Synthesis and Coordination Chemistry of a New N-4-Polydentate Class of Pyridyl-Functionalized Scorpionate Ligands: Complexes of Fe-II, Zn-II, V-IV, Pd-II and Use for Heterobimetallic Systems

The new potentially N-4-multidentate pyridyl-functionalized scorpionates 4-((tris-2,2,2-(pyrazol-1-ypethoxy)methyl)pyridine (TpmPy, (1)) and 4-((tris-2,2,2-(3-phenylpyrazol-1-yl)ethoxy)methyl)pyridine (TpmPy(Ph), (2)) have been synthesized and their coordination behavior toward Fe-II, Ni-II, Zn-II, Cu-II, Pd-II, and V-III centers has been studied. Reaction of (1) with Fe(BF4)(2)center dot 6H(2)O yields [Fe(TpmPy)(2)](BF4)(2) (3), that, in the solid state, shows the sandwich structure with trihapto ligand coordination via the pyrazolyl arms, and is completely low spin (LS) until 400 K. Reactions of 2 equiv of (1) or (2) with Zn-II or Ni-II chlorides give the corresponding metal complexes with general formula [MCl2(TpmPy*)(2)] (M = Zn, Ni; TpmPy* = TpmPy, TpmPy(Ph)) (4-7) where the ligand is able to coordinate through either the pyrazolyl rings (in case of [Ni(TpmPy)(2)Cl-2 (5)) or the pyridyl-side (for [ZnCl2(TpmPy)(2)] (4), [ZnCl2(TpmPy(Ph))(2)] (6) and [NiCl2(TpmPy(Ph))(2)] (7)). The reaction of (1) with VCl3 gives [VOCl2(TpmPy)] (8) that shows the N-3-pyrazolyl coordination-mode. Moreover, (1) and react with cis-[PdCl2(CH3CN)(2)] to give the disubstituted complexes [PdCl2(TprnPy)(2)] (9) and [PdCl2(TpmPy(Ph))(2)] (10), respectively, bearing the scorpionate coordinated via the pyridyl group. Compounds (9) and (10) react with Fe(BF4)(2) to give the heterobimetallic Pd/Fe systems [PdCl2(mu-TpmPy)(2)-Fe](BF4)(2) (11) and [PdCl2(mu-TpmPy(Ph))(2)Fe-2(H2O)(6)]BF4)(4) (13), respectively. Compound (11) can also be formed from reaction of (3) with cis-[PdCl2(CH3CN)(2)], while reaction of (3) with Cu(NO3)(2).2.5H(2)O generates [Fe(mu-TpmPy)(2)-Cu(NO3)(2)](BF4)(2) (12), confirming the multidentate ability of the new chelating ligands. The X-ray diffraction analyses of compounds (1), (3), (4), (5), and (9) are also reported.

A new A(4) model for lepton mixing

We present a new model of the lepton sector that uses a family symmetry A(4) to make predictions for lepton mixing which are invariant under any permutation of the three flavours. We show that those predictions broadly agree with the experimental data, leading to a largish sin(2)theta(12) greater than or similar to 0.34, to vertical bar cos delta vertical bar greater than or similar to 0.7, and to vertical bar 0.5 - sin(2)theta(23)vertical bar greater than or similar to 0.08; cos delta and 0.5 - sin(2)theta(23) are predicted to have identical signs. (C) 2013 Elsevier B.V. All rights reserved.

Efeitos estruturais e cinéticos de micelas invertidas sobre uma amidase de pseudomonas aeruginosa

No presente trabalho foi executado o encapsulamento de células intactas, extracto celular e amidase purificada (E.C. 3.5.1.4) da estirpe L10 e AI3 de Pseudomonas aeruginosa num sistema de micelas invertidas composto pelo surfactante catiónico brometo de tetradeciltrimetilamónio (TTAB) em heptano/octanol 80/20 (v/v). O efeito do encapsulamento no sistema de micelas invertidas foi estudado avaliando a reacção de transamidação para síntese de ácido acetohidroxâmico, catalisada pela amidase expressa por ambas as estirpes. No sistema de micelas invertidas fez-se variar conteúdo de água (w0) e foi estudado o efeito na actividade enzimática e no rendimento de síntese de acetohidroxamato. Os resultados demonstraram um aumento considerável de actividade específica e do rendimento de síntese no sistema de micelas comparativamente ao meio convencional aquoso, sugerindo que a metodologia de encapsulamento do biocatalisador demonstrou potencialidades de utilização na síntese de hidroxamatos, compostos de elevada importância e aplicabilidade. Na variação do conteúdo de água no sistema micelar obteve-se uma curva em sino de actividade específica e de rendimento, com um pico de actividade para w0 = 10, quer em células intactas, extracto celular e amidase purificada de ambas as estirpes. No caso da Pseudomonas aeruginosa L10 alcançaram-se actividades específicas de 8, 11 e 103 UI/mg de proteína e rendimentos de 94, 99 e 40 % respectivamente para células intactas, extracto celular e amidase purificada. Quanto à Pseudomonas aeruginosa AI3 obtiveram-se, respectivamente, actividades específicas de 5, 9 e 163 UI/ mg de proteína e rendimentos de 66, 66 e 28 % para células intactas, extracto celular e amidase purificada. A estabilidade de armazenamento do biocatalisador no sistema de micelas invertidas e em solução aquosa a 24ºC foi avaliada. Este estudo revelou um aumento do t1/2 no sistema de micelas face ao armazenamento em solução aquosa convencional. No caso da Pseudomonas aeruginosa L10 os melhores resultados foram obtidos para a amidase purificada encapsulada revelando um t1/2 de 17 dias. Quanto ao extracto celular da Pseudomonas aeruginosa AI3 demonstrou um t1/2 de 26 dias quando encapsulado no sistema de micelas. O estudo das alterações estruturais na amidase, de ambas as estirpes, devidas ao encapsulamento em micelas invertidas foi realizado recorrendo à espectroscopia de FTIR. Esta análise permitiu verificar que a amidase AI3 não alterou significativamente a sua estrutura secundária em micelas invertidas para diferentes w0. No entanto, no encapsulamento a sua estrutura secundária sofreu alterações face à estrutura do enzima em solução aquosa. A amidase L10 exibe apenas alterações estruturais face à estrutura que exibe em solução aquosa quando confinada em micelas para w0 3,5 e 4.

Substrate interaction with recombinant amidase from Pseudomonas aeruginosa during biocatalysis

The interaction of a variety of substrates with Pseudomonas aeruginosa native amidase (E.C. 3.5.1.4), overproduced in an Escherichia coli strain, was investigated using difference FTIR spectroscopy. The amides used as substrates showed an increase in hydrogen bonding upon association in multimers, which was not seen with esters. Evidence for an overall reduction or weakening of hydrogen bonding while amide and ester substrates are interacting with the enzyme is presented. The results describe a spectroscopic approach for analysis of substrate-amidase interaction and in situ monitoring of the hydrolysis and transferase reaction when amides or esters are used as substrates.

Pseudomonas aeruginosa amidase: Aggregation in recombinant Escherichia coli

The effect of cultivation parameters such as temperature incubation, IPTG induction and ethanol shock on the production of Pseudomonasaeruginosa amidase (E.C.3.5.1.4) in a recombinant Escherichia coli strain in LB ampicillin culture medium was investigated. The highest yield of solubleamidase, relatively to other proteins, was obtained in the condition at 37 degrees C using 0.40 mM IPTG to induce growth, with ethanol. Our results demonstrate the formation of insoluble aggregates containing amidase, which was biologically active, in all tested growth conditions. Addition of ethanol at 25 degrees C in the culture medium improved amidase yield, which quantitatively aggregated in a biologically active form and exhibited in all conditions an increased specific activity relatively to the soluble form of the enzyme. Non-denaturing solubilization of the aggregated amidase was successfully achieved using L-arginine. The aggregates obtained from conditions at 37 degrees C by Furier transform infrared spectroscopy (FTIR) analysis demonstrated a lower content of intermolecular interactions, which facilitated the solubilization step applying non-denaturing conditions. The higher interactions exhibited in aggregates obtained at suboptimal conditions compromised the solubilization yield. This work provides an approach for the characterization and solubilization of novel reported biologically active aggregates of this amidase.

Fungal contamination in swine: a potential occupational health threat

Poor air quality in a pig-confinement building may potentially place farmers at higher health risk than other workers for exposure to airborne pollutants that may reach infectious levels. The aim of this study was to assess worker exposure to fungi in indoor environments in Portuguese swine buildings. Air samples from 7 swine farms were collected at a flow rate of 140 L/min, at 1 m height, onto malt extract agar supplemented with chloramphenicol (MEA). Surfaces samples of the same indoor sites were obtained by swabbing the surfaces. Samples from the floor covering were also collected from four of seven swine farms. All collected samples were incubated at 27°C for 5-7 days. After lab processing and incubation of obtained samples, quantitative colony-forming units (CFU)/m(3), CFU/cm(2), and CFU/g and qualitative results were determined with identification of isolated fungal species. Aspergillus versicolor was the most frequent species found in air (21%), followed by Scopulariopsis brevicaulis (17%) and Penicillium sp. (14%). Aspergillus versicolor was also the most frequent species noted on surfaces (26.6%), followed by Cladosporium sp. (22.4%) and Scopulariopsis brevicaulis (17.5%). Chrysosporium was the most frequently found genera in the new floor covering (38.5%), while Mucor was the most prevalent genera (25.1%) in used floor covering. Our findings corroborate a potential occupational health threat due to fungi exposure and suggest the need for a preventive strategy.

Impact of maritime air mass trajectories on the Western European coast urban aerosol

Lisbon is the largest urban area in the Western European coast. Due to this geographical position the Atlantic Ocean serves as an important source of particles and plays an important role in many atmospheric processes. The main objectives of this study were to (1) perform a chemical characterization of particulate matter (PM2.5) sampled in Lisbon, (2) identify the main sources of particles, (3) determine PM contribution to this urban area, and (4) assess the impact of maritime air mass trajectories on concentration and composition of respirable PM sampled in Lisbon. During 2007, PM2.5 was collected on a daily basis in the center of Lisbon with a Partisol sampler. The exposed Teflon filters were measured by gravimetry and cut into two parts: one for analysis by instrumental neutron activation analysis (INAA) and the other by ion chromatography (IC). Principal component analysis (PCA) and multilinear regression analysis (MLRA) were used to identify possible sources of PM2.5 and determine mass contribution. Five main groups of sources were identified: secondary aerosols, traffic, calcium, soil, and sea. Four-day backtracking trajectories ending in Lisbon at the starting sampling time were calculated using the HYSPLIT model. Results showed that maritime transport scenarios were frequent. These episodes were characterized by a significant decrease of anthropogenic aerosol concentrations and exerted a significant role on air quality in this urban area.

Impact of Sahara dust transport on Cape Verde atmospheric element particles

The objectives of this study were to (1) conduct an elemental characterization of airborne particles sampled in Cape Verde and (2) assess the influence of Sahara desert on local suspended particles. Particulate matter (PM10) was collected in Praia city (14°94'N; 23°49'W) with a low-volume sampler in order to characterize its chemical composition by k0-INAA. The filter samples were first weighed and subsequently irradiated at the Portuguese Research Reactor. Results showed that PM10 concentrations in Cape Verde markedly exceeded the health-based air quality standards defined by the European Union (EU), World Health Organization (WHO), and U.S. Environmental Protection Agency (EPA), in part due to the influence of Sahara dust transport. The PM10 composition was characterized essentially by high concentrations of elements originating from the soil (K, Sm, Co, Fe, Sc, Rb, Cr, Ce, and Ba) and sea (Na), and low concentrations of anthropogenic elements (As, Zn, and Sb). In addition, the high concentrations of PM measured in Cape Verde suggest that health of the population may be less affected compared with other sites where PM10 concentrations are lower but more enriched with toxic elements.

Occupational exposure to poultry dust and effects on the respiratory system in workers

Farmers are occupationally exposed to many respiratory hazards at work and display higher rates of asthma and respiratory symptoms than other workers. Dust is one of the components present in poultry production that increases risk of adverse respiratory disease occurrence. Dust originates from poultry residues, molds, and feathers and is biologically active as it contains microorganisms. Exposure to dust is known to produce a variety of clinical responses, including asthma, chronic bronchitis, chronic airways obstructive disease (COPD), allergic alveolitis, and organic dust toxic syndrome (ODTS). A study was developed to determine particle contamination in seven poultry farms and correlate this with prevalence rate of respiratory defects and record by means of a questionnaire the presence of clinical symptoms associated with asthma and other allergy diseases by European Community Respiratory Health Survey. Poultry farm dust contamination was found to contain higher concentrations of particulate matter (PM) PM5 and PM10. Prevalence rate of obstructive pulmonary disorders was higher in individuals with longer exposure regardless of smoking status. In addition, a high prevalence for asthmatic (42.5%) and nasal (51.1%) symptoms was noted in poultry workers. Data thus show that poultry farm workers are more prone to suffer from respiratory ailments and this may be attributed to higher concentrations of PM found in the dust. Intervention programs aimed at reducing exposure to dust will ameliorate occupational working conditions and enhance the health of workers.

Prevalência da doença pulmonar obstrutiva crónica em Lisboa, Portugal: estudo burden of obstructive lung disease

Introdução - A prevalência da doença pulmonar obstrutiva crónica (DPOC) apresenta valores muito heterogéneos em todo o mundo. A iniciativa Burden of Obstructive Lung Disease (BOLD) foi desenvolvida para que a prevalência da DPOC possa ser avaliada com metodologia uniformizada. O objetivo deste estudo foi estimar a prevalência da DPOC em adultos com 40 ou mais anos numa população alvo de 2 700 000 habitantes na região de Lisboa, de acordo com o protocolo BOLD. Métodos - A amostra foi estratificada de forma aleatória multifaseada selecionando-se 12 freguesias. O inquérito compreendia um questionário com informação sobre fatores de risco para a DPOC e doença respiratória autoreportada; adicionalmente, foi efetuada espirometria com prova de broncodilatação. Resultados - Foram incluídos 710 participantes com questionário e espirometria aceitáveis. A prevalência estimada da DPOC na população no estadio GOLD I+ foi de 14,2% (IC 95%: 11,1; 18,1) e de 7,3% no estadio ii+ (IC 95%: 4,7; 11,3). A prevalência não ajustada foi de 20,2% (IC 95%: 17,4; 23,3) no estadio i+ e de 9,5% (IC 95%: 7,6; 11,9) no estadio ii+. A prevalência da DPOC no estadio GOLD II+ aumentou com a idade, sendo mais elevada no sexo masculino. A prevalência estimada da DPOC no estadio GOLD I+ foi de 9,2% (IC 95%: 5,9; 14,0) nos não fumadores versus 27,4% (IC 95%: 18,5; 38,5) nos fumadores com carga tabágica de ≥ 20 Unidades Maço Ano. Detetou-se uma fraca concordância entre a referência a diagnóstico médico prévio e o diagnóstico espirométrico, com 86,8% de subdiagnósticos. Conclusões - O achado de uma prevalência estimada da DPOC de 14,2% sugere que esta é uma doença comum na região de Lisboa, contudo com uma elevada proporção de subdiagnósticos. Estes dados apontam para a necessidade de aumentar o grau de conhecimento dos profissionais de saúde sobre a DPOC, bem como a necessidade de maior utilização da espirometria nos cuidados de saúde primários.

EVIV: An end-to-end verifiable Internet voting system

Traditionally, a country's electoral system requires the voter to vote at a specific day and place, which conflicts with the mobility usually seen in modern live styles. Thus, the widespread of Internet (mobile) broadband access can be seen as an opportunity to deal with this mobility problem, i.e. the adoption of an Internet voting system can make the live of voter's much more convenient; however, a widespread Internet voting systems adoption relies on the ability to develop trustworthy systems, i.e. systems that are verifiable and preserve the voter's privacy. Building such a system is still an open research problem. Our contribution is a new Internet voting system: EVIV, a highly sound End-to-end Verifiable Internet Voting system, which offers full voter's mobility and preserves the voter's privacy from the vote casting PC even if the voter votes from a public PC, such as a PC at a cybercafe or at a public library. Additionally, EVIV has private vote verification mechanisms, in which the voter just has to perform a simple match of two small strings (4-5 alphanumeric characters), that detect and protect against vote manipulations both at the insecure vote client platform and at the election server side. (c) 2012 Elsevier Ltd. All rights reserved.

Hexanuclear and undecanuclear iron(III) carboxylates as catalyst precursors for cyclohexane oxidation

Two multinuclear complexes [Fe-6(mu(3)-O)(2)(mu(4)-O-2)L-10(OAc)(2)(H2O)(2)]center dot 2.625Et(2)O center dot 2.375H(2)O (1) and [(Fe11Cl)-Cl-III-(mu(4)-O)(3)(mu(3)-O)(5)L-16(dmf)(2.5)(H2O)(0.5)]center dot Et2O center dot 1.25dmf center dot 3.8H(2)O (2), where HL = 3,4,5-trimethoxybenzoic acid and dmf = dimethylformamide, have been prepared from trinuclear iron(III) carboxylates via their structural rearrangement in dimethylformamide or diethyl ether-dimethylformamide 9:1, respectively, and slow vapor diffusion of diethyl ether into the reaction mixture. Both compounds have been characterized by X-ray diffraction, optical, Mossbauer spectroscopy, and magnetic measurements. Complex 1 possesses a hexanuclear ferric peroxido-dioxido {Fe-6(O-2)(O)(2)}(12+) core unit, which adopts a recliner conformation, while complex 2 contains an unprecedented {Fe11O8Cl}(16+) core, in which 9 ferric ions are six-coordinate and the remaining two are five-coordinate. Another structural feature of note of the undecanuclear core is the presence of a deformed cubane entity {Fe-4(mu(3)-O)(mu(4)-O)(3)}(4+). Both complexes act as catalyst precursors for the oxidation of cyclohexane to cyclohexanol and cyclohexanone with aqueous H2O2, in the presence of pyrazinecarboxylic acid. Remarkable TONs and TOFs (the latter mainly for 1) with concomitant quite good yields have been achieved under mild conditions. Moreover, 1 exhibits remarkably high activity in an exceptionally short reaction time (45 min), being unprecedented for any metal catalyzed alkane oxidation by H2O2. The catalytic reactions proceed via Fenton type chemistry.

Monte Carlo simulation of the basic features of the GE Millennium MG single photon emission computed tomography gamma camera

Objective - To describe and validate the simulation of the basic features of GE Millennium MG gamma camera using the GATE Monte Carlo platform. Material and methods - Crystal size and thickness, parallel-hole collimation and a realistic energy acquisition window were simulated in the GATE platform. GATE results were compared to experimental data in the following imaging conditions: a point source of 99mTc at different positions during static imaging and tomographic acquisitions using two different energy windows. The accuracy between the events expected and detected by simulation was obtained with the Mann–Whitney–Wilcoxon test. Comparisons were made regarding the measurement of sensitivity and spatial resolution, static and tomographic. Simulated and experimental spatial resolutions for tomographic data were compared with the Kruskal–Wallis test to assess simulation accuracy for this parameter. Results - There was good agreement between simulated and experimental data. The number of decays expected when compared with the number of decays registered, showed small deviation (≤0.007%). The sensitivity comparisons between static acquisitions for different distances from source to collimator (1, 5, 10, 20, 30cm) with energy windows of 126–154 keV and 130–158 keV showed differences of 4.4%, 5.5%, 4.2%, 5.5%, 4.5% and 5.4%, 6.3%, 6.3%, 5.8%, 5.3%, respectively. For the tomographic acquisitions, the mean differences were 7.5% and 9.8% for the energy window 126–154 keV and 130–158 keV. Comparison of simulated and experimental spatial resolutions for tomographic data showed no statistically significant differences with 95% confidence interval. Conclusions - Adequate simulation of the system basic features using GATE Monte Carlo simulation platform was achieved and validated.

OsRMC, a negative regulator of salt stress response in rice, is regulated by two AP2/ERF transcription factors

High salinity causes remarkable losses in rice productivity worldwide mainly because it inhibits growth and reduces grain yield. To cope with environmental changes, plants evolved several adaptive mechanisms, which involve the regulation of many stress-responsive genes. Among these, we have chosen OsRMC to study its transcriptional regulation in rice seedlings subjected to high salinity. Its transcription was highly induced by salt treatment and showed a stress-dose-dependent pattern. OsRMC encodes a receptor-like kinase described as a negative regulator of salt stress responses in rice. To investigate how OsRMC is regulated in response to high salinity, a salt-induced rice cDNA expression library was constructed and subsequently screened using the yeast one-hybrid system and the OsRMC promoter as bait. Thereby, two transcription factors (TFs), OsEREBP1 and OsEREBP2, belonging to the AP2/ERF family were identified. Both TFs were shown to bind to the same GCC-like DNA motif in OsRMC promoter and to negatively regulate its gene expression. The identified TFs were characterized regarding their gene expression under different abiotic stress conditions. This study revealed that OsEREBP1 transcript level is not significantly affected by salt, ABA or severe cold (5 °C) and is only slightly regulated by drought and moderate cold. On the other hand, the OsEREBP2 transcript level increased after cold, ABA, drought and high salinity treatments, indicating that OsEREBP2 may play a central role mediating the response to different abiotic stresses. Gene expression analysis in rice varieties with contrasting salt tolerance further suggests that OsEREBP2 is involved in salt stress response in rice.

Quality assurance and quality control in mammography: a review of available guidance worldwide

Objectives - Review available guidance for quality assurance (QA) in mammography and discuss its contribution to harmonise practices worldwide. Methods - Literature search was performed on different sources to identify guidance documents for QA in mammography available worldwide in international bodies, healthcare providers, professional/scientific associations. The guidance documents identified were reviewed and a selection was compared for type of guidance (clinical/technical), technology and proposed QA methodologies focusing on dose and image quality (IQ) performance assessment. Results - Fourteen protocols (targeted at conventional and digital mammography) were reviewed. All included recommendations for testing acquisition, processing and display systems associated with mammographic equipment. All guidance reviewed highlighted the importance of dose assessment and testing the Automatic Exposure Control (AEC) system. Recommended tests for assessment of IQ showed variations in the proposed methodologies. Recommended testing focused on assessment of low-contrast detection, spatial resolution and noise. QC of image display is recommended following the American Association of Physicists in Medicine guidelines. Conclusions - The existing QA guidance for mammography is derived from key documents (American College of Radiology and European Union guidelines) and proposes similar tests despite the variations in detail and methodologies. Studies reported on QA data should provide detail on experimental technique to allow robust data comparison. Countries aiming to implement a mammography/QA program may select/prioritise the tests depending on available technology and resources.