Platinum-Based Nanoalloys PtnTM55-n (TM=Co, Rh, Au): A Density Functional Theory Investigation

Structural and electronic properties of the PtnTM55-n (TM = Co, Rh, Au) nanoalloys are investigated using density functional theory within the generalized gradient approximation and employing the all-electron projected augmented wave method. For TM = Co and Rh, the excess energy, which measures the relative energy stability of the nanoalloys, is negative for all Pt compositions. We found that the excess energy has similar values for a wide range of Pt compositions, i.e., n = 20-42 and n = 28-42 for Co and Rh, respectively, with the core shell icosahedron-like configuration (n = 42) being slightly more stable for both Co and Rh systems because of the larger release of the strain energy due to the smaller atomic size of the Co and Rh atoms. For TM = Au, the excess energy is positive for all compositions, except for n = 13, which is energetically favorable due to the formation of the core-shell structure (Pt in the core and Au atoms at the surface). Thus, our calculations confirm that the formation of core-shell structures plays an important role to increase the stability of nanoalloys. The center of gravity of the occupied d-states changes almost linearly as a function of the Pt composition, and hence, based on the d-band model, the magnitude of the adsorption energy of an adsorbate can be tuned by changing the Pt composition. The magnetic moments of PtnCo55-n decrease almost linearly as a function of the Pt composition; however, the same does not hold for PtRh and PtAu. We found an enhancement of the magnetic moments of PtRh by a few times by increasing Pt composition, which we explain by the compression effects induced by the large size of the Pt atoms compared with the Rh atoms.

A baixa estatura leve está associada ao aumento da pressão arterial em adolescentes com sobrepeso

FUNDAMENTO: Estudos têm demonstrado que a desnutrição pré/pós-natal leva a um maior risco de doenças não transmissíveis, como diabetes, hipertensão e obesidade na idade adulta. OBJETIVO: Determinar se os adolescentes com sobrepeso e desnutrição leve [escores-Z altura/idade (HAZ) na faixa de <-1 a > -2] têm pressão arterial mais elevada do que os indivíduos com sobrepeso e com estatura normal (HAZ > -1). MÉTODOS: Os participantes foram classificados como de baixa estatura leve ou de estatura normal, e estratificados de acordo com os percentis de massa corporal para a idade, como sobrepeso, peso normal ou abaixo do peso. As pressões arteriais sistólica (PAS) e diastólica (PAD) foram determinadas de acordo com as diretrizes e a gordura abdominal foi analisada por absorciometria de dupla emissão de raios-X. RESULTADOS: Indivíduos com baixa estatura leve e sobrepeso apresentaram valores mais elevados da PAD (p = 0,001) do que suas contrapartes de baixo peso (69,75 ± 12,03 e 54,46 ± 11,24 mmHg, respectivamente), mas semelhantes àqueles com IMC normal. Não foram encontradas diferenças nos valores de PAD em indivíduos normais, indivíduos com sobrepeso e com baixo peso entre os grupos de estatura normal. Foi encontrado um aumento na PAS (p = 0,01) entre os indivíduos com baixa estatura leve quando comparados os indivíduos com sobrepreso com suas contrapartes de baixo peso e IMC normal (114,70 ± 15,46, 97,38 ± 10,87 e 104,72 ± 12,24 mmHg, respectivamente). Embora não tenham sido observadas diferenças nas médias de PAS entre os grupos de baixa estatura leve e estatura normal, foi encontrado um intercepto significativo (p = 0,01), revelando maior PAS entre os indivíduos com baixa estatura leve. Houve correlação entre PAS e gordura abdominal (r = 0,42, ρ = 0,02) no grupo com baixa estatura leve. CONCLUSÃO: Indivíduos de baixa estatura leve com sobrepeso apresentaram maior PAS do que os de estatura normal e sobrepeso. Esses achados confirmam que a baixa estatura leve aumenta o risco futuro de hipertensão e essas alterações são evidentes em indivíduos jovens.

Avaliação do stent coronário eluidor de everolimus XIENCE TM V na cpopulação feminina latino-americana do estudo de braço único SPIRIT Women: acompanhamento clínico de um ano

INTRODUÇÃO: Os estudos com stents farmacológicos têm avaliado predominantemente populações masculinas de descendência europeia. O estudo de braço único SPIRIT Women avalia o stent eluidor de everolimus XIENCE TM V em lesões de novo complexas em uma população feminina do mundo real, incluindo pacientes latino-americanas. Esta análise permite compreender como essa população responde ao implante de stent, comparativamente a pacientes não-latino-americanas. MÉTODOS: Das 1.572 pacientes matriculadas em 73 locais fora dos Estados Unidos, 138 (9%) foram recrutadas na Argentina, no Brasil e na Venezuela. RESULTADOS: As lesões-alvo tinham diâmetro de referência do vaso entre 2,25 mm e 4 mm e extensão da lesão ≤ 28 mm. As características basais foram semelhantes entre os grupos, com exceção de maior prevalência de hipertensão arterial, infarto do miocárdio (IM) de parede anterior e história familiar de doença arterial coronária na coorte latino-americana. As lesões tendiam a ser mais complexas em mulheres latino-americanas, com menor diâmetro de referência do vaso-alvo, maior extensão da lesão, maior excentricidade e angulação e mais lesões tipo B2/C. Os eventos foram adjudicados de acordo com as definições do Academic Research Consortium. Em um ano, o desfecho combinado de morte por todas as causas, IM e revascularização do vaso-alvo (RVA) foi de 12,1% na população não-latino-americana e de 10,1% na população latino-americana (P = 0,58). CONCLUSÕES: Em um ano, os baixos índices de eventos cardíacos adversos, incluindo trombose do stent, falha da lesão-alvo, morte cardíaca, IM e RVA nas mulheres latino-americanas foram comparáveis aos das mulheres não-latino-americanas, apesar da maior complexidade das lesões. Esses resultados demonstram a segurança e a eficácia do stent XIENCE TM V nessa pequena coorte de pacientes latino-americanas, à semelhança do que é observado com populações maiores e mais variadas.

87 Rb-NMR-Untersuchungen an Trirubidiumhydrogendisulfat

In einer Vielzahl von Ionenkristallen mit Wasserstoffbrücken kann der Übergang aus einer paraelektrischen in eine elektrisch geordnete Phase mittels Substitution der Deuteronen durch Protonen um typischerweise 100 K abgesenkt werden. Die Ursache dieses Isotopieeffekts wird in Tunnelmoden der Protonen, in der Kopplung der Protonen untereinander oder in der Geometrie bzw. Symmetrie der Wasserstoffbrücke gesucht. Als Modellsubstanzen zur Untersuchung bieten sich die Trialkalihydrogendisulfate an. Hier sind die Wasserstoffbrücken, welche die Sulfattetraeder lokal zu Dimeren vernetzen, weit voneinander getrennt. Daher wird kein langreichweitiges Wasserstoffbrückennetzwerk ausgebildet.Bei den in dieser Arbeit untersuchten Rb3H1-xDx(SO4)2-Kristallen tritt der Phasenübergang im deuterierten Kristall bei 82 K auf und ist in protonierten Proben vollständig unterdrückt. Es wurde die 87Rb-NMR eingesetzt, weil damit Untersuchungen von Struktur und Dynamik im gesamten Konzentrationsbereich möglich sind. Die Meßgröße ist der elektrische Feldgradient (EFG), welcher durch die umgebenden Ionenladungen erzeugt wird.Durch orientierungsabhängige Messungen wurde gezeigt, daß die drei in der paraelektrischen Phase von Rb3D(SO4)2 vorkommenden EFG sich nicht durch Symmetrieoperationen ineinander überführen lassen. Es liegen somit kleine Abweichungen von einer monoklinen Symmetrie vor. Am Übergang in die antiferroelektrische Phase vervierfacht sich die Anzahl der kristallografisch inäquivalenten Einbaulagen. Aus dem Vergleich von NMR und Röntgenbeugung kann geschlossen werden, daß die Abweichungen von der monoklinen Raumgruppe und die elektrische Ordnung primär durch die Wasserstoffkerne verursacht werden. Aus der Aufspaltung der Resonanzlinien wurde ein statischer kritischer Exponent von  = 0,21  0,03 ermittelt, der mit trikritischem Verhalten verträglich ist. Die longitudinale Relaxation der Kernspinmagnetisierung wird durch Fluktuationen des EFG verursacht. Am Phasenübergang sind diese Fluktuationen an der Einbaulage der Rubidiumatome vergleichsweise groß und stark anisotrop. Beides läßt sich gut beschreiben, wenn angenommen wird, daß nur die Dynamik der Wasserstoffkerne die Kernspins relaxieren läßt. Für die longitudinale Relaxation wurde ebenfalls ein kritisches Verhalten am Phasenübergang gefunden. Der Exponent beträgt in deuterierten Proben  = -0,67 +- 0,07 und ist für die teildeuterierte Proben mit x = 0,5 größer:  = -1,15 +- 0,15. In der vorliegenden Arbeit konnte gezeigt werden, daß zur Beschreibung der NMR an verschiedenen Kernsorten weder, wie zuvor in der Literatur diskutiert, asymmetrische Wasserstoffbrücken noch Tunnelmoden erforderlich sind. Die hier erstmalig in den Trialkalihydrogendisulfaten gefundenen konzentrationsabhängigen kritischen Exponenten bilden einen neuen Prüfstein für die Modelle des Isotopieeffekts, die sich bisher primär auf die Erklärung der Phasenübergangstemperatur beschränkt haben.

Die Bedeutung des § 2 Abs. 1 BetrVG für den Umfang und die Schranken der Mitbestimmung nach § 87 BetrVG

Die vorliegende Arbeit befasst sich mit der Bedeutung des § 2 Abs. 1 BetrVG für die Reichweite und die Grenzen der Mitbestimmung des Betriebsrates nach § 87 BetrVG.. Ebenso wie im BetrVG 1952 bildet auch im BetrVG 1972 und im BetrVG 2001 der vierte Teil mit den Regelungen über die Mitwirkung und Mitbestimmung der Arbeitnehmer das eigentliche Kernstück des Gesetzes. Zentralvorschrift für die Mitbestimmung des Betriebsrats in sozialen Angelegenheiten ist dabei § 87 BetrVG. Diese Regelung umfasst alle Arbeitsbedingungen, die nicht schon gesetzlich oder tariflich geregelt sind, anderseits aber oft nur einheitlich für alle Arbeitnehmer im Betrieb geregelt werden können. Soweit die Tatbestandsvoraussetzungen der einzelnen Gegenstände in § 87 Abs. 1 Nr. 1 bis Nr. 13 BetrVG erfüllt sind, hat der Betriebsrat eine umfassende funktionelle Zuständigkeit zur Mitbestimmung in sämtlichen sozialen Angelegenheiten. Aufgabe der vorliegenden Arbeit soll es daher sein, Rechtsnatur, Struktur und Anwendungsbereich des Gebots der vertrauensvollen Zusammenarbeit und der Mitbestimmungsrechte gem. § 87 BetrVG zu klären. Hier ist insbesondere zu erörtern, ob Mitbestimmungsrechte des Betriebsrats gem. § 87 Abs. 1 BetrVG außerhalb des Katalogs der gesetzlichen Vorschriften aus dem Grundsatz der vertrauensvollen Zusammenarbeit herzuleiten sind. Ein weiterer Schwerpunkt liegt in der Herausarbeitung der Korrektur- und Schrankenfunktion des § 2 Abs. 1 BetrVG im Bereich der Mitbestimmung nach § 87 Abs. 1 BetrVG.

High mobility rates during the period of the "Celtic migrations"? - 87 Sr, 86 Sr and delta 18 O evidence from Early La Tène Europe

Although the period of the historic “Celtic migrations” is archaeologically extensively studied, the long-lasting question whether mass migration or increased individual mobility caused the expansion of the La Tène culture throughout continental Europe persist. Strontium (Sr) and in part oxygen (O) isotope analysis of human remains from the early La Tène cemeteries of Nebringen (Germany), Münsingen-Rain (Switzerland), Monte Bibele (Italy) and the Czech cemeteries of Radovesice I, Radovesice II and Kutná Hora was, therefore, carried out to investigate the importance of residential changes during this time period. These isotope analyses showed that most analysed individuals either came from the area they were buried in or from the surrounding area of the cemetery. An exception was formed by the Czech cemeteries, where almost a quarter of the studied individuals appeared non-local. Together with Nebringen, these cemeteries also had the most varied Sr isotope ratios, which suggest highly mobile communities in which individuals regularly changed their residency. The isotopic ratios of the cemeteries of Münsingen-Rain and Monte Bibele appeared far less varied. In part, these differences might be explained by the community structures of these cemeteries. Morphological kinship analysis in Münsingen-Rain demonstrated biological relatedness among most of the analysed individuals. These related individuals also shared similar isotope signatures, which suggest an origin from the surrounding Aar Valley. In the vicinity of the cemetery of Monte Bibele, an associated settlement site was discovered. The deceased presumably not only shared this settlement, but also cultivated the same land plots. Dispersed settlement structures were suggested for Nebringen, Radovesice and Kutná Hora, as these agriculturally favourable landscapes were densely populated during prehistoric times. Connected to these community structures are the prevailing geological conditions in these areas. Both Münsingen-Rain and Monte Bibele are located in a region where homogeneous geological conditions prevail, whereas the landscapes of Nebringen, Radovesice and Kutná Hora are characterised by complex heterogeneous geological conditions. As the majority of individuals in Nebringen and the Czech cemeteries correspond to the expected isotope values for the studied areas, regularly changing land plots might have contributed to the observed variation. Although mass migration as depicted by the historical sources was not observed individual mobility of a small part of these studied communities certainly played a role. Males appeared, thereby, to have slightly more often a non-local birthplace or moved during childhood. Male mobility was, however, not always associated with burial as a warrior. Females, on the other hand, originated more often from the region. Patrilocal residential patterns, with the exception of the Czech cemeteries, were nevertheless not observed. Objects and ideas also seem to have been exchanged freely, as there are no indications that individuals with particular grave goods came from specific areas. It rather appears that the individuals buried with them were either local or had different places of origin. This can be explained by the fact that the exact origin of grave goods is difficult to establish and the occurrence of similar 87Sr/86Sr values in different areas. This study provided important new insights on the period of the “Celtic migrations” and the way of life of these prehistoric people.

Blood glucose and prognosis in children with presumed severe malaria: is there a threshold for 'hypoglycaemia'?

OBJECTIVES: Hypoglycaemia (glucose <2.2 mmol/l) is a defining feature of severe malaria, but the significance of other levels of blood glucose has not previously been studied in children with severe malaria. METHODS: A prospective study of 437 consecutive children with presumed severe malaria was conducted in Mali. We defined hypoglycaemia as <2.2 mmol/l, low glycaemia as 2.2-4.4 mmol/l and hyperglycaemia as >8.3 mmol/l. Associations between glycaemia and case fatality were analysed for 418 children using logistic regression models and a receiver operator curve (ROC). RESULTS: There was a significant difference between blood glucose levels in children who died (median 4.6 mmol/l) and survivors (median 7.6 mmol/l, P < 0.001). Case fatality declined from 61.5% of the hypoglycaemic children to 46.2% of those with low glycaemia, 13.4% of those with normal glycaemia and 7.6% of those with hyperglycaemia (P < 0.001). Logistic regression showed an adjusted odds ratio (AOR) of 0.75 (0.64-0.88) for case fatality per 1 mmol/l increase in baseline blood glucose. Compared to a normal blood glucose, hypoglycaemia and low glycaemia both significantly increased the odds of death (AOR 11.87, 2.10-67.00; and 5.21, 1.86-14.63, respectively), whereas hyperglycaemia reduced the odds of death (AOR 0.34, 0.13-0.91). The ROC [area under the curve at 0.753 (95% CI 0.684-0.820)] indicated that glycaemia had a moderate predictive value for death and identified an optimal threshold at glycaemia <6.1 mmol/l, (sensitivity 64.5% and specificity 75.1%). CONCLUSIONS: If there is a threshold of blood glucose which defines a worse prognosis, it is at a higher level than the current definition of 2.2 mmol/l.

A remotely interrogated all-optical Rb-87 magnetometer

Atomic magnetometry was performed at Earth's magnetic field over a free-space distance of ten meters. Two laser beams aimed at a distant alkali-vapor cell excited and detected the Rb-87 magnetic resonance, allowing the magnetic field within the cell to be interrogated remotely. Operated as a driven oscillator, the magnetometer measured the geomagnetic field with less than or similar to 3.5 pT precision in a similar to 2 s data acquisition; this precision was likely limited by ambient field fluctuations. The sensor was also operated in self-oscillating mode with a 5.3 pT root Hz noise floor. Further optimization will yield a high-bandwidth, fully remote magnetometer with sub-pT sensitivity. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4747206]

Land use/cover change using Remote Sensing and Geographic Information Systems : Pic Macaya National Park, Haiti

A post classification change detection technique based on a hybrid classification approach (unsupervised and supervised) was applied to Landsat Thematic Mapper (TM), Landsat Enhanced Thematic Plus (ETM+), and ASTER images acquired in 1987, 2000 and 2004 respectively to map land use/cover changes in the Pic Macaya National Park in the southern region of Haiti. Each image was classified individually into six land use/cover classes: built-up, agriculture, herbaceous, open pine forest, mixed forest, and barren land using unsupervised ISODATA and maximum likelihood supervised classifiers with the aid of field collected ground truth data collected in the field. Ground truth information, collected in the field in December 2007, and including equalized stratified random points which were visual interpreted were used to assess the accuracy of the classification results. The overall accuracy of the land classification for each image was respectively: 1987 (82%), 2000 (82%), 2004 (87%). A post classification change detection technique was used to produce change images for 1987 to 2000, 1987 to 2004, and 2000 to 2004. It was found that significant changes in the land use/cover occurred over the 17- year period. The results showed increases in built up (from 10% to 17%) and herbaceous (from 5% to 14%) areas between 1987 and 2004. The increase of herbaceous was mostly caused by the abandonment of exhausted agriculture lands. At the same time, open pine forest and mixed forest areas lost (75%) and (83%) of their area to other land use/cover types. Open pine forest (from 20% to 14%) and mixed forest (from18 to 12%) were transformed into agriculture area or barren land. This study illustrated the continuing deforestation, land degradation and soil erosion in the region, which in turn is leading to decrease in vegetative cover. The study also showed the importance of Remote Sensing (RS) and Geographic Information System (GIS) technologies to estimate timely changes in the land use/cover, and to evaluate their causes in order to design an ecological based management plan for the park.