely due to problems associated with obtaining comprehensive pedigree information to estimate inbreeding. In the critically endangered black rhinoceros, a species that experienced severe demographic reductions, we used model selection to identify factors associated with variation in reproductive success (number of offspring). Factors examined as predictors of reproductive success were age, home range size, number of nearby mates, reserve location, and multilocus heterozygosity (a proxy for inbreeding). Multilocus heterozygosity predicted male reproductive success (p< 0.001, explained deviance >58%) and correlated with male home range size (p < 0.01, r(2) > 44%). Such effects were not apparent in females, where reproductive success was determined by age (p < 0.01, explained deviance 34%) as females raise calves alone and choose between, rather than compete for, mates. This first report of a 3-way association between an individual male's heterozygosity, reproductive output, and territory size in a large vertebrate is consistent with an asymmetry in the level of intrasexual competition and highlights the relevance of sex-biased inbreeding for the management of many conservation-priority species. Our results contrast with the idea that wild populations of threatened taxa may possess some inherent difference from most nonthreatened populations that necessitates the use of detailed pedigrees to study inbreeding effects. Despite substantial variance in male reproductive success, the increased fitness of more heterozygous males limits the loss of heterozygosity. Understanding how individual differences in genetic diversity mediate the outcome of intrasexual competition will be essential for effective management, particularly in enclosed populations, where individuals have restricted choice about home range location and where the reproductive impact of translocated animals will depend upon the background distribution in individual heterozygosity.

Graphitized silicon carbide microbeams: wafer-level, self-aligned graphene on silicon wafers.

Currently proven methods that are used to obtain devices with high-quality graphene on silicon wafers involve the transfer of graphene flakes from a growth substrate, resulting in fundamental limitations for large-scale device fabrication. Moreover, the complex three-dimensional structures of interest for microelectromechanical and nanoelectromechanical systems are hardly compatible with such transfer processes. Here, we introduce a methodology for obtaining thousands of microbeams, made of graphitized silicon carbide on silicon, through a site-selective and wafer-scale approach. A Ni-Cu alloy catalyst mediates a self-aligned graphitization on prepatterned SiC microstructures at a temperature that is compatible with silicon technologies. The graphene nanocoating leads to a dramatically enhanced electrical conductivity, which elevates this approach to an ideal method for the replacement of conductive metal films in silicon carbide-based MEMS and NEMS devices.

Captive-housed male cheetahs (Acinonyx jubatus soemmeringii) form naturalistic coalitions: measuring associations and calculating chance encounters.

Cheetahs are known to reproduce poorly in captivity and research suggests that the reasons for this are behavioral, rather than physiological. In the wild, male cheetahs remain in stable groups, or coalitions, throughout their lifetime. Appropriate social group housing is important in enhancing welfare and reproductive success in captivity and this study examined the effect of changes in social group composition on the behavior of four male cheetahs: two siblings and two half siblings. During the study, the cheetahs were housed both in pairs and as a group of four, before one male was relocated. The remaining cheetahs were then housed in a trio. Affiliative behaviors were frequently shown within pairs and overt aggression was seldom observed. Association indices were calculated for each cheetah pair and corrected for chance encounters based on data generated from a Monte Carlo simulation. The indices showed that two coalitions existed before the relocated male departed. Following the relocation of one of the half siblings, the remaining cheetahs appeared to form a coalition of three, as the indices of association between the unrelated male and the siblings increased and allogrooming between unrelated individuals was observed. The findings of this study indicate that natural social groupings of male cheetahs can be successfully replicated in captivity, which could potentially improve the chances of reproductive success when they are introduced to female cheetahs.

KDM2A Deficiency in the Liver Promotes Abnormal Liver Function and Potential Liver Damage.

Dysregulation of metabolic functions in the liver impacts the development of diabetes and metabolic disorders. Normal liver function can be compromised by increased inflammation via the activation of signaling such as nuclear factor (NF)-κB signaling. Notably, we have previously identified lysine demethylase 2A (KDM2A)-as a critical negative regulator of NF-κB. However, there are no studies demonstrating the effect of KDM2A on liver function. Here, we established a novel liver-specific Kdm2a knockout mouse model to evaluate KDM2A's role in liver functions. An inducible hepatic deletion of Kdm2a, Alb-Cre-Kdm2afl/fl (Kdm2a KO), was generated by crossing the Kdm2a floxed mice (Kdm2afl/fl) we established with commercial albumin-Cre transgenic mice (B6.Cg-Tg(Alb-cre)21Mgn/J). We show that under a normal diet, Kdm2a KO mice exhibited increased serum alanine aminotransferase (ALT) activity, L-type triglycerides (TG) levels, and liver glycogen levels vs. WT (Kdm2afl/fl) animals. These changes were further enhanced in Kdm2a liver KO mice in high-fat diet (HFD) conditions. We also observed a significant increase in NF-κB target gene expression in Kdm2a liver KO mice under HFD conditions. Similarly, the KO mice exhibited increased immune cell infiltration. Collectively, these data suggest liver-specific KDM2A deficiency may enhance inflammation in the liver, potentially through NF-κB activation, and lead to liver dysfunction. Our study also suggests that the established Kdm2afl/fl mouse model may serve as a powerful tool for studying liver-related metabolic diseases.

Nephrogenic systemic fibrosis: what internists need to know.

Nephrogenic systemic fibrosis (NSF) is an emerging entity that affects the skin and internal organs in patients with renal insufficiency and may end in death. More than 215 cases have been reported to the NSF registry at Yale University and more than 700 cases have been reported world-wide. There is a growing concern about gadolinium contrast media as being the major player in NSF development. Given the lack of established effective therapy, gadolinium avoidance along with careful consideration of the predisposing factors is the vital approach. Clinicians must be aware of the risks and benefits of gadolinium administration especially in patients with chronic kidney disease.

Uptake and localisation of lead in the root system of Brassica juncea.

The uptake and distribution of Pb sequestered by hydroponically grown (14days growth) Brassica juncea (3days exposure; Pb activities 3.2, 32 and 217microM) was investigated. Lead uptake was restricted largely to root tissue. Examination using scanning transmission electron microscopy-energy dispersive spectroscopy revealed substantial and predominantly intracellular uptake at the root tip. Endocytosis of Pb at the plasma membrane was not observed. A membrane transport protein may therefore be involved. In contrast, endocytosis of Pb into a subset of vacuoles was observed, resulting in the formation of dense Pb aggregates. Sparse and predominantly extracellular uptake occurred at some distance from the root tip. X-ray photoelectron spectroscopy confirmed that the Pb concentration was greater in root tips. Heavy metal rhizofiltration using B. juncea might therefore be improved by breeding plants with profusely branching roots. Uptake enhancement using genetic engineering techniques would benefit from investigation of plasma membrane transport mechanisms.

A X-ray photoelectron spectroscopy study of HDTMAB distribution within organoclays.

X-ray photoelectron spectroscopy (XPS) in combination with X-ray diffraction (XRD) and high-resolution thermogravimetric analysis (HRTG) has been used to investigate the surfactant distribution within the organoclays prepared at different surfactant concentrations. This study demonstrates that the surfactant distribution within the organoclays depends strongly on the surfactant loadings. In the organoclays prepared at relative low surfactant concentrations, the surfactant cations mainly locate in the clay interlayer, whereas the surfactants occupy both the clay interlayer space and the interparticle pores in the organoclays prepared at high surfactant concentrations. This is in accordance with the dramatic pore volume decrease of organoclays compared to those of starting clays. XPS survey scans show that, at low surfactant concentration (<1.0CEC), the ion exchange between Na+ and HDTMA+ is dominant, whereas both cations and ion pairs occur in the organoclays prepared at high concentrations (>1.0CEC). High-resolution XPS spectra show that the modification of clay with surfactants has prominent influences on the binding energies of the atoms in both clays and surfactants, and nitrogen is the most sensitive to the surfactant distribution within the organoclays.

X-ray Photoelectron Spectroscopic and Raman microscopic investigation of the variscite group minerals: Variscite, strengite, scorodite and mansfieldite.

Several structurally related AsO4 and PO4 minerals, were studied with Raman microscopy and X-ray Photoelectron Spectroscopy (XPS). XPS revealed only Fe, As and O for scorodite. The Fe 2p, As 3d, and O 1s indicated one position for Fe2+, while 2 different environments for O and As were observed. The O 1s at 530.3eV and the As 3d 5/2 at 43.7eV belonged to AsO4, while minor bands for O 1s at 531.3eV and As 3d 5/2 at 44.8eV were due to AsO4 groups exposed on the surface possibly forming OH-groups. Mansfieldite showed, besides Al, As and O, a trace of Co. The PO4 equivalent of mansfieldite is variscite. The change in crystal structure replacing As with P resulted in an increase in the binding energy (BE) of the Al 2p by 2.9eV. The substitution of Fe3+ for Al3+ in the structure of strengite resulted in a Fe 2p at 710.8eV. An increase in the Fe 2p BE of 4.8eV was found between mansfieldite and strengite. The scorodite Raman OH-stretching region showed a sharp band at 3513cm-1 and a broad band around 3082cm-1. The spectrum of mansfieldite was like that of scorodite with a sharp band at 3536cm-1 and broader maxima at 3100cm-1 and 2888cm-1. Substituting Al in the arsenate structure instead of Fe resulted in a shift of the metal-OH-stretching mode by 23cm-1 towards higher wavenumbers due to a slightly longer H-bonding in mansfieldite compared to scorodite. The intense band for scorodite at 805cm-1 was ascribed to the symmetric stretching mode of the AsO4. The medium intensity bands at 890, 869, and 830cm-1 were ascribed to the internal modes. A significant shift towards higher wavenumbers was observed for mansfieldite. The strengite Raman spectrum in the 900-1150cm-1 shows a strong band at 981cm-1 accompanied by a series of less intense bands. The 981cm-1 band was assigned to the PO4 symmetric stretching mode, while the weak band at 1116cm-1 was the corresponding antisymmetric stretching mode. The remaining bands at 1009, 1023 and 1035cm-1 were assigned to υ1(A1) internal modes in analogy to the interpretation of the AsO4 bands for scorodite and mansfieldite. The variscite spectrum showed a shift towards higher wavenumbers in comparison to the strengite spectrum with the strongest band observed at 1030cm-1 and was assigned to the symmetric stretching mode of the PO4, while the corresponding antisymmetric stretching mode was observed at 1080cm-1. Due to the band splitting component bands were observed at 1059, 1046, 1013 and 940cm-1. The AsO4 symmetric bending modes for scorodite were observed at 381 and 337cm-1, while corresponding antisymmetric bending modes occurred at 424, 449 and 484cm-1. Comparison with other arsenate and phosphate minerals showed that both XPS and Raman spectroscopy are fast and non-destructive techniques to identify these minerals based on their differences in chemistry and the arsenate/phosphate vibrational modes due to changes in the symmetry and the unique fingerprint region of the lattice modes.

Single-Crystalline 3C-SiC anodically Bonded onto Glass: An Excellent Platform for High-Temperature Electronics and Bioapplications.

Single-crystal cubic silicon carbide has attracted great attention for MEMS and electronic devices. However, current leakage at the SiC/Si junction at high temperatures and visible-light absorption of the Si substrate are main obstacles hindering the use of the platform in a broad range of applications. To solve these bottlenecks, we present a new platform of single crystal SiC on an electrically insulating and transparent substrate using an anodic bonding process. The SiC thin film was prepared on a 150 mm Si with a surface roughness of 7 nm using LPCVD. The SiC/Si wafer was bonded to a glass substrate and then the Si layer was completely removed through wafer polishing and wet etching. The bonded SiC/glass samples show a sharp bonding interface of less than 15 nm characterized using deep profile X-ray photoelectron spectroscopy, a strong bonding strength of approximately 20 MPa measured from the pulling test, and relatively high optical transparency in the visible range. The transferred SiC film also exhibited good conductivity and a relatively high temperature coefficient of resistance varying from -12 000 to -20 000 ppm/K, which is desirable for thermal sensors. The biocompatibility of SiC/glass was also confirmed through mouse 3T3 fibroblasts cell-culturing experiments. Taking advantage of the superior electrical properties and biocompatibility of SiC, the developed SiC-on-glass platform offers unprecedented potentials for high-temperature electronics as well as bioapplications.

XPS study of the major minerals in bauxite: gibbsite, bayerite and (pseudo-)boehmite.

Synthetic corundum (Al2O3), gibbsite (Al(OH)3), bayerite (Al(OH)3), boehmite (AlO(OH)) and pseudoboehmite (AlO(OH)) have been studied by high resolution XPS. The chemical compositions based on the XPS survey scans were in good agreement with the expected composition. High resolution Al2p scans showed no significant changes in binding energy, with all values between 73.9 and 74.4 eV. Only bayerite showed two transitions, associated with the presence of amorphous material in the sample. More information about the chemical and crystallographic environment was obtained from the O1s high resolution spectra. Here a clear distinction could be made between oxygen in the crystal structure, hydroxyl groups and adsorbed water. Oxygen in the crystal structure was characterised by a binding energy of about 530.6 eV in all minerals. Hydroxyl groups, present either in the crystal structure or on the surface, exhibited binding energies around 531.9 eV, while water on the surface showed binding energies around 533.0 eV. A distinction could be made between boehmite and pseudoboehmite based on the slightly lower ratio of oxygen to hydroxyl groups and water in pseudoboehmite.

Cosegregation of bipolar disorder and autosomal-dominant medullary cystic kidney disease in a large family.

OBJECTIVE: The authors report a large family in which bipolar disorder appears to cosegregate with autosomal-dominant medullary cystic kidney disease. METHOD: Information regarding diagnostic criteria for bipolar disorder and medullary cystic kidney disease were gathered from family members through formal research interviews, hospital admission records, imaging reports, and laboratory data. RESULTS: Of the seven members with medullary cystic kidney disease, five had bipolar I disorder, one had unipolar depression, and one had a hyperthymic phenotype. Information was not available on two members. CONCLUSIONS: The cosegregation in this family suggests a close proximity between genes for the two disorders. The two known loci of medullary cystic kidney disease are in regions of chromosomes 1 and 16 that have been previously linked to bipolar disorder and schizophrenia. This family may be a useful resource for positional cloning of bipolar candidate genes.

Chemical bonding and electronic structures of microcline, orthoclase and the plagioclase series by X-ray photoelectron spectroscopy.

A detailed analysis was undertaken of the X-ray photoelectron spectra obtained from microcline, orthoclase and several samples of plagioclase with varying Na/Ca ratio. Comparison of the spectra was made based on the chemical bonding and structural differences in the Al- and Si-coordination within each specimen. The spectra for Si 2p and Al 2p vary with the change in symmetry between microcline and orthoclase, while in plagioclase an increase in Al-O-Si linkages results in a small but observable decrease in binding energy. The overall shapes of the O 1s peaks observed in all spectra are similar and show shifts similar to those observed for Si 2p and Al 2p. The lower-VB spectra for microcline and orthoclase are similar intermediate between α-SiO2 and α-Al2O3 in terms of binding energies. In the plagioclase series increasing coupled substitution of Na and Si for Ca and Al results in a change of the overall shape of the spectra, showing a distinct broadening associated with the presence of two separate but overlapping bands similar to the 21 eV band observed for quartz and the 23 eV band observed for corundum. The bonding character for microcline and orthoclase is more covalent than that of α-Al2O3, but less than that of α-SiO2. In contrast, the plagioclase samples show two distinct bonding characters that are comparable with those of α-SiO2 and α-Al2O3.

Landscape Analysis of Adult Florida Panther Habitat.

Historically occurring throughout the southeastern United States, the Florida panther is now restricted to less than 5% of its historic range in one breeding population located in southern Florida. Using radio-telemetry data from 87 prime-aged (≥3 years old) adult panthers (35 males and 52 females) during the period 2004 through 2013 (28,720 radio-locations), we analyzed the characteristics of the occupied area and used those attributes in a random forest model to develop a predictive distribution map for resident breeding panthers in southern Florida. Using 10-fold cross validation, the model was 87.5 % accurate in predicting presence or absence of panthers in the 16,678 km2 study area. Analysis of variable importance indicated that the amount of forests and forest edge, hydrology, and human population density were the most important factors determining presence or absence of panthers. Sensitivity analysis showed that the presence of human populations, roads, and agriculture (other than pasture) had strong negative effects on the probability of panther presence. Forest cover and forest edge had strong positive effects. The median model-predicted probability of presence for panther home ranges was 0.81 (0.82 for females and 0.74 for males). The model identified 5579 km2 of suitable breeding habitat remaining in southern Florida; 1399 km2 (25%) of this habitat is in non-protected private ownership. Because there is less panther habitat remaining than previously thought, we recommend that all remaining breeding habitat in south Florida should be maintained, and the current panther range should be expanded into south-central Florida. This model should be useful for evaluating the impacts of future development projects, in prioritizing areas for panther conservation, and in evaluating the potential impacts of sea-level rise and changes in hydrology.

Monooxygenase stereoselectivity in the biosynthesis of stereoisomeric spiroacetals in the cucumber fly, Bactrocera cucumis.

[reaction: see text] The stereoselectivity of hydroxylation of alkyltetrahydropyran-2-ols (or their biological equivalents) in the formation of stereoisomers of 2,8-dimethyl-1,7-dioxaspiro[5.5]undecanes in male Bactrocera cucumis has been investigated. Racemic, (6R)-, and (6S)-6-methyl-2-[5-(2)H(1)]-n-pentyltetrahydropyran-2-ol was administered under an [(18)O(2)]-enriched atmosphere. The stereochemistry and isotopic composition of generated spiroacetals were monitored by combined enantioselective GC-MS. The monooxygenase(s) strongly prefers the (6S)-substrate and furnishes predominantly the (S)-alcohol and then the (2S,6R,8S)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane. The (2S,6S,8R) and (2R,6S,8S) (E,Z)-isomers appear to be derived in vivo predominantly from (R)-hydroxylation of the (6S)-tetrahydropyranol.

Sex pheromone biosynthesis in the female olive fruit-fly. Double labelling from [18O2]-dioxygen into 1,7-dioxaspiro[5.5]undecane.

The demonstration that both oxygen atoms of 1,7-dioxaspiro[5.5]undecane (1), the sex-pheromone of the female olive fly, originate from dioxygen, strongly implicates monooxygenase mediated processes in assembly of (1), and reveals unexpected complexity in the formation of its nine-carbon precursor.

Recommending a value for the Newtonian gravitational constant.

The primary objective of the CODATA Task Group on Fundamental Constants is 'to periodically provide the scientific and technological communities with a self-consistent set of internationally recommended values of the basic constants and conversion factors of physics and chemistry based on all of the relevant data available at a given point in time'. I discuss why the availability of these recommended values is important and how it simplifies and improves science. I outline the process of determining the recommended values and introduce the principles that are used to deal with discrepant results. In particular, I discuss the specific challenges posed by the present situation of gravitational constant experimental results and how these principles were applied to the most recent 2010 recommended value. Finally, I speculate about what may be expected for the next recommended value of the gravitational constant scheduled for evaluation in 2014.

Photoelectrochemical characterization of hydrogenated TiO2 nanotubes as photoanodes for sensing applications.

In this work, hydrogenated TiO2 nanotubes (H-TNTs) electrodes were successfully fabricated via the anodization of a titanium sheet followed by a hydrogenation process. Oxygen vacancies were induced in the crystalline structure of TiO2 nanotubes (TNTs) as shallow donors that enhance the electronic conductivity of the TNTs. This improvement in the electronic conductivity and photoelectrocatalytic (PEC) performance was confirmed and evaluated by a photoelectrochemical characterization. Most importantly, the H-TNTs electrode was able to degrade potassium hydrogen phthalate (strong adsorbent) and glucose (weak adsorbent) indiscriminately. The corresponding photocurrents at the H-TNTs were 2-fold greater than that of the TNTs samples for the same concentrations of the organic compounds. This suggests that the H-TNTs electrode can be a promising sensor for the PEC determination of individual organic compounds or as an aggregative parameter of organic compounds (e.g., chemical oxygen demand).