Coinage metals trinuclear metallocycles: old and new aspects of this class of compounds

Coinage metals trinuclear metallocycles: old and new aspects of this class of compounds Galassi R. a, Oumarou C. S. a, Omary A. M. b, Nesterov V. b, Burini A.a aSchool of Science and Technology, Chemistry Division, University of Camerino, Via S. Agostino 1, 62032 Camerino; e-mail: [email protected] b Department of Chemistry, University of North Texas, Denton, 1155 Union Circle, TX 76203, USA; e-mail: [email protected] Azoles such as imidazoles and pyrazoles are optimal bridging ligands to obtain C,N or N,N trinuclear coinage metals metallocycles. Since past decade till now, few worldwide research groups including us have focused their attention to their synthesis and characterization.[1] Moreover, the photophysical properties[2] the extended network of metallophilic bondings in the supramolecular structure and the pi-acid/pi-base chemistry[3] of these compounds directed the research to theoretical studies bringing to a better interpretation of the experimental behaviors.[4] Here we report the synthesis of new coinage metals metallocycles and their spectroscopic characterizations highlighting points of continuity with the previous analogs and new features for new perspective research lines. As in example, the 1-vinylimidazole resembles the acid-base chemistry of the 1-benzylimidazole gold(I) metallocycle, while substitution in position 4,5 of 1-benzylimidazole with electron-withdrawing group, do not allow the formation of metallocycles with the same synthethic route and mononuclear gold(I) derivatives have been obtained. The nature of the heterocycle and of the substituents, in addition to their position in the azolate ligand defines and tunes the properties of the final products. References: 1) Galassi, R.; Burini, A.; Omary-Rawanashed, M., Omary, M. A., Comm. Inorg. Chem. 2014, in submission. 2) Rawashdeh-Omary, M. A.; Omary, M. A.; Fackler Jr, J. P, Galassi R., Pietroni, B. R.; Burini, A. J. Am. Chem. Soc 2001, 123; 9689-9691. 3) Burini, A.;. Fackler Jr, J. P; Galassi R., Grant, T. A.. Omary, M. A; Rawashdeh-Omary, M. A.; Pietroni, B. R.; Staples R. J. J. Am. Chem. Soc., 2000; 11264-11265. 4) Galassi, R.; Ricci, S.; Burini, A.; Macchioni, A; Marmottini, F.; Tekarli, S. M.; Nesterov, N.V.; Omary, M. A. Inorg. Chem. 2013, 52, 14124-14137

Feeding practices and physical inactivity contributions to childhood overweight

OBJECTIVE: To review the literature in order to show how current feeding and physical activity practices may contribute to childhood overweight. DATA SOURCE: Ovid Journals, Highwire and SciELO, selecting original and review articles from 1997 to 2007, published in English and Portuguese. DATA SYNTHESIS: The periodic assessment of children nutritional status is important to diagnose their current health status and to predict their adult life prognosis. In Brazil, the prevalence of childhood obesity is progressively increasing in all social classes and its frequency varies from five to 18%, according to the region assessed. The association between the health, demographic and behavioral transition and the change in feeding practices can explain the increasing prevalence of childhood overweight. The current food consumption with high fat, sugar and sodium intake and low intake of whole cereals, fruits and vegetables associated to physical inactivity due to the excessive use of computers, electronic games and television may play a role in childhood obesity. This life style can be explained by changing family habits and school environment. CONCLUSIONS: These data suggest considerable influence of environmental factors, mainly nutritional habits and physical inactivity, on the increasing prevalence of childhood overweight.OBJETIVO: Revisar estudos que abordam as práticas alimentares atuais e o padrão de atividade física como contribuintes do excesso de peso na infância. FONTES DE DADOS: Ovid Journals, Highwire e SciELO, com seleção de artigos originais e de revisão nos últimos dez anos (1997 a 2007), na língua portuguesa e inglesa. SÍNTESE DE DADOS: O acompanhamento do estado nutricional de crianças permite diagnosticar seu estado de saúde atual, bem como predizer parcialmente seu prognóstico na vida adulta. A prevalência de obesidade infantil, no Brasil, apresenta aumento progressivo em todas as classes sociais e sua freqüência varia entre cinco a 18%, dependendo da região estudada. A associação da transição epidemiológica, demográfica e comportamental e a alteração do hábito alimentar são apontadas como fatores causais do aumento progressivo da obesidade infantil. Práticas alimentares caracterizadas por elevado teor de lipídios, sacarose e sódio e por reduzido consumo de cereais integrais, frutas e hortaliças associadas à inatividade física decorrente do uso de computadores, jogos eletrônicos e televisores influenciam parte considerável de crianças. Este estilo de vida reflete os hábitos familiares e pode ser influenciado pelo ambiente escolar no qual a criança está inserida. CONCLUSÕES: Os dados sugerem influência considerável dos fatores ambientais, principalmente hábitos alimentares e inatividade física, no crescente aumento da prevalência de excesso de peso na população pediátrica.Universidade Estadual Paulista Faculdade de Medicina de BotucatuUniversidade Federal do Rio de JaneiroUnesp FMB Departamento de PediatriaUniversidade Federal de São Paulo (UNIFESP) Escola Paulista de Medicina Departamento de FisiologiaUnesp FMBUNIFESP, EPM, Depto. de FisiologiaSciEL

Groundwater modeling of the withdrawal sustainability of Cannara artesian aquifer (Umbria-Italy)

L\u2019acquifero di Cannara (Umbria, Italia) \ue8 noto da oltre un secolo ed \ue8 uno dei principali punti di approvvigionamento di acqua potabile nella Regione Umbria. All'inizio veniva utilizzato per scopi irrigui, poich\ue9 quest'area era prevalentemente agricola fino agli anni '60. Le acque sotterranee, sfruttate da Umbra Acque S.p.A. (Societ\ue0 che fornisce l\u2019acqua potabile), sono a 150 m al di sotto il livello del suolo e sono contenute in un acquifero poroso confinato, che in origine aveva caratteristiche artesiane. Lo sfruttamento di 200-300 l/s con nove pozzi ha causato una riduzione del livello piezometrico, mantenendo le condizioni di acquifero confinato, ad eccezione di un periodo molto breve durante il quale la falda \ue8 stata depressurizzata in seguito alla siccit\ue0 e per l'aumento dei prelievi di emergenza in sostituzione di altri rifornimenti idrici potabili (da sorgenti). La presenza occasionale di ioni ferro e ammonio conferma il confinamento delle acque sotterranee la loro facies idrochimica in un ambiente redox, mentre nelle aree vicine e negli acquiferi superficiali si registrano contaminanti antropogenici (nitrati e solventi clorurati). Per la protezione di queste acque sotterranee di interesse strategico (il pi\uf9 importante campo pozzi in Umbria), sono stati rivisti tutti i dati idrologici e idrochimici disponibili e studiata la ricarica dell'acquifero. Le aliquote di prelievi idrici sostenibili e le aree di salvaguardia delle acque sotterranee sono state identificate utilizzando un modello numerico di flusso. Sono state proposte ulteriori azioni per monitorare le acque sotterranee negli acquiferi superficiale e artesiano, insieme ad una sistemazione dei pozzi esistenti.The Cannara aquifer (Umbria, Italy) has been known for more than a century, and is one of the main drinking water supplies in the Umbria Region. In the beginning it was used for irrigation purposes, since this area was mainly agricultural up to the 1960s. The groundwater\u2014exploited by Umbra Acque S.p.A. (a Company supplying drinking water)\u2014is 150 m under ground level and is contained in a porous confined aquifer, which originally had artesian characteristics. Exploitation of 200\u2013300 l/s with nine wells caused a reduction of piezometric level, maintaining the confined aquifer conditions, except for a very short period during which the aquifer was depressurised by drought, and for increase of emergency withdrawals replacing other water supplies (from springs) for drinking purposes. The occasional presence of iron and ammonium ions confirms the confinement of the groundwater and their hydrochemical facies in a redox environment, while in nearby areas and shallow aquifers anthropogenic contaminants (nitrates and chlorinated solvents) are reported. For the protection of this aquifer of strategic interest (the most important well field in Umbria), all hydrological and hydrochemical data available have been reviewed, and the aquifer recharge studied. Sustainable rates of withdrawal, and groundwater protection areas have been identified using a numerical flow model. Further action for monitoring groundwater of both shallow and artesian aquifers, together with well-revamping, have been proposed

Cupriphication of gold to sensitize d10–d10 metal–metal bonds and near-unity phosphorescence quantum yields

Outer-shell s0/p0 orbital mixing with d10 orbitals and symmetry reductionuponcupriphicationofcyclic trinucleartrigonal-planargold(I) complexes are found to sensitize ground-state Cu(I)–Au(I) covalent bonds and near-unity phosphorescence quantum yields. Heterobimetallic Au4Cu2 {[Au4(μ-C2,N3-EtIm)4Cu2(μ-3,5-(CF3)2Pz)2], (4a)}, Au2Cu {[Au2(μ-C2,N3-BzIm)2Cu(μ-3,5-(CF3)2Pz)], (1) and [Au2(μ-C2, N3-MeIm)2Cu(μ-3,5-(CF3)2Pz)], (3a)}, AuCu2 {[Au(μ-C2,N3-MeIm)Cu2(μ3,5-(CF3)2Pz)2], (3b) and [Au(μ-C2,N3-EtIm)Cu2(μ-3,5-(CF3)2Pz)2], (4b)} and stacked Au3/Cu3 {[Au(μ-C2,N3-BzIm)]3[Cu(μ-3,5-(CF3)2Pz)]3, (2)} formuponreactingAu3 {[Au(μ-C2,N3-(N-R)Im)]3 ((N-R)Im = imidazolate; R =benzyl/methyl/ethyl =BzIm/MeIm/EtIm)} with Cu3 {[Cu(μ-3,5(CF3)2Pz)]3 (3,5-(CF3)2Pz = 3,5-bis(trifluoromethyl)pyrazolate)}. The crystal structures of 1 and 3a reveal stair-step infinite chains whereby adjacent dimer-of-trimer units are noncovalently packed via twoAu(I)⋯Cu(I)metallophilicinteractions,whereas 4a exhibitsa hexanuclear cluster structure wherein two monomer-of-trimer units are linked by a genuine d10–d10 polar-covalent bond with ligandunassisted Cu(I)–Au(I) distances of 2.8750(8) Å each—the shortest such an intermolecular distance ever reported between any two d10 centers so as to deem it a “metal–metal bond” vis-à-vis “metallophilic interaction.” Density-functional calculations estimate 35– 43kcal/molbindingenergy,akintotypicalM–Msingle-bondenergies. Congruently, FTIR spectra of4a showmultiple far-IR bands within 65– 200 cm−1, assignable to vCu-Au as validated by both the Harvey–Gray method of crystallographic-distance-to-force-constant correlation and dispersive density functional theory computations. Notably, the heterobimetallic complexes herein exhibit photophysical properties that are favorable to those for their homometallic congeners, due to threefold-to-twofold symmetry reduction, resulting in cuprophilicsensitizationinextinctioncoefficientandsolid-state photoluminescence quantum yields approaching unity (ΦPL = 0.90–0.97 vs. 0–0.83 for Au3 and Cu3 precursors), which bodes well for potential future utilization in inorganic and/or organic LED applications

Change detection of isolated housing using a new hybrid approach based on object classification with optical and TerraSAR-X data

Optical and microwave high spatial resolution images are now available for a wide range of applications. In this work, they have been applied for the semi-automatic change detection of isolated housing in agricultural areas. This article presents a new hybrid methodology based on segmentation of high-resolution images and image differencing. This new approach mixes the main techniques used in change detection methods and it also adds a final segmentation process in order to classify the change detection product. First, isolated building classification is carried out using only optical data. Then, synthetic aperture radar (SAR) information is added to the classification process, obtaining excellent results with lower complexity cost. Since the first classification step is improved, the total change detection scheme is also enhanced when the radar data are used for classification. Finally, a comparison between the different methods is presented and some conclusions are extracted from the study. © 2011 Taylor & Francis.Vidal Pantaleoni, A.; Moreno Cambroreno, MDR. (2011). Change detection of isolated housing using a new hybrid approach based on object classification with optical and TerraSAR-X data. International Journal of Remote Sensing. 32(24):9621-9635. doi:10.1080/01431161.2011.571297S962196353224BLAES, X., VANHALLE, L., & DEFOURNY, P. (2005). Efficiency of crop identification based on optical and SAR image time series. Remote Sensing of Environment, 96(3-4), 352-365. doi:10.1016/j.rse.2005.03.010Chen, Y., Shi, P., Fung, T., Wang, J., & Li, X. (2007). Object‐oriented classification for urban land cover mapping with ASTER imagery. International Journal of Remote Sensing, 28(20), 4645-4651. doi:10.1080/01431160500444731Dalla Mura, M., Benediktsson, J. A., Bovolo, F., & Bruzzone, L. (2008). An Unsupervised Technique Based on Morphological Filters for Change Detection in Very High Resolution Images. IEEE Geoscience and Remote Sensing Letters, 5(3), 433-437. doi:10.1109/lgrs.2008.917726Dell’Acqua, F., & Gamba, P. (2006). Discriminating urban environments using multiscale texture and multiple SAR images. International Journal of Remote Sensing, 27(18), 3797-3812. doi:10.1080/01431160600557572Haralick, R. M., Shanmugam, K., & Dinstein, I. (1973). Textural Features for Image Classification. IEEE Transactions on Systems, Man, and Cybernetics, SMC-3(6), 610-621. doi:10.1109/tsmc.1973.4309314Im, J., Jensen, J. R., & Tullis, J. A. (2008). Object‐based change detection using correlation image analysis and image segmentation. International Journal of Remote Sensing, 29(2), 399-423. doi:10.1080/01431160601075582Lhomme, S., He, D., Weber, C., & Morin, D. (2009). A new approach to building identification from very‐high‐spatial‐resolution images. International Journal of Remote Sensing, 30(5), 1341-1354. doi:10.1080/01431160802509017LOBO, A., CHIC, O., & CASTERAD, A. (1996). Classification of Mediterranean crops with multisensor data: per-pixel versus per-object statistics and image segmentation. International Journal of Remote Sensing, 17(12), 2385-2400. doi:10.1080/01431169608948779Lu, D., Mausel, P., Brondízio, E., & Moran, E. (2004). Change detection techniques. International Journal of Remote Sensing, 25(12), 2365-2401. doi:10.1080/0143116031000139863Shimabukuro, Y. E., Almeida‐Filho, R., Kuplich, T. M., & de Freitas, R. M. (2007). Quantifying optical and SAR image relationships for tropical landscape features in the Amazônia. International Journal of Remote Sensing, 28(17), 3831-3840. doi:10.1080/01431160701236829Stramondo, S., Bignami, C., Chini, M., Pierdicca, N., & Tertulliani, A. (2006). Satellite radar and optical remote sensing for earthquake damage detection: results from different case studies. International Journal of Remote Sensing, 27(20), 4433-4447. doi:10.1080/01431160600675895Yuan, D., & Elvidge, C. D. (1996). Comparison of relative radiometric normalization techniques. ISPRS Journal of Photogrammetry and Remote Sensing, 51(3), 117-126. doi:10.1016/0924-2716(96)00018-

Avaliação do estado nutricional de cadelas com câncer de mama

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Management and destination for residues from electrical discharge lamps

The use of gas discharge lamps is an important instrument to reduce energy demand and to increase efficiency at the end use of energy. It has been considered under the electrical energy reduction purposes. In this work the environment point of view was aggregated. After the bulb life time end the final destination of the harmful elements contained in it must be treated with focus on management of hazardous waste. Large data variability on the amount of Mercury (Hg) detected inside the discharge tube of the lamps were observed, particularly at fluorescent bulbs. The current situation in Brazil, where electricity generation is not based on burning coal and a greater market diffusion of bulbs based on Hg technology can induce increase in the emission of Hg during the bulb life cycle, unlike at the U.S. and other countries. Investments for the main equipments to quantify Hg content in discharge tubes from lamps were discussed and estimated.A utilização de fonte de luz elétrica eficiente tem sido uma prática crescente e atual, mesmo quando esse produto deixa de ser produzido localmente e necessita ser importado. Numa avaliação exclusivamente sob o prisma energético e quando comparada com fonte incandescente: a lâmpada a descarga em gases pode reduzir a demanda de energia elétrica e aumentar a eficiência em uso final. Neste artigo a análise que foi realizada agregou base ambiental importante. Terminada a vida útil da lâmpada a descarga, o destino final deve ser melhor considerado e com foco na gestão de resíduos perigosos. É bastante ampla a variabilidade que pode ser observada na literatura em relação á quantidade de Mercúrio (Hg) presente em lâmpadas a descarga, particularmente aquelas do tipo fluorescente. Na situação brasileira atual, cuja geração de eletricidade não tem base predominante na queima de carvão, uma maior difusão no mercado local de fonte de luz com base no Hg pode induzir uma elevação na emissão desse elemento nocivo durante o ciclo de vida da lâmpada, diferentemente dos EUA e outros países. O Hg e os resíduos potencialmente perigosos, particularmente aqueles que são encontrados nas fontes primárias de luz elétrica artificial, utilizadas localmente, deverão ser monitorados e controlados. Eles não devem continuar sendo descartados juntamente aos demais resíduos humanos e recolhidos sem qualquer cuidado especial e eficaz. Investimentos e necessidades para adequação de espaço laboratorial e aquisição dos principais equipamentos para quantificar Hg contido em tubos de descarga elétrica em lâmpadas foram discutidos e dimensionados.Asociación de Universidades Grupo Montevide

Food-dependent, exercise-induced gastrointestinal distress

Among athletes strenuous exercise, dehydration and gastric emptying (GE) delay are the main causes of gastrointestinal (GI) complaints, whereas gut ischemia is the main cause of their nausea, vomiting, abdominal pain and (blood) diarrhea. Additionally any factor that limits sweat evaporation, such as a hot and humid environment and/or body dehydration, has profound effects on muscle glycogen depletion and risk for heat illness. A serious underperfusion of the gut often leads to mucosal damage and enhanced permeability so as to hide blood loss, microbiota invasion (or endotoxemia) and food-born allergen absorption (with anaphylaxis). The goal of exercise rehydration is to intake more fluid orally than what is being lost in sweat. Sports drinks provide the addition of sodium and carbohydrates to assist with intestinal absorption of water and muscle-glycogen replenishment, respectively. However GE is proportionally slowed by carbohydrate-rich (hyperosmolar) solutions. On the other hand, in order to prevent hyponatremia, avoiding overhydration is recommended. Caregiver's responsibility would be to inform athletes about potential dangers of drinking too much water and also advise them to refrain from using hypertonic fluid replacements