Orbital interactions and chemical reactivity of metal particles and metal surfaces

A review is presented with 101 refs. on chem. bonding to metal surfaces and small metal particles demonstrating the power of symmetry concepts to predict changes in chem. bonding. Ab-initio calcns. of chemisorption to small particles, as well as semiempirical extended Hueckel calcns. applied to the study of the reactivity of metal slabs are reviewed. On small metal particles, classical notions of electron promotion and hybridization are found to apply. The surroundings of a metal atom (ligands in complexes, other metal atoms at surfaces), affect bonding and reactivity through the prehybridization they induce. A factor specific for large particles and surfaces is the required localization of electrons on the atoms involved in the metal surface bond. At the surface, the bond energy is found to relate to the grou8p orbital local d. of states at the Fermi level. The use of this concept is extensively discussed and illustrated for chemisorption of CO and dissocn. of NO on metal surfaces. A discussion is given of the current decompn. schemes of bond energies and related concepts (exchange (Pauli)-repulsion, polarization, charge transfer). The role of non-orthogonality of fragment orbitals and of kinetic and potential energy for Pauli repulsion and (orbital) polarization is analyzed. Numerous examples are discussed to demonstrate the impact of those concepts on chem. bonding theor

PS18kh: A New Tidal Disruption Event with a Non-axisymmetric Accretion Disk

We present the discovery of PS18kh, a tidal disruption event discovered at the center of SDSS J075654.53+341543.6 (d ≃ 322 Mpc) by the Pan-STARRS Survey for Transients. Our data set includes pre-discovery survey data from Pan-STARRS, the All-sky Automated Survey for Supernovae, and the Asteroid Terrestrial-impact Last Alert System as well as high-cadence, multiwavelength follow-up data from ground-based telescopes and Swift, spanning from 56 days before peak light until 75 days after. The optical/UV emission from PS18kh is well-fit as a blackbody with temperatures ranging from T ≃ 12,000 K to T ≃ 25,000 K and it peaked at a luminosity of L ≃ 8.8 × 10 erg s . PS18kh radiated E = (3.45 ± 0.22) × 10 erg over the period of observation, with (1.42 ± 0.20) × 10 erg being released during the rise to peak. Spectra of PS18kh show a changing, boxy/double-peaked Hα emission feature, which becomes more prominent over time. We use models of non-axisymmetric accretion disks to describe the profile of the Hα line and its evolution. We find that at early times the high accretion rate leads the disk to emit a wind which modifies the shape of the line profile and makes it bell-shaped. At late times, the wind becomes optically thin, allowing the non-axisymmetric perturbations to show up in the line profile. The line-emitting portion of the disk extends from r ∼ 60r to an outer radius of r ∼ 1400r and the perturbations can be represented either as an eccentricity in the outer rings of the disk or as a spiral arm in the inner disk. 43 -1 50 50 in g out

Management of MDR-TB in HIV co-infected patients in Eastern Europe: Results from the TB:HIV study

OBJECTIVES: Mortality among HIV patients with tuberculosis (TB) remains high in Eastern Europe (EE), but details of TB and HIV management remain scarce. METHODS: In this prospective study, we describe the TB treatment regimens of patients with multi-drug resistant (MDR) TB and use of antiretroviral therapy (ART). RESULTS: A total of 105 HIV-positive patients had MDR-TB (including 33 with extensive drug resistance) and 130 pan-susceptible TB. Adequate initial TB treatment was provided for 8% of patients with MDR-TB compared with 80% of those with pan-susceptible TB. By twelve months, an estimated 57.3% (95%CI 41.5-74.1) of MDR-TB patients had started adequate treatment. While 67% received ART, HIV-RNA suppression was demonstrated in only 23%. CONCLUSIONS: Our results show that internationally recommended MDR-TB treatment regimens were infrequently used and that ART use and viral suppression was well below the target of 90%, reflecting the challenging patient population and the environment in which health care is provided. Urgent improvement of management of patients with TB/HIV in EE, in particular for those with MDR-TB, is needed and includes widespread access to rapid TB diagnostics, better access to and use of second-line TB drugs, timely ART initiation with viral load monitoring, and integration of TB/HIV care

Effects of Global Warming on Ancient Mammalian Communities and Their Environments

Current global warming affects the composition and dynamics of mammalian communities and can increase extinction risk; however, long-term effects of warming on mammals are less understood. Dietary reconstructions inferred from stable isotopes of fossil herbivorous mammalian tooth enamel document environmental and climatic changes in ancient ecosystems, including C(3)/C(4) transitions and relative seasonality.Here, we use stable carbon and oxygen isotopes preserved in fossil teeth to document the magnitude of mammalian dietary shifts and ancient floral change during geologically documented glacial and interglacial periods during the Pliocene (approximately 1.9 million years ago) and Pleistocene (approximately 1.3 million years ago) in Florida. Stable isotope data demonstrate increased aridity, increased C(4) grass consumption, inter-faunal dietary partitioning, increased isotopic niche breadth of mixed feeders, niche partitioning of phylogenetically similar taxa, and differences in relative seasonality with warming.Our data show that global warming resulted in dramatic vegetation and dietary changes even at lower latitudes (approximately 28 degrees N). Our results also question the use of models that predict the long term decline and extinction of species based on the assumption that niches are conserved over time. These findings have immediate relevance to clarifying possible biotic responses to current global warming in modern ecosystems

Recent Shift in Climate Relationship Enables Prediction of the Timing of Bird Breeding

Large-scale climate processes influence many aspects of ecology including breeding phenology, reproductive success and survival across a wide range of taxa. Some effects are direct, for example, in temperate-zone birds, ambient temperature is an important cue enabling breeding effort to coincide with maximum food availability, and earlier breeding in response to warmer springs has been documented in many species. In other cases, time-lags of up to several years in ecological responses have been reported, with effects mediated through biotic mechanisms such as growth rates or abundance of food supplies. Here we use 23 years of data for a temperate woodland bird species, the great tit (Parus major), breeding in deciduous woodland in eastern England to demonstrate a time-lagged linear relationship between the on-set of egg laying and the winter index of the North Atlantic Oscillation such that timing can be predicted from the winter index for the previous year. Thus the timing of bird breeding (and, by inference, the timing of spring events in general) can be predicted one year in advance. We also show that the relationship with the winter index appears to arise through an abiotic time-lag with local spring warmth in our study area. Examining this link between local conditions and larger-scale processes in the longer-term showed that, in the past, significant relationships with the immediately preceding winter index were more common than those with the time-lagged index, and especially so from the late 1930s to the early 1970s. However, from the mid 1970s onwards, the time-lagged relationship has become the most significant, suggesting a recent change in climate patterns. The strength of the current time-lagged relationship suggests that it might have relevance for other temperature-dependent ecological relationships

Evidence of Infection by H5N2 Highly Pathogenic Avian Influenza Viruses in Healthy Wild Waterfowl

The potential existence of a wild bird reservoir for highly pathogenic avian influenza (HPAI) has been recently questioned by the spread and the persisting circulation of H5N1 HPAI viruses, responsible for concurrent outbreaks in migratory and domestic birds over Asia, Europe, and Africa. During a large-scale surveillance programme over Eastern Europe, the Middle East, and Africa, we detected avian influenza viruses of H5N2 subtype with a highly pathogenic (HP) viral genotype in healthy birds of two wild waterfowl species sampled in Nigeria. We monitored the survival and regional movements of one of the infected birds through satellite telemetry, providing a rare evidence of a non-lethal natural infection by an HP viral genotype in wild birds. Phylogenetic analysis of the H5N2 viruses revealed close genetic relationships with H5 viruses of low pathogenicity circulating in Eurasian wild and domestic ducks. In addition, genetic analysis did not reveal known gallinaceous poultry adaptive mutations, suggesting that the emergence of HP strains could have taken place in either wild or domestic ducks or in non-gallinaceous species. The presence of coexisting but genetically distinguishable avian influenza viruses with an HP viral genotype in two cohabiting species of wild waterfowl, with evidence of non-lethal infection at least in one species and without evidence of prior extensive circulation of the virus in domestic poultry, suggest that some strains with a potential high pathogenicity for poultry could be maintained in a community of wild waterfowl

Why do we treat adolescent idiopathic scoliosis? What we want to obtain and to avoid for our patients. SOSORT 2005 Consensus paper

BACKGROUND: Medicine is a scientific art: once science is not clear, choices are made according to individual and collective beliefs that should be better understood. This is particularly true in a field like adolescent idiopathic scoliosis, where currently does not exist definitive scientific evidence on the efficacy either of conservative or of surgical treatments. AIM OF THE STUDY: To verify the philosophical choices on the final outcome of a group of people believing and engaged in a conservative treatment of idiopathic scoliosis. METHODS: We performed a multifaceted study that included a bibliometric analysis, a questionnaire, and a careful Consensus reaching procedure between experts in the conservative treatment of scoliosis (SOSORT members). RESULTS: The Consensus reaching procedure has shown to be useful: answers changed in a statistically significant way, and 9 new outcome criteria were included. The most important final outcomes were considered Aesthetics (100%), Quality of life and Disability (more than 90%), while more than 80% of preferences went to Back Pain, Psychological well-being, Progression in adulthood, Breathing function, Scoliosis Cobb degrees (radiographic lateral flexion), Needs of further treatments in adulthood. DISCUSSION: In the literature prevail outcome criteria driven by the contingent treatment needs or the possibility to have measurement systems (even if it seems that usual clinical and radiographic methods are given much more importance than more complex Disability or Quality of Life instruments). SOSORT members give importance to a wide range of outcome criteria, in which clinical and radiographic issues have the lowest importance. CONCLUSION: We treat our patients for what they need for their future (Breathing function, Needs of further treatments in adulthood, Progression in adulthood), and their present too (Aesthetics, Disability, Quality of life). Technical matters, such as rib hump or radiographic lateral alignment and rotation, but not lateral flexion, are secondary outcomes and only instrumental to previously reported primary outcomes. We advocate a multidimensional, comprehensive evaluation of scoliosis patients, to gather all necessary data for a complete therapeutic approach, that goes beyond x-rays to reach the person and the family

An overlooked connection: serotonergic mediation of estrogen-related physiology and pathology

BACKGROUND: In humans, serotonin has typically been investigated as a neurotransmitter. However, serotonin also functions as a hormone across animal phyla, including those lacking an organized central nervous system. This hormonal action allows serotonin to have physiological consequences in systems outside the central nervous system. Fluctuations in estrogen levels over the lifespan and during ovarian cycles cause predictable changes in serotonin systems in female mammals. DISCUSSION: We hypothesize that some of the physiological effects attributed to estrogen may be a consequence of estrogen-related changes in serotonin efficacy and receptor distribution. Here, we integrate data from endocrinology, molecular biology, neuroscience, and epidemiology to propose that serotonin may mediate the effects of estrogen. In the central nervous system, estrogen influences pain transmission, headache, dizziness, nausea, and depression, all of which are known to be a consequence of serotonergic signaling. Outside of the central nervous system, estrogen produces changes in bone density, vascular function, and immune cell self-recognition and activation that are consistent with serotonin's effects. For breast cancer risk, our hypothesis predicts heretofore unexplained observations of the opposing effects of obesity pre- and post-menopause and the increase following treatment with hormone replacement therapy using medroxyprogesterone. SUMMARY: Serotonergic mediation of estrogen has important clinical implications and warrants further evaluation