The disinfection by-product (DBP) formation potential (FP) of natural organic matter (NOM) in surface water sources has been studied with reference to the key water quality determinants (WQDs) of UV ...absorption (UV254), colour, and dissolved organic carbon (DOC) concentration. The data set used encompassed raw and treated water sampled over a 30-month period from 30 water treatment works (WTWs) across Scotland, all employing conventional clarification. Both trihalomethane (THM) and haloacetic acid (HAA) FPs were considered. In addition to the standard bulk WQDs, the DOC content was fractionated and analysed for the hydrophobic (HPO) and hydrophilic (HPI) fractions. Results were quantified in terms of the yield (dDBPFP/dWQD) and the linear regression coefficient R2 of the yield trend.
The NOM in the raw waters was found to comprise 30–84% (average 66%) of the more reactive HPO material, with this proportion falling to 18–63% (average 50%) in the treated water. Results suggested UV254 to be as good an indicator of DBPFP as DOC or HPO for the raw waters, with R2 values ranging from 0.79 to 0.82 for THMs and from 0.71 to 0.73 for HAAs for these three determinants. For treated waters the corresponding values were significantly lower at 0.52–0.67 and 0.46–0.47 respectively, reflecting the lower HPO concentration and thus UV254 absorption and commensurately reduced precision due to the limit of detection of the analytical instrument.
It is concluded that fractionation offers little benefit in attempting to discern or predict chlorinated carbonaceous DBP yield for the waters across the geographical region studied. UV254 offered an adequate estimate of DBPFP based on a mean yield of ∼2600 and ∼2800 μg per cm−1 absorbance for THMFP for the raw and treated waters respectively and ∼3800 and2900 μg cm−1 for HAAFP, albeit with reduced precision for the treated waters.
•Impact of clarification of surface water on DBPFP studied for THMs and HAAs.•Study based on 30 WTW sites over 30 month period, and both raw and treated waters.•Trends in R2 for DBPFP vs UV254 and DOC were the same for the two DBPs.•UV254 and DOC were as good an indicator of DBPFP as hydrophobic carbon concentration.•Change in DBP yield from raw to treated water corresponds to change in HPO fraction.
Whether Andean populations are genetically adapted to high altitudes has long been of interest. Initial studies focused on physiological changes in the O₂ transport system that occur with ...acclimatization in newcomers and their comparison with those of long-resident Andeans. These as well as more recent studies indicate that Andeans have somewhat larger lung volumes, narrower alveolar to arterial O₂ gradients, slightly less hypoxic pulmonary vasoconstrictor response, greater uterine artery blood flow during pregnancy, and increased cardiac O
utilization, which overall suggests greater efficiency of O₂ transfer and utilization. More recent single nucleotide polymorphism and whole-genome sequencing studies indicate that multiple gene regions have undergone recent positive selection in Andeans. These include genes involved in the regulation of vascular control, metabolic hemostasis, and erythropoiesis. However, fundamental questions remain regarding the functional links between these adaptive genomic signals and the unique physiological attributes of highland Andeans. Well-designed physiological and genome association studies are needed to address such questions. It will be especially important to incorporate the role of epigenetic processes (i.e.; non-sequence-based features of the genome) that are vital for transcriptional responses to hypoxia and are potentially heritable across generations. In short, further exploration of the interaction among genetic, epigenetic, and environmental factors in shaping patterns of adaptation to high altitude promises to improve the understanding of the mechanisms underlying human adaptive potential and clarify its implications for human health.
Superconductivity originates from pairing of electrons near the Fermi energy. The Fermi surface topology and pairing symmetry are thus two pivotal characteristics of a superconductor. ...Superconductivity in one monolayer (1 ML) FeSe thin film has attracted great interest recently due to its intriguing interfacial properties and possibly high superconducting transition temperature over 65 K. Here, we report high-resolution measurements of the Fermi surface and superconducting gaps in 1 ML FeSe using angle-resolved photoemission spectroscopy. Two ellipselike electron pockets are clearly resolved overlapping with each other at the Brillouin zone corner. The superconducting gap is nodeless but moderately anisotropic, which puts strong constraint on determining the pairing symmetry. The gap maxima locate on the d_{xy} bands along the major axis of the ellipse and four gap minima are observed at the intersections of electron pockets. The gap maximum location combined with the Fermi surface geometry deviate from a single d-wave, extended s-wave or s_{±} gap function, suggesting an important role of the multiorbital nature of Fermi surface and orbital-dependent pairing in 1 ML FeSe. The gap minima location may be explained by a sign change on the electron pockets, or a competition between intra- and interorbital pairing.
Myelin water imaging (MWI) promises to be invaluable in understanding neurological diseases like MS. However, a limitation of MWI is signal to noise ratio. Recently, a number of investigators have ...performed MWI at field strengths higher than 1.5 T. Our goal was to determine if myelin water imaging at increased SNR, arising from the use of a small bore 7 T MR system with optimized coil geometry, enables the production of superior myelin water maps with increased spatial detail and enables better correlations with histology. Ten formalin-fixed MS brain samples underwent a 32-echo T2 relaxation experiment which measured myelin water fraction (MWF) on a 7-T animal MRI scanner. MWF correlated strongly qualitatively and quantitatively with luxol fast blue staining for myelin mean (range): R2=0.78 (0.56–0.95), p<0.0001. The quality and detail of 7 T myelin water maps were far superior to that previously seen at 1.5 T, allowing for visualization of fine structures such as the normal prominent myelination of the deeper cortical layers, the alveus of the hippocampus and rings of preserved myelin in a concentric Balo's lesion. 7 T imaging will allow detailed assessment of myelin pathology to a degree not possible with lower field strengths.
On the Joys of Missing Data LITTLE, Todd D; JORGENSEN, Terrence D; LANG, Kyle M ...
Journal of pediatric psychology,
03/2014, Letnik:
39, Številka:
2
Journal Article
Recenzirano
We provide conceptual introductions to missingness mechanisms--missing completely at random, missing at random, and missing not at random--and state-of-the-art methods of handling missing ...data--full-information maximum likelihood and multiple imputation--followed by a discussion of planned missing designs: Multiform questionnaire protocols, 2-method measurement models, and wave-missing longitudinal designs. We reviewed 80 articles of empirical studies published in the 2012 issues of the Journal of Pediatric Psychology to present a picture of how adequately missing data are currently handled in this field. To illustrate the benefits of using multiple imputation or full-information maximum likelihood and incorporating planned missingness into study designs, we provide example analyses of empirical data gathered using a 3-form planned missing design.
Manganese tricarbonyl complexes are promising catalysts for CO2 reduction, but complexes in this family are often photosensitive and decompose rapidly upon exposure to visible light. In this report, ...synthetic and photochemical studies probe the initial steps of light-driven speciation for Mn(CO)3(Rbpy)Br complexes bearing a range of 4,4′-disubstituted 2,2′-bipyridyl ligands (Rbpy, where R = tBu, H, CF3, NO2). Transient absorption spectroscopy measurements for Mn(CO)3(Rbpy)Br coordination compounds with R = tBu, H, and CF3 in acetonitrile reveal ultrafast loss of a CO ligand on the femtosecond time scale, followed by solvent coordination on the picosecond time scale. The Mn(CO)3(NO2 bpy)Br complex is unique among the four compounds in having a longer-lived excited state that does not undergo CO release or subsequent solvent coordination. The kinetics of photolysis and solvent coordination for light-sensitive complexes depend on the electronic properties of the disubstituted bipyridyl ligand. The results indicate that both metal-to-ligand charge-transfer (MLCT) and dissociative ligand-field (d–d) excited states play a role in the ultrafast photochemistry. Taken together, the findings suggest that more robust catalysts could be prepared with appropriately designed complexes that avoid crossing between the excited states that drive photochemical CO loss.
Hybrid materials that link light capture and conversion technologies with the ability to drive reductive chemical transformations are attractive as components in photoelectrosynthetic cells. We show ...that thin-film polypyridine surface coatings provide a molecular interface to assemble cobalt porphyrin catalysts for hydrogen evolution onto a visible-light-absorbing p-type gallium phosphide semiconductor. Spectroscopic techniques, including grazing angle attenuated total reflection Fourier transform infrared spectroscopy, confirm that the cobalt centers of the porphyrin macrocycles coordinate to pyridyl nitrogen sites of the organic surface coating. The cobalt porphyrin surface concentration and fraction of pyridyl sites coordinated to a cobalt center are quantified using complementary methods of ellipsometry, inductively coupled plasma mass spectrometry, and X-ray photoelectron spectroscopy. In aqueous solutions under simulated solar illumination the modified cathode is photochemically active for hydrogen production, generating the product gas with near-unity Faradaic efficiency at a rate of ≈10 μL min–1 cm–2 when studied in a three-electrode configuration and polarized at the equilibrium potential of the H+/H2 couple. This equates to a photoelectrochemical hydrogen evolution reaction activity of 17.6 H2 molecules s–1 Co–1, the highest value reported to date for a molecular-modified semiconductor. Key features of the functionalized photocathode include (1) the relative ease of synthetic preparation made possible by application of an organic surface coating that provides molecular recognition sites for immobilizing the cobalt porphyrin complexes at the semiconductor surface and (2) the use of visible light to drive cathodic fuel-forming reactions in aqueous solutions with no added organic acids or sacrificial chemical reductants.
Metabolites of the kynurenine pathway (KP) of tryptophan (TRP) degradation have been closely linked to the pathogenesis of several neurodegenerative disorders. Recent work has highlighted the ...therapeutic potential of inhibiting two critical regulatory enzymes in this pathway—kynurenine-3-monooxygenase (KMO) and tryptophan-2,3-dioxygenase (TDO). Much evidence indicates that the efficacy of KMO inhibition arises from normalizing an imbalance between neurotoxic 3-hydroxykynurenine (3-HK); quinolinic acid (QUIN) and neuroprotective kynurenic acid (KYNA) KP metabolites. However, it is not clear if TDO inhibition is protective via a similar mechanism or if this is instead due to increased levels of TRP—the substrate of TDO. Here, we find that increased levels of KYNA relative to 3-HK are likely central to the protection conferred by TDO inhibition in a fruit fly model of Huntington’s disease and that TRP treatment strongly reduces neurodegeneration by shifting KP flux toward KYNA synthesis. In fly models of Alzheimer’s and Parkinson’s disease, we provide genetic evidence that inhibition of TDO or KMO improves locomotor performance and ameliorates shortened life span, as well as reducing neurodegeneration in Alzheimer’s model flies. Critically, we find that treatment with a chemical TDO inhibitor is robustly protective in these models. Consequently, our work strongly supports targeting of the KP as a potential treatment strategy for several major neurodegenerative disorders and suggests that alterations in the levels of neuroactive KP metabolites could underlie several therapeutic benefits.
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