A PCP Pincer Ligand for Coordination Polymers with Versatile Chemical Reactivity: Selective Activation of CO2 Gas over CO Gas in the Solid State

A tetra(carboxylated) PCP pincer ligand has been synthesized as a building block for porous coordination polymers (PCPs). The air- and moisture-stable PCP metalloligands are rigid tetratopic linkers that are geometrically akin to ligands used in the synthesis of robust metal-organic frameworks (MOFs). Here, the design principle is demonstrated by cyclometalation with Pd(II) Cl and subsequent use of the metalloligand to prepare a crystalline 3D MOF by direct reaction with Co(II) ions and structural resolution by single crystal X-ray diffraction. The Pd-Cl groups inside the pores are accessible to post-synthetic modifications that facilitate chemical reactions previously unobserved in MOFs: a Pd-CH3 activated material undergoes rapid insertion of CO2 gas to give Pd-OC(O)CH3 at 1 atm and 298 K. However, since the material is highly selective for the adsorption of CO2 over CO, a Pd-N3 modified version resists CO insertion under the same conditions

Reducing emissions in London schools with photovoltaics

This paper examines the potential for PV to improve the performance of primary schools in London. Disaggregate data including energy use is compared with modelled PV generation, showing that electricity demand could theoretically be met in 59% of the schools investigated. The impact of several key factors is then considered, including architectural heritage, building age and form. The results show that the greatest PV potential exists in newer schools, as well as those that are shorter and with less dense forms

CPT and Lorentz-invariance violation

The largest gap in our understanding of nature at the fundamental level is perhaps a unified description of gravity and quantum theory. Although there are currently a variety of theoretical approaches to this question, experimental research in this field is inhibited by the expected Planck-scale suppression of quantum-gravity effects. However, the breakdown of spacetime symmetries has recently been identified as a promising signal in this context: a number of models for underlying physics can accommodate minuscule Lorentz and CPT violation, and such effects are amenable to ultrahigh-precision tests. This presentation will give an overview of the subject. Topics such as motivations, the SME test framework, mechanisms for relativity breakdown, and experimental tests will be reviewed. Emphasis is given to observations involving antimatter.Comment: 6 page

Conformational effects on the Circular Dichroism of Human Carbonic Anhydrase II: a multilevel computational study

Circular Dichroism (CD) spectroscopy is a powerful method for investigating conformational changes in proteins and therefore has numerous applications in structural and molecular biology. Here a computational investigation of the CD spectrum of the Human Carbonic Anhydrase II (HCAII), with main focus on the near-UV CD spectra of the wild-type enzyme and it seven tryptophan mutant forms, is presented and compared to experimental studies. Multilevel computational methods (Molecular Dynamics, Semiempirical Quantum Mechanics, Time-Dependent Density Functional Theory) were applied in order to gain insight into the mechanisms of interaction between the aromatic chromophores within the protein environment and understand how the conformational flexibility of the protein influences these mechanisms. The analysis suggests that combining CD semi empirical calculations, crystal structures and molecular dynamics (MD) could help in achieving a better agreement between the computed and experimental protein spectra and provide some unique insight into the dynamic nature of the mechanisms of chromophore interactions

Suitability of 210Pbex, 137Cs and 239+240Pu as soil erosion tracers in western Kenya

Land degradation resulting from soil erosion is a global concern, with the greatest risk in developing countries where food and land resources can be limited. The use of fallout radionuclides (FRNs) is a proven method for determining short and medium-term rates of soil erosion, to help improve our understanding of soil erosion processes. There has been limited use of these methods in tropical Africa due to the analytical challenges associated with 137Cs, where inventories are an order of magnitude lower than in the Europe. This research aimed to demonstrate the usability of 239+240Pu as a soil erosion tracer in western Kenya compared to conventional isotopes 210Pbex and 137Cs through the determination of FRN depth profiles at reference sites. Across six reference sites 239+240Pu showed the greatest potential, with the lowest coefficient of variation and the greatest peak-to-detection limit ratio of 640 compared to 5 and 1 for 210Pbex and 137Cs respectively. Additionally, 239+240Pu was the only radionuclide to meet the 'allowable error' threshold, demonstrating applicability to large scale studies in Western Kenya where the selection of suitable reference sites presents a significant challenge. The depth profile of 239+240Pu followed a polynomial function, with the maximum areal activities found between depths 3 and 12 cm, where thereafter areal activities decreased exponentially. As a result, 239+240Pu is presented as a robust tracer to evaluate soil erosion patterns and amounts in western Kenya, providing a powerful tool to inform and validate mitigation strategies with improved understanding of land degradation

90,000 year-old specialised bone technology in the Aterian Middle Stone Age of North Africa

The question of cognitive complexity in early Homo sapiens in North Africa is intimately tied to the emergence of the Aterian culture (~145 ka). One of the diagnostic indicators of cognitive complexity is the presence of specialised bone tools, however significant uncertainty remains over the manufacture and use of these artefacts within the Aterian techno-complex. In this paper we report on a bone artefact from Aterian Middle Stone Age (MSA) deposits in Dar es-Soltan 1 cave on the Atlantic coast of Morocco. It comes from a layer that can be securely dated to ~90 ka. The typological characteristics of this tool, which suggest its manufacture and use as a bone knife, are comparatively similar to other bone artefacts from dated Aterian levels at the nearby site of El Mnasra and significantly different from any other African MSA bone technology. The new find from Dar es-Soltan 1 cave combined with those from El Mnasra suggest the development of a bone technology unique to the Aterian

On the conservation of the slow conformational dynamics within the amino acid kinase family: NAGK the paradigm

N-Acetyl-L-Glutamate Kinase (NAGK) is the structural paradigm for examining the catalytic mechanisms and dynamics of amino acid kinase family members. Given that the slow conformational dynamics of the NAGK (at the microseconds time scale or slower) may be rate-limiting, it is of importance to assess the mechanisms of the most cooperative modes of motion intrinsically accessible to this enzyme. Here, we present the results from normal mode analysis using an elastic network model representation, which shows that the conformational mechanisms for substrate binding by NAGK strongly correlate with the intrinsic dynamics of the enzyme in the unbound form. We further analyzed the potential mechanisms of allosteric signalling within NAGK using a Markov model for network communication. Comparative analysis of the dynamics of family members strongly suggests that the low-frequency modes of motion and the associated intramolecular couplings that establish signal transduction are highly conserved among family members, in support of the paradigm sequence→structure→dynamics→function © 2010 Marcos et al

Dietary Supplementation with Soluble Plantain Non-Starch Polysaccharides Inhibits Intestinal Invasion of Salmonella Typhimurium in the Chicken

Soluble fibres (non-starch polysaccharides, NSP) from edible plants but particularly plantain banana (Musa spp.), have been shown in vitro and ex vivo to prevent various enteric pathogens from adhering to, or translocating across, the human intestinal epithelium, a property that we have termed contrabiotic. Here we report that dietary plantain fibre prevents invasion of the chicken intestinal mucosa by Salmonella. In vivo experiments were performed with chicks fed from hatch on a pellet diet containing soluble plantain NSP (0 to 200 mg/d) and orally infected with S.Typhimurium 4/74 at 8 d of age. Birds were sacrificed 3, 6 and 10 d post-infection. Bacteria were enumerated from liver, spleen and caecal contents. In vitro studies were performed using chicken caecal crypts and porcine intestinal epithelial cells infected with Salmonella enterica serovars following pre-treatment separately with soluble plantain NSP and acidic or neutral polysaccharide fractions of plantain NSP, each compared with saline vehicle. Bacterial adherence and invasion were assessed by gentamicin protection assay. In vivo dietary supplementation with plantain NSP 50 mg/d reduced invasion by S.Typhimurium, as reflected by viable bacterial counts from splenic tissue, by 98.9% (95% CI, 98.1–99.7; P<0.0001). In vitro studies confirmed that plantain NSP (5–10 mg/ml) inhibited adhesion of S.Typhimurium 4/74 to a porcine epithelial cell-line (73% mean inhibition (95% CI, 64–81); P<0.001) and to primary chick caecal crypts (82% mean inhibition (95% CI, 75–90); P<0.001). Adherence inhibition was shown to be mediated via an effect on the epithelial cells and Ussing chamber experiments with ex-vivo human ileal mucosa showed that this effect was associated with increased short circuit current but no change in electrical resistance. The inhibitory activity of plantain NSP lay mainly within the acidic/pectic (homogalacturonan-rich) component. Supplementation of chick feed with plantain NSP was well tolerated and shows promise as a simple approach for reducing invasive salmonellosis

Education can improve the negative perception of a threatened long-lived scavenging bird, the Andean condor

Human-wildlife conflicts currently represent one of the main conservation problems for wildlife species around the world. Vultures have serious conservation concerns, many of which are related to people's adverse perception about them due to the belief that they prey on livestock. Our aim was to assess local perception and the factors influencing people's perception of the largest scavenging bird in South America, the Andean condor. For this, we interviewed 112 people from Valle Fértil, San Juan province, a rural area of central west Argentina. Overall, people in the area mostly have an elementary education, and their most important activity is livestock rearing. The results showed that, in general, most people perceive the Andean condor as an injurious species and, in fact, some people recognize that they still kill condors. We identified two major factors that affect this perception, the education level of villagers and their relationship with livestock ranching. Our study suggests that conservation of condors and other similar scavengers depends on education programs designed to change the negative perception people have about them. Such programs should be particularly focused on ranchers since they are the ones who have the worst perception of these scavengers. We suggest that highlighting the central ecological role of scavengers and recovering their cultural value would be fundamental to reverse their persecution and their negative perception by people.Fil: Cailly Arnulphi, Verónica Beatríz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Juan. Centro de Investigaciones de la Geosfera y Biosfera. Universidad Nacional de San Juan. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones de la Geosfera y Biosfera; ArgentinaFil: Lambertucci, Sergio Agustin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte. Instituto de Investigaciones en Biodiversidad y Medioambiente. Universidad Nacional del Comahue. Centro Regional Universidad Bariloche. Instituto de Investigaciones en Biodiversidad y Medioambiente; ArgentinaFil: Borghi, Carlos Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Juan. Centro de Investigaciones de la Geosfera y Biosfera. Universidad Nacional de San Juan. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones de la Geosfera y Biosfera; Argentin