Mechanistic Aspects for the Formation of Copper Dimer Bridged by Phosphonic Acid and Extending Its Dimensionality by Organic and Inorganic Linkers: Synthesis, Structural Characterization, Magnetic Properties, and Theoretical Studies

Six new copper metal complexes with formulas Cu(H2O)(2,2'-bpy) (H2L)](2) center dot H4L center dot 4 H2O (1), {Cu(H2O)(2,2'-bpy)-(H3L)}(2)(H2L)]center dot 2H(2)O (2), Cu(H2O)(1,10-phen)(H2L)](2)center dot 6H(2)O (3), Cu(2,2'-bpy)(H2L)](n)center dot nH(2)O (4), Cu(1,10-phen)(H2L)](n)center dot 3nH(2)O (5), and {Cu(2,2'-bpy)(MoO3)}(2)(L)](n)center dot 2nH(2)O (6) have been synthesized starting from p-xylylenediphosphonic acid (H4L) and 2,2'-bipyridine (2,2'-bpy) or 1,10-phenanthroline (1,10-phen) as secondary linkers and characterized by single crystal X-ray diffraction analysis, IR spectroscopy, and thermogravimetric (TG) analysis. All the complexes were synthesized by hydrothermal methods. A dinuclear motif (Cu-dimer) bridged by phosphonic acid represents a new class of simple building unit (SBU) in the construction of coordination architectures in metal phosphonate chemistry. The initial pH of the reaction mixture induced by the secondary linker plays an important role in the formation of the molecular phosphonates 1, 2, and 3. Temperature dependent hydrothermal synthesis of the compounds 1, 2, and 3 reveals the mechanism of the self assembly of the compounds based on the solubility of the phosphonic acid H4L. Two-dimensional coordination polymers 4, 5, and 6, which are formed by increasing the pH of the reaction mixture, comprise Cu-dimers as nodes, organic (H2L) and inorganic (Mo4O12) ligands as linkers. The void space-areas, created by the (4,4) connected nets in compounds 4 and 5, are occupied by lattice water molecules. Thus compounds 4 and 5 have the potential to accommodate guest species/molecules. Variable temperature magnetic studies of the compounds 3, 4, 5, and 6 reveal the antiferromagnetic interactions between the two Cu(II) ions in the eight membered ring, observed in their crystal structures. A density functional theory (DFT) calculation correlates the conformation of the Cu-dimer ring with the magnitude of the exchange parameter based on the torsion angle of the conformation.

Role of different factors affecting interdiffusion in Cu(Ga) and Cu(Si) solid solutions

A detailed diffusion study was carried out on Cu(Ga) and Cu(Si) solid solutions in order to assess the role of different factors in the behaviour of the diffusing components. The faster diffusing species in the two systems, interdiffusion, intrinsic and impurity diffusion coefficients, are determined to facilitate the discussion. It was found that Cu was more mobile in the Cu-Si system, whereas Ga was the faster diffusing species in the Cu-Ga system. In both systems, the interdiffusion coefficients increased with increasing amount of solute (e.g. Si or Ga) in the matrix (Cu). Impurity diffusion coefficients for Si and Ga in Cu, found out by extrapolating interdiffusion coefficient data to zero composition of the solute, were both higher than the Cu tracer diffusion coefficient. These observed trends in diffusion behaviour could be rationalized by considering: (i) formation energies and concentration of vacancies, (ii) elastic moduli (indicating bond strengths) of the elements and (iii) the interaction parameters and the related thermodynamic factors. In summary, we have shown here that all the factors introduced in this paper should be considered simultaneously to understand interdiffusion in solid solutions. Otherwise, some of the aspects may look unusual or even impossible to explain.

Role of electrical resistance of electrodes in modeling of discharging and charging of flooded lead-acid batteries

Electrical resistance of both the electrodes of a lead-acid battery increases during discharge due to formation of lead sulfate, an insulator. Work of Metzendorf 1] shows that resistance increases sharply at about 65% conversion of active materials, and battery stops discharging once this critical conversion is reached. However, these aspects are not incorporated into existing mathematical models. Present work uses the results of Metzendorf 1], and develops a model that includes the effect of variable resistance. Further, it uses a reasonable expression to account for the decrease in active area during discharge instead of the empirical equations of previous work. The model's predictions are compared with observations of Cugnet et al. 2]. The model is as successful as the non-mechanistic models existing in literature. Inclusion of variation in resistance of electrodes in the model is important if one of the electrodes is a limiting reactant. If active materials are stoichiometrically balanced, resistance of electrodes can be very large at the end of discharge but has only a minor effect on charging of batteries. The model points to the significance of electrical conductivity of electrodes in the charging of deep discharged batteries. (C) 2014 Elsevier B.V. All rights reserved.

Role of upward leaders in modifying the induced currents in solitary down-conductors during a nearby lightning strike to ground

Electromagnetic field produced by a lightning strike to ground causes significant induction to tall objects in the vicinity. The frequency of occurrence of such nearby ground strikes can be higher than the number of direct strikes. Therefore, a complete knowledge on these induced currents is of practical relevance. However, limited efforts towards the characterisation of such induced currents in tall down-conductors could be seen in the literature. Due to the intensification of the background field caused by the descending stepped leader, tall towers/down-conductors can launch upward leaders of significant length. The nonlinearity in the conductance of upward leader and the surrounding corona sheath can alter the characteristics of the induced currents. Preliminary aspects of this phenomenon have been studied by the author previously and the present work aims to perform a detailed investigation on the role of upward leaders in modifying the characteristics of the induced currents. A consistent model for the upward leader, which covers all the essential electrical aspects of the phenomena, is employed. A first order arc model for representing the conductance of upward leader and a field dependant quadratic conductivity model for the corona sheath is employed. The initial gradient in the upward leader and the field produced by the return stroke forms the excitation. The dynamic electromagnetic response is determined by solving the wave equation using thin-wire time-domain formulation. Simulations are carried out initially to ascertain the role of individual parameters, including the length of the upward leader. Based on the simulation results, it is shown that the upward leader enhances the induced current, and when significant in length, can alter the waveshape of induced current from bipolar oscillatory to unipolar. The duration of the induced current is governed by the length of upward leader, which in turn is dependant on the return stroke current and the effective length of the down-conductor. If the current during the upward leader developmental phase is considered along with that after the stroke termination to ground, it would present a bipolar current pulse. (C) 2015 Elsevier Ltd. All rights reserved.

The putative role of some conserved water molecules in the structure and function of human transthyretin

Human transthyretin (hTTR) is a multifunctional protein that is involved in several neurodegenerative diseases. Besides the transportation of thyroxin and vitamin A, it is also involved in the proteolysis of apolipoprotein A1 and A beta peptide. Extensive analyses of 32 high-resolution X-ray and neutron diffraction structures of hTTR followed by molecular-dynamics simulation studies using a set of 15 selected structures affirmed the presence of 44 conserved water molecules in its dimeric structure. They are found to play several important roles in the structure and function of the protein. Eight water molecules stabilize the dimeric structure through an extensive hydrogen-bonding network. The absence of some of these water molecules in highly acidic conditions (pH <= 4.0) severely affects the interfacial hydrogen-bond network, which may destabilize the native tetrameric structure, leading to its dissociation. Three pairs of conserved water molecules contribute to maintaining the geometry of the ligand-binding cavities. Some other water molecules control the orientation and dynamics of different structural elements of hTTR. This systematic study of the location, absence, networking and interactions of the conserved water molecules may shed some light on various structural and functional aspects of the protein. The present study may also provide some rational clues about the conserved water-mediated architecture and stability of hTTR.

The role of androgens in fetal growth: observational study in two genetic models of disordered androgen signalling.

OBJECTIVE: To examine the role of androgens on birth weight in genetic models of altered androgen signalling. SETTING: Cambridge Disorders of Sex Development (DSD) database and the Swedish national screening programme for congenital adrenal hyperplasia (CAH). PATIENTS: (1) 29 girls with XY karyotype and mutation positive complete androgen insensitivity syndrome (CAIS); (2) 43 girls and 30 boys with genotype confirmed CAH. MAIN OUTCOME MEASURES: Birth weight, birth weight-for-gestational-age (birth weight standard deviation score (SDS)) calculated by comparison with national references. RESULTS: Mean birth weight SDS in CAIS XY infants was higher than the reference for girls (mean, 95% CI: 0.4, 0.1 to 0.7; p=0.02) and was similar to the national reference for boys (0.1, -0.2 to 0.4). Birth weight SDS in CAH girls was similar to the national reference for girls (0.0, -0.2 to 0.2) and did not vary by severity of gene mutation. Birth weight SDS in CAH boys was also similar to the national reference for boys (0.2, -0.2 to 0.6). CONCLUSION: CAIS XY infants have a birth weight distribution similar to normal male infants and birth weight is not increased in infants with CAH. Alterations in androgen signalling have little impact on birth weight. Sex dimorphism in birth size is unrelated to prenatal androgen exposure.

La calidad de vida y salud desde una antropología cristiana

Resumen: Este trabajo examina con atento discernimiento los términos “calidad de vida” y “promoción de la salud” que identifican uno de los principales objetivos de las sociedades contemporáneas. En el mismo se cita la encíclica Evangelium vitae que dice “La llamada ‘calidad de vida’ se interpreta principal o exclusivamente como eficiencia económica, consumismo desordenado, belleza y goce de la vida física, olvidando las dimensiones más profundas -relacionales, espirituales y religiosas- de la existencia” (n. 23). Todas las dimensiones de la persona -la corpórea, la psicológica, la espiritual y la moral- han de promoverse en armonía. Esto supone la presencia de condiciones sociales y ambientales aptas para favorecer ese desarrollo armonioso. En la actualidad la expresión “calidad de vida” no está fundada en una antropología filosófica y teológica, favoreciendo una noción restrictiva y selectiva. En referencia al concepto de salud también ha sufrido una desviación análoga. Se debe proteger y cuidar la salud como equilibrio físico, psíquico y espiritual del ser humano. Se analiza, asimismo, el concepto de “bien común” en relación a la sociedad, la democracia y el trabajo de la política en la construcción del mismo. En el texto se discute sobre la priorización de intervenciones de salud y se presentan posibles respuestas. Se muestran criterios de decisión al momento de distribuir recursos entre las distintas necesidades de salud, buscando definir principios éticos relevantes para una priorización de intervenciones.

Basque nominalizations and the role of structural Case in the licensing of null arguments

[EN] This article investigates the question of the licensing of null arguments in the so-called pro-drop languages. By focusing on the licensing of null subjects in the different types of -T(Z)E nominalizations in Basque, it aims at defining in a precise way the crucial feature that makes pro-drop possible in a clause. The central claim is that what licenses subject-drop is the assignment of structural Case. That is, it is argued that a subject can be null if and only if it is assigned structural Case. Different aspects of T(Z)E nominalizations are also explored, which show that even if these clauses are similar in the surface, they can be syntactically very different and furthermore, that infinitive clauses marked with the same nominalizing morpheme can also have diverging structures.

Some aspects of the ecology of the leatherback turtle Dermochelys coriacea at Laguna Jalova, Costa Rica

The ecology and reproductive biology of the leatherback turtle (Dennochelys coriacea) was studied on a high-energy nesting beach near Laguna Jalova, Costa Rica, between 28 March and 8 June 1985. The peak of nesting was between 15 April and 21 May. Leatherbacks here measured an average 146.6 cm straightline standard carapace length and laid an average 81.57 eggs. The eggs measured a mean 52.12 mm diameter and weighed an average of 85.01 g. Significant positive relationships were found between the carapace lengths of nesters and their clutch sizes and average diameter and weight of eggs. The total clutch weighed between 4.02 and 13.39 kg, and yolkless eggs accounted for an average 12.4% of this weight. The majority of nesters dug shallow (<24 cm) body pits and spent an average 81 minutes at the nest site. A significant number of c1utcbes were laid below the berm crest. In a hatchery 42.2% of the eggs hatched, while in natural nests 70.2% hatched. The average hatchling carapace length was 59.8 mm and weight was 44.6 g. The longevity of leatherback tracks and nests on the beach was affected by weather. One nester was recaptured about one year later off the coast of Mississippi, U.S.A. Egg poaching was intense on some sections of the Costa Rican coast. Four aerial surveys in four different months provided the basis for comparing density of nesting on seven sectors of the Caribbean coast of Costa Rica. The beach at Jalova is heavily used by green turtles (Chelonia mydJJs) after the leatherback nesting season. The role of the Parque Nacional Tortuguero in conserving the leatherback and green turtle is discussed.(PDF file contains 20 pages.)

Nourriture et santé dans la médecine grecque ancienne

Presentado en el IIe Colloque International de l'IEHA: « Un aliment sain dans un corps sain ». Perspectives historiques - «Healthy Food in a Healthy Body», organizado por el Institut Européen d'Histoire de l'Alimentation y celebrado en Tours los días 14 y 15 de diciembre de 2002.

On innate and specific aspects of human language

Mixel Aurnague, Kepa Korta and Jesus M. Larrazabal (eds.)

Fundamental aspects of the feeding of the amphipod Gammarus (R.) balcanicus (Crustacea, Amphipoda). [Translation from: Nauchn.Dokl.vyssh.Shkoly (Biol.Nauk) 1970(7) 12-16, 1970]

The amphipods are major food items for many commercial fishes, and they are used as protein food for agricultural animals. In the present paper are presented the results of four-year observations on the feeding of Gammarus balcanicus in nature and in an aquarium. Among the studied aspects were the dependence of daily food ration on sex and physiological state (with and without eggs) and feeding on different kinds of plant food. The study concludes that Gammarus balcanicus willingly feed on soft half-decayed plant residues; into their ration also enters food of animal origin. In contrast to other amphipods, G. balcanicus eats representatives of its own species very rarely, and only dead or immobile ones.

How central are clients in sexual networks created by commercial sex?

Sex workers are traditionally considered important vectors of transmission of sexually transmitted infections (STI). The role of clients is commonly overlooked, partially due to the lack of evidence on clients' position in the sexual network created by commercial sex. Contrasting the diffusion importance of sex workers and their clients in the map of their sexual encounters in two Web-mediated communities, we find that from diffusion perspective, clients are as important as sex workers. Their diffusion importance is closely linked to the geography of the sexual encounters: as a result of different movement patterns, travelling clients shorten network distances between distant network neighborhoods and thus facilitate contagion among them more than sex workers, and find themselves more often in the core of the network by which they could contribute to the persistence of STIs in the community. These findings position clients into the set of the key actors and highlight the role of human mobility in the transmission of STIs in commercial sexual networks.

Teatro sombrio: o demônio em cena nos trópicos: o papel do teatro Anchietano no processo de colonização da América portuguesa no século XVI

O teatro anchietano, que articula a educação, a arte e a religião por meio de um interessante intercâmbio de signos, configurou-se como um dos mais relevantes instrumentos pedagógicos utilizados pela Companhia de Jesus na América Portuguesa durante o século XVI. Suas práticas discursivas acerca do Diabo e de seu séquito infernal tinham por objetivos, a partir da construção de uma pedagogia do medo, a promoção do catolicismo entre os indígenas e a adaptação desses povos à cultura euro-cristã, garantindo, desta forma, a viabilidade da colonização desses domínios ultramarinos pertencentes à coroa portuguesa. O processo de elaboração das representações culturais, característico dos encontros e confrontos entre os mundos europeu e indígena, a gestação de novos modelos de organização social e de valores, por meio do crivo da mestiçagem cultural, serão levados em conta para a análise da ação missionária jesuítica. Na presente dissertação analisaremos esses aspectos tendo por base o Auto de São Lourenço escrito pelo padre José de Anchieta.

Structure-function analysis of USP1: insights into the role of Ser313 phosphorylation site and the effect of cancer-associated mutations on autocleavage

Background: In complex with its cofactor UAF1, the USP1 deubiquitinase plays an important role in cellular processes related to cancer, including the response to DNA damage. The USP1/UAF1 complex is emerging as a novel target in cancer therapy, but several aspects of its function and regulation remain to be further clarified. These include the role of the serine 313 phosphorylation site, the relative contribution of different USP1 sequence motifs to UAF1 binding, and the potential effect of cancer-associated mutations on USP1 regulation by autocleavage. Methods: We have generated a large set of USP1 structural variants, including a catalytically inactive form (C90S), non-phosphorylatable (S313A) and phosphomimetic (S313D) mutants, deletion mutants lacking potential UAF1 binding sites, a mutant (GG/AA) unable to undergo autocleavage at the well-characterized G670/G671 diglycine motif, and four USP1 mutants identified in tumor samples that cluster around this cleavage site (G667A, L669P, K673T and A676T). Using cell-based assays, we have determined the ability of these mutants to bind UAF1, to reverse DNA damage-induced monoubiquitination of PCNA, and to undergo autocleavage. Results: A non-phosphorylatable S313A mutant of USP1 retained the ability to bind UAF1 and to reverse PCNA ubiquitination in cell-based assays. Regardless of the presence of a phosphomimetic S313D mutation, deletion of USP1 fragment 420-520 disrupted UAF1 binding, as determined using a nuclear relocation assay. The UAF1 binding site in a second UAF1-interacting DUB, USP46, was mapped to a region homologous to USP1(420-520). Regarding USP1 autocleavage, co-expression of the C90S and GG/AA mutants did not result in cleavage, while the cancer-associated mutation L669P was found to reduce cleavage efficiency. Conclusions: USP1 phosphorylation at S313 is not critical for PCNA deubiquitination, neither for binding to UAF1 in a cellular environment. In this context, USP1 amino acid motif 420-520 is necessary and sufficient for UAF1 binding. This motif, and a homologous amino acid segment that mediates USP46 binding to UAF1, map to the Fingers sub-domain of these DUBs. On the other hand, our results support the view that USP1 autocleavage may occur in cis, and can be altered by a cancer-associated mutation.