377 research outputs found

    Regioselective formation of\ud [2-(η5-cyclopentadienyl)-2-fluorenylpropane]-titanium complexes:\ud precursors, synthesis, structure and reactivity

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    The 2-cyclopentadienyl-2-fluorenylpropane ligand has been converted into the monometalated derivatives M[CMe2(C5H4)(C13H9)] (M=Li, Tl,) and CMe2[C5H4(SiMe3)](C13H9). These alkylating reagents have been characterized, and used to synthesize a new series of organotitanium (IV) complexes. The trimethylsilyl derivative was treated with TiCl4 to give the monocyclopentadienyl compound [Ti{CMe2(η5-C5H4)(C13H9)}Cl3]. Reaction of the thallium derivative with [Ti(η5-C5R5)Cl3] afforded the ‘mixed-ring’ dicyclopentadienyl complexes [Ti{CMe2(η5-C5H4)(C13H9)}(η5-C5R5)Cl2] (R=H, Me), whereas the reaction of TiCl4 with two equivalents of the lithium compound led to the dicyclopentadienyl complex [Ti{CMe2(η5-C5H4)(C13H9)}2Cl2]. The monocyclopentadienyl compound [Ti{CMe2(η5-C5H4)(C13H9)}Cl3] was readily hydrolyzed to give [Ti{CMe2(η5-C5H4)(C13H9)}Cl2]2(μ-O) in wet acetone (0.5% H2O). The dicyclopentadienyl derivative [Ti{CMe2(η5-C5H4)(C13H9)}(η5-C5Me5)Cl2] was further converted into [Ti{CMe2(η5-C5H4)(C13H9)}(η5-C5Me5)Me2] by alkylation with LiMe. Structural data of the titanium complexes demonstrate the η5-coordination of the cyclopentadienyl ring of the ancillary ligand, whereas the fluorenyl ring is not coordinated to the metal center. This mode of coordination is confirmed by the X-ray crystal structure analysis of [Ti{CMe2(η5-C5H4)(C13H9)}2Cl2]

    Microbial aetiology of healthcare associated pneumonia in Spain: a prospective, multicentre, case-control study

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    Introduction: Healthcare-associated pneumonia (HCAP) is actually considered a subgroup of hospital-acquired pneumonia due to the reported high risk of multidrug-resistant pathogens in the USA. Therefore, current American Thoracic Society/Infectious Diseases Society of America guidelines suggest a nosocomial antibiotic treatment for HCAP. Unfortunately, the scientific evidence supporting this is contradictory. Methods: We conducted a prospective multicentre case-control study in Spain, comparing clinical presentation, outcomes and microbial aetiology of HCAP and community-acquired pneumonia (CAP) patients matched by age (±10 years), gender and period of admission (±10 weeks). Results: 476 patients (238 cases, 238 controls) were recruited for 2 years from June 2008. HCAP cases showed significantly more comorbidities (including dysphagia), higher frequency of previous antibiotic use in the preceding month, higher pneumonia severity score and worse clinical status (Charslon and Barthel scores). While microbial aetiology did not differ between the two groups (HCAP and CAP: Streptococcus pneumoniae: 51% vs 55%; viruses: 22% vs 12%; Legionella: 4% vs 9%; Gram-negative bacilli: 5% vs 4%; Pseudomonas aeruginosa: 4% vs 1%), HCAP patients showed worse mortality rates (1-month: HCAP, 12%; CAP 5%; 1-year: HCAP, 24%; CAP, 9%), length of hospital stay (9 vs 7 days), 1-month treatment failure (5.5% vs 1.5%) and readmission rate (18% vs 11%) (p<0.05, each). Conclusions: Despite a similar clinical presentation, HCAP was more severe due to patients' conditions (comorbidities) and showed worse clinical outcomes. Microbial aetiology of HCAP did not differ from CAP indicating that it is not related to increased mortality and in Spain most HCAP patients do not need nosocomial antibiotic coverage

    Entrepreneurial sons, patriarchy and the Colonels' experiment in Thessaly, rural Greece

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    Existing studies within the field of institutional entrepreneurship explore how entrepreneurs influence change in economic institutions. This paper turns the attention of scholarly inquiry on the antecedents of deinstitutionalization and more specifically, the influence of entrepreneurship in shaping social institutions such as patriarchy. The paper draws from the findings of ethnographic work in two Greek lowland village communities during the military Dictatorship (1967–1974). Paradoxically this era associated with the spread of mechanization, cheap credit, revaluation of labour and clear means-ends relations, signalled entrepreneurial sons’ individuated dissent and activism who were now able to question the Patriarch’s authority, recognize opportunities and act as unintentional agents of deinstitutionalization. A ‘different’ model of institutional change is presented here, where politics intersects with entrepreneurs, in changing social institutions. This model discusses the external drivers of institutional atrophy and how handling dissensus (and its varieties over historical time) is instrumental in enabling institutional entrepreneurship

    Vulnerability to Rainfall-Induced Landslide of Three Communities in Infanta, Quezon, Philippines

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    Four successive tropical cyclones hit the Philippines and brought damages to several towns in the provinces of Quezon and Aurora between November 14 and December 4 in 2004. The municipalities of Infanta, Real, and General Nakar were severely damaged and as a result the communities were exposed to physical risks and experienced socio-economic difficulties. To affect policies and plans in avoiding risks brought about by disasters that may happen in the future, the vulnerabilities to rainfall-induced landslide of the three most devastated barangays in Infanta, Quezon, namely Pinaglapatan, Ilog, and Magsaysay, were determined using an agent-based model. This study determined the vulnerability of three communities based on the framework that vulnerability is influenced by the amount and intensity of rainfall received by the area in a given time, the conditions of the biophysical characteristics of the area, and the socio-economic profile of the community in the area. A time series model to capture the long-term rainfall pattern in the area was developed with consideration to the occurrences of extreme events. Biophysical studies were conducted on the study sites to determine their respective characteristics using topography (slope and elevation), land-use, and soil type as parameters. Through a respondent-type survey, the socio-economic profiles of the communities were characterized using income, livelihood, participation in social networks, and existence of community early warning systems, among others, as parameters. Because of the barangay

    Accelerated inbreeding depression suggests synergistic epistasis for deleterious mutations in Drosophila melanogaster

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    Epistasis may have important consequences for a number of issues in quantitative genetics and evolutionary biology. In particular, synergistic epistasis for deleterious alleles is relevant to the mutation load paradox and the evolution of sex and recombination. Some studies have shown evidence of synergistic epistasis for spontaneous or induced deleterious mutations appearing in mutation-accumulation experiments. However, many newly arising mutations may not actually be segregating in natural populations because of the erasing action of natural selection. A demonstration of synergistic epistasis for naturally segregating alleles can be achieved by means of inbreeding depression studies, as deleterious recessive allelic effects are exposed in inbred lines. Nevertheless, evidence of epistasis from these studies is scarce and controversial. In this paper, we report the results of two independent inbreeding experiments carried out with two different populations of Drosophila melanogaster. The results show a consistent accelerated inbreeding depression for fitness, suggesting synergistic epistasis among deleterious alleles. We also performed computer simulations assuming different possible models of epistasis and mutational parameters for fitness, finding some of them to be compatible with the results observed. Our results suggest that synergistic epistasis for deleterious mutations not only occurs among newly arisen spontaneous or induced mutations, but also among segregating alleles in natural populationsWe acknowledge the support by Uvigo Marine Research Centre funded by the “Excellence in Research (INUGA)” Programme from the Regional Council of Culture, Education and Universities, with co-funding from the European Union through the ERDF Operational Programme Galicia 2014-2020. This work was funded by Agencia Estatal de Investigación (AEI) (CGL2016-75904-C2-1-P), Xunta de Galicia (ED431C 2016-037) and Fondos Feder: “Unha maneira de facer Europa.” SD was founded by a predoctoral (FPI) grant from Ministerio de Economía y Competitividad, SpainS

    CorE from Myxococcus xanthus Is a Copper-Dependent RNA Polymerase Sigma Factor

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    The dual toxicity/essentiality of copper forces cells to maintain a tightly regulated homeostasis for this metal in all living organisms, from bacteria to humans. Consequently, many genes have previously been reported to participate in copper detoxification in bacteria. Myxococcus xanthus, a prokaryote, encodes many proteins involved in copper homeostasis that are differentially regulated by this metal. A σ factor of the ECF (extracytoplasmic function) family, CorE, has been found to regulate the expression of the multicopper oxidase cuoB, the P1B-type ATPases copA and copB, and a gene encoding a protein with a heavy-metal-associated domain. Characterization of CorE has revealed that it requires copper to bind DNA in vitro. Genes regulated by CorE exhibit a characteristic expression profile, with a peak at 2 h after copper addition. Expression rapidly decreases thereafter to basal levels, although the metal is still present in the medium, indicating that the activity of CorE is modulated by a process of activation and inactivation. The use of monovalent and divalent metals to mimic Cu(I) and Cu(II), respectively, and of additives that favor the formation of the two redox states of this metal, has revealed that CorE is activated by Cu(II) and inactivated by Cu(I). The activation/inactivation properties of CorE reside in a Cys-rich domain located at the C terminus of the protein. Point mutations at these residues have allowed the identification of several Cys involved in the activation and inactivation of CorE. Based on these data, along with comparative genomic studies, a new group of ECF σ factors is proposed, which not only clearly differs mechanistically from the other σ factors so far characterized, but also from other metal regulators

    Regulatory Effect of Connexin 43 on Basal Ca2+ Signaling in Rat Ventricular Myocytes

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    Background: It has been found that gap junction-associated intracellular Ca 2+ [Ca 2+]i disturbance contributes to the arrhythmogenesis and hyperconstriction in diseased heart. However, whether functional gaps are also involved in the regulation of normal Ca 2+ signaling, in particular the basal [Ca 2+] i activities, is unclear. Methods and Results: Global and local Ca 2+ signaling and gap permeability were monitored in cultured neonatal rat ventricular myocytes (NRVMs) and freshly isolated mouse ventricular myocytes by Fluo4/AM and Lucifer yellow (LY), respectively. The results showed that inhibition of gap communication by heptanol, Gap 27 and flufenamic acid or interference of connexin 43 (Cx43) with siRNA led to a significant suppression of LY uptake and, importantly, attenuations of global Ca 2+ transients and local Ca 2+ sparks in monolayer NRVMs and Ca 2+ sparks in adult ventricular myocytes. In contrast, overexpression of rat-Cx43 in NRVMs induced enhancements in the above measurements, and so did in HEK293 cells expressing rat Cx43. Additionally, membrane-permeable inositol 1,4,5-trisphosphate (IP3 butyryloxymethyl ester) and phenylephrine, an agonist of adrenergic receptor, could relieve the inhibited Ca 2+ signal and LY uptake by gap uncouplers, whereas blockade of IP 3 receptor with xestospongin C or 2-aminoethoxydiphenylborate mimicked the effects of gap inhibitors. More importantly, all these gap-associated effects on Ca 2+ signaling were also found in single NRVMs that only have hemichannels instead of gap junctions. Further immunostaining/immunoblotting single myocytes with antibod
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