H2 purification by functionalized graphdiyne – role of nitrogen doping

A nitrogen modified graphdiyne is investigated concerning its performance for hydrogen purification from CH4 and CO by density functional theory with dispersion correction and transition state theory. After nitrogen doping, the porous N-graphdiyne nano-mesh shows a reduced H2 diffusion barrier and increased CH4/CO diffusion barriers, hence leading to an enhanced hydrogen purification capability.

The repertoire of nitrogen assimilation in Rhodococcus: Catalysis, pathways and relevance in biotechnology and bioremediation

The Rhodococcus genus exhibits diverse enzymatic activity that can be exploited in the conversion of natural and anthropogenic nitrogenous compounds. This catalytic response provides a selective advantage in terms of available nutrients while also serving to remove otherwise harmful xenobiotics. This review provides a critical assessment of the literature on bioconversion of organo-nitrogen compounds with a consideration of applications in bioremediation and commercial biotechnology. By examining the major nitro-organic compounds (amino acids, amines, nitriles, amides and nitroaromatics) in turn, the considerable repertoire of Rhodococcus spp. is established. The available published enzyme reaction data is coupled with genomic characterisation to provide a molecular basis for Rhodococcus enzyme activity with an assessment of the cellular properties that aid substrate accessibility and ensure stability. The metabolic gene clusters associated with the observed reaction pathways are identified and future directions in enzyme optimisation and metabolic engineering are assessed. © 2014 Society of Chemical Industry.

Removal characteristics of ammonium nitrogen from wastewater by modified Ca-bentonites

A modified inorganic bentonite (Na/Al) based on purified Ca-bentonite was prepared through exchanging Al and Na ions in the interlayer space of Ca-bentonite. The structural properties of purified and modified bentonites were characterized by XRD and SEM analysis. Batch experiments were performed for the adsorption of ammonium nitrogen and different experimental conditions were studied in order to investigate the optimum adsorption conditions. Comparative experiments were also carried out for natural Ca-bentonite (RB), unmodified purified bentonite (PB) and modified purified bentonite (MB). Through the thermodynamic analysis, the ammonium nitrogen adsorption process can be spontaneous, the standard heat was −41.46kJmol −1 , and the adsorption process based on ion exchange adsorption. The ammonium nitrogen adsorption capacity of MB (46.904mg/g) was improved compared to raw bentonite (RB) (26.631mg/g), which was among the highest values of ammonium nitrogen adsorption compared with other adsorbents according to the literatures. The described process provides a potential pathway for the removal of ammonium nitrogen at low concentrations encountered in most natural waters.

The characterisation of Ureaplasma species isolated from the Chorioamnion of women who deliver late Preterm

This thesis investigated, for the first time, the prevalence of Ureaplasma species infection within the placentae of women who delivered in the late preterm stages of pregnancy. The presence of these microorganisms was associated with either severe inflammation within the placenta or, for some women, there were no pregnancy complications and these women delivered at term. Ureaplasmas are able to vary their surface exposed lipoproteins and we demonstrated that different host immune responses were generated in vivo to different sized surface lipoproteins. This may explain why ureaplasma infections do not always result in adverse pregnancy and neonatal outcomes.

Environmental context for late Holocene human occupation of the South Wellesley Archipelago, Gulf of Carpentaria, northern Australia

A 2400 year record of environmental change is reported from a wetland on Bentinck Island in the southern Gulf of Carpentaria, northern Australia. Three phases of wetland development are identified, with a protected coastal setting from ca. 2400 to 500 years ago, transitioning into an estuarine mangrove forest from ca. 500 years ago to the 1940s, and finally to a freshwater swamp over the past +60 years. This sequence reflects the influence of falling sea-levels, development of a coastal dune barrier system, prograding shorelines, and an extreme storm (cyclone) event. In addition, there is clear evidence of the impacts that human abandonment and resettlement have on the island's fire regimes and vegetation. A dramatic increase in burning and vegetation thickening was observed after the cessation of traditional Indigenous Kaiadilt fire management practices in the 1940s, and was then reversed when people returned to the island in the 1980s. In terms of the longer context for human occupation of the South Wellesley Archipelago, it is apparent that the mangrove phase provided a stable and productive environment that was conducive for human settlement of this region over the past 1000 years.

Anthropogenic nitrogen deposition predicts local grassland primary production worldwide

Humans dominate many important Earth system processes including the nitrogen (N) cycle. Atmospheric N deposition affects fundamental processes such as carbon cycling, climate regulation, and biodiversity, and could result in changes to fundamental Earth system processes such as primary production. Both modelling and experimentation have suggested a role for anthropogenically altered N deposition in increasing productivity, nevertheless, current understanding of the relative strength of N deposition with respect to other controls on production such as edaphic conditions and climate is limited. Here we use an international multiscale data set to show that atmospheric N deposition is positively correlated to aboveground net primary production (ANPP) observed at the 1-m2 level across a wide range of herbaceous ecosystems. N deposition was a better predictor than climatic drivers and local soil conditions, explaining 16% of observed variation in ANPP globally with an increase of 1 kg N·ha-1·yr-1 increasing ANPP by 3%. Soil pH explained 8% of observed variation in ANPP while climatic drivers showed no significant relationship. Our results illustrate that the incorporation of global N deposition patterns in Earth system models are likely to substantially improve estimates of primary production in herbaceous systems. In herbaceous systems across the world, humans appear to be partially driving local ANPP through impacts on the N cycle.

Consistent responses of soil microbial communities to elevated nutrient inputs in grasslands across the globe

Soil microorganisms are critical to ecosystem functioning and the maintenance of soil fertility. However, despite global increases in the inputs of nitrogen (N) and phosphorus (P) to ecosystems due to human activities, we lack a predictive understanding of how microbial communities respond to elevated nutrient inputs across environmental gradients. Here we used high-throughput sequencing of marker genes to elucidate the responses of soil fungal, archaeal, and bacterial communities using an N and P addition experiment replicated at 25 globally distributed grassland sites. We also sequenced metagenomes from a subset of the sites to determine how the functional attributes of bacterial communities change in response to elevated nutrients. Despite strong compositional differences across sites, microbial communities shifted in a consistent manner with N or P additions, and the magnitude of these shifts was related to the magnitude of plant community responses to nutrient inputs. Mycorrhizal fungi and methanogenic archaea decreased in relative abundance with nutrient additions, as did the relative abundances of oligotrophic bacterial taxa. The metagenomic data provided additional evidence for this shift in bacterial life history strategies because nutrient additions decreased the average genome sizes of the bacterial community members and elicited changes in the relative abundances of representative functional genes. Our results suggest that elevated N and P inputs lead to predictable shifts in the taxonomic and functional traits of soil microbial communities, including increases in the relative abundances of faster-growing, copiotrophic bacterial taxa, with these shifts likely to impact belowground ecosystems worldwide.

Conversion of n-type CuTCNQ into p-type nitrogen-doped CuO and the implication for room temperature gas sensing

Sensors to detect toxic and harmful gases are usually based on metal oxides that are operated at elevated temperature. However, enabling gas detection at room temperature (RT) is a significant ongoing challenge. Here, we address this issue by demonstrating that microrods of semiconducting CuTCNQ (TCNQ=7,7,8,8-tetracyanoquinodimethane) with nanostructured features can be employed as conductometric gas sensors operating at 50°C for detection of oxidizing and reducing gases such as NO2 and NH3. The sensor is evaluated at RT and up to 200°C. It was found that CuTCNQ is transformed into a N-doped CuO material with p-type conductivity when annealed at the maximum temperature. This is the first time that such a transformation, from a semiconducting charge transfer material into a N-doped metal oxide is detected. It is shown here that both the surface chemistry and the type of majority charge carrier within the sensing layer is critically important for the type of response towards oxidizing and reducing gases. A detailed physical description of NO2 and NH3 sensing mechanism at CuTCNQ and N-doped CuO is provided to explain the difference in the response. For the N-doped CuO sensor, a detection limit of 1 ppm for NO2 and 10 ppm for NH3 are achieved.

Diagnosing adult Attention Deficit Hyperactivity Disorder: Are late onset and subthreshold ciagnoses valid?

Objective Diagnosing attention deficit hyperactivity disorder (ADHD) in adults is difficult when diagnosticians cannot establish an onset before the DSM-IV criterion of age 7 or if the number of symptoms recalled does not achieve DSM’s diagnosis threshold. Method The authors addressed the validity of DSM-IV’s age-at-onset and symptom threshold criteria by comparing four groups of adults: 127 subjects with full ADHD who met all DSM-IV criteria for childhood-onset ADHD, 79 subjects with late-onset ADHD who met all criteria except the age-at-onset criterion, 41 subjects with subthreshold ADHD who did not meet full symptom criteria for ADHD, and 123 subjects without ADHD who did not meet any criteria. The authors hypothesized that subjects with late-onset and subthreshold ADHD would show patterns of psychiatric comorbidity, functional impairment, and familial transmission similar to those seen in subjects with full ADHD. Result Subjects with late-onset and full ADHD had similar patterns of psychiatric comorbidity, functional impairment, and familial transmission. Most children with late onset of ADHD (83%) were younger than 12. Subthreshold ADHD was milder and showed a different pattern of familial transmission than the other forms of ADHD. Conclusions The data about the clinical features of probands and the pattern of transmission of ADHD among relatives found little evidence for the validity of subthreshold ADHD among such subjects, who reported a lifetime history of some symptoms that never met DSM-IV’s threshold for diagnosis. In contrast, the results suggested that late-onset adult ADHD is valid and that DSM-IV’s age-at-onset criterion is too stringent.

Neuropsychological studies of late onset and subthreshold diagnoses of adult Attention-Deficit/Hyperactivity Disorder

Background Diagnosing attention-deficit/hyperactivity disorder (ADHD) in adults is difficult when the diagnostician cannot establish an onset prior to the DSM-IV criterion of age 7 or if the number of symptoms recalled does not achieve the DSM-IV threshold for diagnosis. Because neuropsychological deficits are associated with ADHD, we addressed the validity of the DSM-IV age at onset and symptom threshold criteria by using neuropsychological test scores as external validators. Methods We compared four groups of adults: 1) full ADHD subjects met all DSM-IV criteria for childhood-onset ADHD; 2) late-onset ADHD subjects met all criteria except the age at onset criterion; 3) subthreshold ADHD subjects did not meet full symptom criteria; and 4) non-ADHD subjects did not meet any of the above criteria. Results Late-onset and full ADHD subjects had similar patterns of neuropsychological dysfunction. By comparison, subthreshold ADHD subjects showed few neuropsychological differences with non-ADHD subjects. Conclusions Our results showing similar neuropsychological underpinning in subjects with late-onset ADHD suggest that the DSM-IV age at onset criterion may be too stringent. Our data also suggest that ADHD subjects who failed to ever meet the DSM-IV threshold for diagnosis have a milder form of the disorder.

Charged-controlled separation of nitrogen from natural gas using boron nitride fullerene

Natural gas (the main component is methane) has been widely used as a fuel and raw material in industry. Removal of nitrogen (N2) from methane (CH4) can reduce the cost of natural gas transport and improve its efficiency. However, their extremely similar size increases the difficulty of separating N2 from CH4. In this study, we have performed a comprehensive investigation of N2 and CH4 adsorption on different charge states of boron nitride (BN) nanocage fullerene, B36N36, by using a density functional theory approach. The calculational results indicate that B36N36 in the negatively charged state has high selectivity in separating N2 from CH4. Moreover, once the extra electron is removed from the BN nanocage, the N2 will be released from the material. This study demonstrates that the B36N36 fullerene can be used as a highly selective and reusable material for the separation of N2 from CH4. The study also provides a clue to experimental design and application of BN nanomaterials for natural gas purification.

Postglacial Early Permian (late Sakmarian-early Artinskian) shallow-marine carbonate deposition along a 2000 km transect from Timor to west Australia

Late Sakmarian to early Artinskian (Early Permian) carbonate deposition was widespread in the marine intracratonic rift basins that extended into the interior of Eastern Gondwana from Timor in the north to the northern Perth Basin in the south. These basins spanned about 20° of paleolatitude (approximately 35°S to 55°S). This study describes the type section of the Maubisse Limestone in Timor-Leste, and compares this unit with carbonate sections in the Canning Basin (Nura Nura Member of the Poole Sandstone), the Southern Carnarvon Basin (Callytharra Formation) and the northern Perth Basin (Fossil Cliff Member of the Holmwood Shale). The carbonate units have no glacial influence and formed part of a major depositional cycle that, in the southern basins, overlies glacially influenced strata and lies a short distance below mudstone containing marine fossils and scattered dropstones (perhaps indicative of sea ice). In the south marine conditions became more restricted and were replaced by coal measures at the top of the depositional sequence. In the north, the carbonate deposits are possibly bryozoan–crinoidal mounds; whereas in the southern basins they form laterally continuous relatively thin beds, deposited on a very low-gradient seafloor, at the tops of shale–limestone parasequences that thicken upward in parasequence sets. All marine deposition within the sequence took place under very shallow (inner neritic) conditions, and the limestones have similar grain composition. Bryozoan and crinoidal debris dominate the grain assemblages and brachiopod shell fragments, foraminifera and ostracod valves are usually common. Tubiphytes ranged as far south as the Southern Carnarvon Basin, albeit rarely, but is more common to the north. Gastropod and bivalve shell debris, echinoid spines, solitary rugose corals and trilobite carapace elements are rare. The uniformity of the grain assemblage and the lack of tropical elements such as larger fusulinid foraminifera, colonial corals or dasycladacean algae indicate temperate marine conditions with only a small increase in temperature to the north. The depositional cycle containing the studied carbonate deposits represents a warmer phase than the preceding glacially influenced Asselian to early Sakmarian interval and the subsequent cool phase of the “mid” Artinskian that is followed by significant warming during the late Artinskian–early Kungurian. The timing of cooler and warmer intervals in the west Australian basins seems out-of-phase with the eastern Australian succession, but this may be a problem of chronostratigraphic miscorrelation due to endemic faunas and palynofloras.

Nitrogen-doped graphene films from chemical vapor deposition of pyridine: Influence of process parameters on the electrical and optical properties

Graphene films were produced by chemical vapor deposition (CVD) of pyridine on copper substrates. Pyridine-CVD is expected to lead to doped graphene by the insertion of nitrogen atoms in the growing sp2 carbon lattice, possibly improving the properties of graphene as a transparent conductive film. We here report on the influence that the CVD parameters (i.e., temperature and gas flow) have on the morphology, transmittance, and electrical conductivity of the graphene films grown with pyridine. A temperature range between 930 and 1070 °C was explored and the results were compared to those of pristine graphene grown by ethanol-CVD under the same process conditions. The films were characterized by atomic force microscopy, Raman and X-ray photoemission spectroscopy. The optical transmittance and electrical conductivity of the films were measured to evaluate their performance as transparent conductive electrodes. Graphene films grown by pyridine reached an electrical conductivity of 14.3 × 105 S/m. Such a high conductivity seems to be associated with the electronic doping induced by substitutional nitrogen atoms. In particular, at 930 °C the nitrogen/carbon ratio of pyridine-grown graphene reaches 3%, and its electrical conductivity is 40% higher than that of pristine graphene grown from ethanol-CVD.

Estrogen receptor α regulates area-adjusted bone mineral content in late pubertal girls

Context: Whether the action of estrogen in skeletal development depends on estrogen receptor α as encoded by the ESR1 gene is unknown. Objectives: The aim of this study was to establish whether the gain in area-adjusted bone mineral content (ABMC) in girls occurs in late puberty and to examine whether the magnitude of this gain is related to ESR1 polymorphisms. Design: We conducted a cross-sectional analysis. Setting: The study involved the Avon Longitudinal Study of Parents and Children (ALSPAC), a population-based prospective study. Participants: Participants included 3097 11-yr-olds with DNA samples, dual x-ray absorptiometry measurements, and pubertal stage information. Outcomes: Outcome measures included separate prespecified analyses in boys and girls of the relationship between ABMC derived from total body dual x-ray absorptiometry scans and Tanner stage and of the interaction between ABMC, Tanner stage, and ESR1 polymorphisms. Results: Total body less head and spinal ABMC were higher in girls in Tanner stages 4 and 5, compared with those in Tanner stages 1, 2, and 3. In contrast, height increased throughout puberty. No differences were observed in ABMC according to Tanner stage in boys. For rs2234693 (PvuII) and rs9340799 (XbaI) polymorphisms, differences in spinal ABMC in late puberty were 2-fold greater in girls who were homozygous for the C and G alleles, respectively (P = 0.001). For rs7757956, the difference in total body less head ABMC in late puberty was 50% less in individuals homozygous or heterozygous for the A allele (P = 0.006). Conclusions: Gains in ABMC in late pubertal girls are strongly associated with ESR1 polymorphisms, suggesting that estrogen contributes to this process via an estrogen receptor α-dependent pathway.

SecB binds only to a late native-like intermediate in the folding pathway of barstar and not to the unfolded state

SecB is a cytosolic, tetrameric chaperone of Escherichia coli which maintains precursor proteins in a translocation competent state. We have investigated the effect of SecB on the refolding kinetics of the small protein barstar in I M guanidine hydrochloride at pH 7.0 and 25 degrees C using fluorescence spectroscopy. We show that SecB does not bind either the native or the unfolded states of barstar but binds to a late near-native intermediate along the folding pathway. For barstar, polypeptide collapse and formation of a hydrophobic surface are required for binding to SecB. SecB does not change the apparent rate constant of barstar refolding. The kinetic data for SecB binding to barstar are not consistent with simple kinetic partitioning models.