X-ray absorption study of Ti-activated sodium aluminum hydride

Ti K-edge x-ray absorption near edge spectroscopy (XANES) was used to explore the Ti valence and coordination in Ti-activated sodium alanate. An empirical relationship was established between the Ti valence and the Ti K-edge onset based on a set of standards. This relationship was used to estimate oxidation states of the titanium catalyst in 2 mol% and 4 mol% Ti-doped NaAlH4. These results demonstrate that the formal titanium valence is zero in doped sodium alanate and nearly invariant during hydrogen cycling. A qualitative comparison of the edge fine structure suggests that the Ti is present on the surface in the form of amorphous TiAl3.Comment: 3 pages, 4 figures, submitted to Appl. Phys. Let

Thermochemistry of Alane Complexes for Hydrogen Storage: A Theoretical and Experimental Comparison

Knowledge of the relative stabilities of alane (AlH3) complexes with electron donors is essential for identifying hydrogen storage materials for vehicular applications that can be regenerated by off-board methods; however, almost no thermodynamic data are available to make this assessment. To fill this gap, we employed the G4(MP2) method to determine heats of formation, entropies, and Gibbs free energies of formation for thirty-eight alane complexes with NH3-nRn (R = Me, Et; n = 0-3), pyridine, pyrazine, triethylenediamine (TEDA), quinuclidine, OH2-nRn (R = Me, Et; n = 0-2), dioxane, and tetrahydrofuran (THF). Monomer, bis, and selected dimer complex geometries were considered. Using these data, we computed the thermodynamics of the key formation and dehydrogenation reactions that would occur during hydrogen delivery and alane regeneration, from which trends in complex stability were identified. These predictions were tested by synthesizing six amine-alane complexes involving trimethylamine, triethylamine, dimethylethylamine, TEDA, quinuclidine, and hexamine, and obtaining upper limits of delta G for their formation from metallic aluminum. Combining these computational and experimental results, we establish a criterion for complex stability relevant to hydrogen storage that can be used to assess potential ligands prior to attempting synthesis of the alane complex. Based on this, we conclude that only a subset of the tertiary amine complexes considered and none of the ether complexes can be successfully formed by direct reaction with aluminum and regenerated in an alane-based hydrogen storage system.Comment: Accepted by the Journal of Physical Chemistry

Intensive Rotational Grazing Systems for Dairying in a Subtropical Environment: Animal, Plant, and Soil Responses

Forage species, stocking rate, and supplementation rate effects upon performance of lactating dairy cows were studied. Forage mass and nutritive value and nutrient concentration in shallow groundwater also were measured. Cows (n = 44) grazed bermudagrass (Cynodon dactylon) or rhizoma peanut (Arachis glabrata), stocked at 4.9 or 7.4 cows ha-1, and 2.5 or 4.9 cows ha-1, respectively. Pelleted concentrate:whole cottonseed (80:20) was offered twice daily post milking at 1 kg per 2 or 3 kg of daily milk production. Cows grazing rhizoma peanut produced more (P = .076) milk per day but had greater (P = .028) loss of body condition. Higher stocking rates caused greater (P \u3e .070) weight loss. Greater supplementation increased (P \u3c .05) production of milk, fat and protein, but also increased (P \u3c .044) weight and body condition losses. Higher stocking rates and lower supplementation reduced pasture (P \u3c .001) herbage mass. Rhizoma peanut herbage was higher in nutritive value than bermudagrass. Nutrient concentrations in shallow groundwater were not affected by treatments. Use of pasture for lactating cows has potential in Florida, but low milk production and loss of body condition during summer pose management challenges

Convergence of the Generalized Volume Averaging Method on a Convection-Diffusion Problem: A Spectral Perspective

A mixed formulation is proposed and analyzed mathematically for coupled convection-diffusion in heterogeneous medias. Transfer in solid parts driven by pure diffusion is coupled with convection-diffusion transfer in fluid parts. This study is carried out for translation-invariant geometries (general infinite cylinders) and unidirectional flows. This formulation brings to the fore a new convection-diffusion operator, the properties of which are mathematically studied: its symmetry is first shown using a suitable scalar product. It is proved to be self-adjoint with compact resolvent on a simple Hilbert space. Its spectrum is characterized as being composed of a double set of eigenvalues: one converging towards −∞ and the other towards +∞, thus resulting in a nonsectorial operator. The decomposition of the convection-diffusion problem into a generalized eigenvalue problem permits the reduction of the original three-dimensional problem into a two-dimensional one. Despite the operator being nonsectorial, a complete solution on the infinite cylinder, associated to a step change of the wall temperature at the origin, is exhibited with the help of the operator’s two sets of eigenvalues/eigenfunctions. On the computational point of view, a mixed variational formulation is naturally associated to the eigenvalue problem. Numerical illustrations are provided for axisymmetrical situations, the convergence of which is found to be consistent with the numerical discretization

An environmental threshold for degree of phosphorus saturation in sandy soils.

ABSTRACT soil is completely saturated with P There is critical need for a practical indicator to assess the potential by local conditions and generally reflects local surface for phosphorus (P) movement from a given site to surface waters, water criteria for P. The Netherlands has established a either via surface runoff or subsurface drainage. The degree of phosphorus saturation (DPS), which relates a measure of P already adwater quality goal for ground water of 0.15 mg total P sorbed by a soil to its P adsorption capacity, could be a good indicator , and their studies have shown that leaching of P of that soil's P release capability. Our primary objective was to find could occur especially from manure-contaminated soils a suitable analytical protocol for determining DPS and to examine S andy soils in the Suwannee River basin of northern phorus (WSP) (assessed using either deionized water Florida have little ability to adsorb P, and yet many or 0.01 M CaCl 2 ) and each method of DPS calculation; dairies in the Suwannee River basin routinely apply and (iv) examine the possibility of defining a threshold P-rich lagoon effluent onto permanent sprayfields for DPS value for Florida's sandy soils. waste disposal and nutrient recycling. Increased P loading to these sites may lead to P loss through runoff and subsurface drainage, contributing to surface water MATERIALS AND METHODS quality degradation. Improved P management of these Study Site fields requires the evaluation of soil P concentrations The Suwannee River basin was selected for this study. Many relative to the soil's ability to adsorb P. of the dairies found in the middle Suwannee River basin, Recent studies suggest that the DPS, which relates proximal to the Suwannee and Santa Fe Rivers, are situated ammonium oxalate-extractable P to the sum of oxalateatop a geomorphic zone classified as the Chiefland Limestone extractable Fe and Al (DPS Ox ), is a good indicator of a Plain. The upper surface of the aquifer system is relatively soil's potential to release P (Hooda et al., 2000). This close to the surface and layers above it are thin and unconfined concept was first introduced in the Netherlands, where (Andrews, 1992). The surficial aquifer system is largely reit has been shown that P concentrations in the soil solucharged by rainfall that percolates downward through the tion can exceed a critical concentration well before the loose surficial clastic sediments. Water naturally discharges from the aquifer through evaporation, transpiration, spring flow, and downward seepage into the underlying Floridan aqui

The pleasures and perils of inheritance

Facing death, reflecting on one’s legacies (material and ethical, personal and political) and the legal and interpersonal attempts to resolve or prevent inheritance conflicts, all bring to the fore constructions of memory and identity, intergenerational relations, and the complexities of doing and undoing family and kinship. Consequently, drawing attention to inheritance, keeping sight of it, and bringing it into play is a useful piece of the puzzle of ageing across a range of disciplines and this article provides an overview of some of the key themes in this emerging field

Novel multiple sclerosis susceptibility loci implicated in epigenetic regulation

We conducted a genome-wide association study (GWAS) on multiple sclerosis (MS) susceptibility in German cohorts with 4888 cases and 10,395 controls. In addition to associations within the major histocompatibility complex (MHC) region, 15 non-MHC loci reached genome-wide significance. Four of these loci are novel MS susceptibility loci. They map to the genes L3MBTL3, MAZ, ERG, and SHMT1. The lead variant at SHMT1 was replicated in an independent Sardinian cohort. Products of the genes L3MBTL3, MAZ, and ERG play important roles in immune cell regulation. SHMT1 encodes a serine hydroxymethyltransferase catalyzing the transfer of a carbon unit to the folate cycle. This reaction is required for regulation of methylation homeostasis, which is important for establishment and maintenance of epigenetic signatures. Our GWAS approach in a defined population with limited genetic substructure detected associations not found in larger, more heterogeneous cohorts, thus providing new clues regarding MS pathogenesis

The Forgotten Side of Partisanship: Negative Party Identification in Four Anglo-American Democracies

Early studies of electoral behavior proposed that party identification could be negative as well as positive. Over time, though, the concept became mostly understood as a positive construct. The few studies that took negative identification into account tended to portray it as a marginal factor that went “hand-in-hand” with positive preferences. Recent scholarship in psychology reaffirms, however, that negative evaluations are not simply the bipolar opposite of positive ones. This article considers negative party identification from this standpoint, and evaluates its impact in recent national elections in Australia, Canada, New Zealand, and the United States. Our findings highlight the autonomous power of negative partisanship. They indicate as well that ideology has an influence on both positive and negative partisan identification

Global effect of the COVID-19 pandemic on paediatric cancer care: a cross-sectional study

BACKGROUND: Although mortality due to COVID-19 has been reportedly low among children with cancer, changes in health-care services due to the pandemic have affected cancer care delivery. This study aimed to assess the effect of the COVID-19 pandemic on childhood cancer care worldwide. METHODS: A cross-sectional survey was distributed to paediatric oncology providers worldwide from June 22 to Aug 21, 2020, through the St Jude Global Alliance and International Society for Paediatric Oncology listservs and regional networks. The survey included 60 questions to assess institution characteristics, the number of patients diagnosed with COVID-19, disruptions to cancer care (eg, service closures and treatment abandonment), adaptations to care, and resources (including availability of clinical staff and personal protective equipment). Surveys were included for analysis if respondents answered at least two thirds of the items, and the responses were analysed at the institutional level. FINDINGS: Responses from 311 health-care professionals at 213 institutions in 79 countries from all WHO regions were included in the analysis. 187 (88%) of 213 centres had the capacity to test for SARS-CoV-2 and a median of two (range 0-350) infections per institutution were reported in children with cancer. 15 (7%) centres reported complete closure of paediatric haematology-oncology services (median 10 days, range 1-75 days). Overall, 2% (5 of 213) of centres were no longer evaluating new cases of suspected cancer, while 43% (90 of 208) of the remaining centers described a decrease in newly diagnosed paediatric cancer cases. 73 (34%) centres reported increased treatment abandonment (ie, failure to initiate cancer therapy or a delay in care of 4 weeks or longer). Changes to cancer care delivery included: reduced surgical care (153 [72%]), blood product shortages (127 [60%]), chemotherapy modifications (121 [57%]), and interruptions to radiotherapy (43 [28%] of 155 institutions that provided radiotherapy before the pandemic). The decreased number of new cancer diagnoses did not vary based on country income status (p=0·14). However, unavailability of chemotherapy agents (p=0·022), treatment abandonment (p<0·0001), and interruptions in radiotherapy (p<0·0001) were more frequent in low-income and middle-income countries than in high-income countries. These findings did not vary based on institutional or national numbers of COVID-19 cases. Hospitals reported using new or adapted checklists (146 [69%] of 213), processes for communication with patients and families (134 [63%]), and guidelines for essential services (119 [56%]) as a result of the pandemic. INTERPRETATION: The COVID-19 pandemic has considerably affected paediatric oncology services worldwide, posing substantial disruptions to cancer diagnosis and management, particularly in low-income and middle-income countries. This study emphasises the urgency of an equitably distributed robust global response to support paediatric oncology care during this pandemic and future public health emergencies. FUNDING: American Lebanese Syrian Associated Charities. TRANSLATION: For the Spanish translation of the abstract see Supplementary Materials section

GHQ increases among Scottish 15 year olds 1987–2006

BACKGROUND: Increases in a number of psychosocial disorders have been identified among Western youth in the second half of the Twentieth century. However findings are not consistent, trends are complex, and comparisons over time are hampered by methodological problems. METHODS: Data were drawn from three samples identical in respect of age (15 years), school year (final year of statutory schooling) and geographical location (the West of Scotland). Each sample was administered the 12-item General Health Questionnaire, a measure of self-report psychological distress, in 1987 (N = 505), 1999 (N = 2,196) and 2006 (N = 3,194). Analyses were conducted to examine changes in: GHQ 'caseness'; individual items; and factors, derived via confirmatory factor analysis representing (a) 'negative' and 'positive' items, and (b) 'anxiety and depression', 'loss of confidence or self-esteem' and 'anhedonia and social dysfunction'. RESULTS: Based on the standard (2/3) cut-off, 'caseness' rates in 1987, 1999 and 2006 were 12.7, 15.1 and 21.5% (males) and 18.8, 32.5 and 44.1% (females). Similar increases were observed with more stringent 'caseness' cut-offs. Examination of individual items showed some to have increased much more markedly over time than others. There were larger increases among females for all except two items and some evidence, among both genders, of steeper increases among 'negative' items compared with 'positive' ones. However, the differences in slope were very small compared with the overall increases in both types. CONCLUSIONS: Data from three samples identical in respect of age, school year and geographical location, show marked increases in GHQ-12 'caseness' among females between 1987 and 1999 and among both males and females between 1999 and 2006. Although slightly steeper increases in 'negative' items raise the possibility that endorsing such symptoms may have become more acceptable, these were small in comparison with increases in all dimensions of psychological distress. The next step is to identify causal explanations for the increases reported here