Synthesis, Antimicrobial and Antiproliferative Activity of Novel Silver(I) Tris(pyrazolyl)methanesulfonateand 1,3,5-Triaza-7-phosphadamantane Complexes

Five new silver(I) complexes of formulas [Ag(Tpms)] (1), [Ag(Tpms)-(PPh3)] (2), [Ag(Tpms)(PCy3)] (3), [Ag(PTA)][BF4] (4), and [Ag(Tpms)(PTA)] (5) {Tpms = tris(pyrazol-1-yl)methanesulfonate, PPh3 = triphenylphosphane, PCy3 = tricyclohexylphosphane, PTA = 1,3,5-triaza-7-phosphaadamantane) have been synthesized and fully characterized by elemental analyses, H-1, C-13, and P-31 NMR, electrospray ionization mass spectrometry (ESI-MS), and IR spectroscopic techniques. The single crystal X-ray diffraction study of 3 shows the Tpms ligand acting in the N-3-facially coordinating mode, while in 2 and 5 a N2O-coordination is found, with the SO3 group bonded to silver and a pendant free pyrazolyl ring. Features of the tilting in the coordinated pyrazolyl rings in these cases suggest that this inequivalence is related with the cone angles of the phosphanes. A detailed study of antimycobacterial and antiproliferative properties of all compounds has been carried out. They were screened for their in vitro antimicrobial activities against the standard strains Enterococcus faecalis (ATCC 29922), Staphylococcus aureus (ATCC 25923), Streptococcus pneumoniae (ATCC 49619), Streptococcus pyogenes (SF37), Streptococcus sanguinis (SK36), Streptococcus mutans (UA1S9), Escherichia coli (ATCC 25922), and the fungus Candida albicans (ATCC 24443). Complexes 1-5 have been found to display effective antimicrobial activity against the series of bacteria and fungi, and some of them are potential candidates for antiseptic or disinfectant drugs. Interaction of Ag complexes with deoxyribonucleic acid (DNA) has been studied by fluorescence spectroscopic techniques, using ethidium bromide (EB) as a fluorescence probe of DNA. The decrease in the fluorescence of DNA EB system on addition of Ag complexes shows that the fluorescence quenching of DNA EB complex occurs and compound 3 is particularly active. Complexes 1-5 exhibit pronounced antiproliferative activity against human malignant melanoma (A375) with an activity often higher than that of AgNO3, which has been used as a control, following the same order of activity inhibition on DNA, i.e., 3 > 2 > 1 > 5 > AgNO3 >> 4.

Trends in properties of para-substituted 3-(phenylhydrazo)pentane-2,4-diones

Trends between the Hammett's sigma(p) and related normal sigma(n)(p), inductive sigma(I), resonance sigma(R), negative sigma(-)(p) and positive sigma(+)(p) polar conjugation and Taft's sigma(o)(p) substituent constants and the N-H center dot center dot center dot O distance, delta(N-H) NMR chemical shift, oxidation potential (E-p/2(ox), measured in this study by cyclic voltammetry (CV)) and thermodynamic parameters (pK, Delta G(0), Delta H-0 and Delta S-0) of the dissociation process of unsubstituted 3-(phenylhydrazo)pentane-2,4-dione (HL1) and its para-substituted chloro (HL2), carboxy (HL3), fluoro (HL4) and nitro (HL5) derivatives were recognized. The best fits were found for sigma(p) and/or sigma(-)(p) in the cases of d(N center dot center dot center dot O), delta(N-H) and E-p/2(ox), showing the importance of resonance and conjugation effects in such properties, whereas for the above thermodynamic properties the inductive effects (sigma(I)) are dominant. HL2 exists in the hydrazo form in DMSO solution and in the solid state and contains an intramolecular H-bond with the N center dot center dot center dot O distance of 2.588(3)angstrom. It was also established that the dissociation process of HL1-5 is non-spontaneous, endothermic and entropically unfavourable, and that the increase in the inductive effect (sigma(I)) of para-substitutents (-H < -Cl < -COOH < -F < -NO2) leads to the corresponding growth of the N center dot center dot center dot O distance and decrease of the pK and of the changes of Gibbs free energy, of enthalpy and of entropy for the HL1-5 acid dissociation process. The electrochemical behaviour of HL1-5 was interpreted using theoretical calculations at the DFT/HF hybrid level, namely in terms of HOMO and LUMO compositions, and of reactivities induced by anodic and cathodic electron-transfers. Copyright (C) 2010 John Wiley & Sons, Ltd.

Segurança e sinalização na vizinhança de áreas escolares: estudos de casos em Santarém

A vizinhança viária dos estabelecimentos escolares constitui-se como um local de concentração de peões e de ciclistas, cuja movimentação conflitua com os veículos automóveis, quer sejam de natureza particular ou pública. O ambiente urbano em que se localiza o edifício escolar, a natureza da rede viária que lhe serve de acesso, a faixa etária e o número de alunos que a frequentam, são fatores que são determinantes no estudo de soluções que induzam e estimulem os comportamentos em segurança de todos os intervenientes, nomeadamente os escolares e os condutores. Com efeito, escolas em ambiente urbano requerem o estudo de composições viárias diferentes das localizadas em ambiente rural, da mesma forma que estabelecimentos do Ensino Básico ou Secundário apresentam comportamentos de utentes perfeitamente distintos. O planeamento inadequado e a dinâmica do crescimento e da transformação das cidades são alguns dos fatores que ao longo dos anos se traduziram em impactos muitas vezes negativos na segurança e fluidez do tráfego junto às escolas, resultados que deveriam representar a prioridade dos órgãos de trânsito nacionais e municipais. Alguns países do mundo e algumas cidades da Europa têm entretanto investido na implementação de várias medidas para mitigar os referidos impactes. Aproveitando-se como referência as melhores práticas sobre a temática segurança viária e os casos de sucesso desenvolvidos, pretendeu-se com este trabalho elaborar uma proposta de projeto para dois estabelecimentos de ensino da cidade de Santarém. Os resultados da análise prévia às condições particulares de segurança existentes e a comparação com outros estabelecimentos localizados na zona urbana da cidade, foram determinantes para esta escolha. Com base nos dados obtidos e nas características dos tráfegos pedonal e viário, são apresentadas duas soluções distintas que poderão ser genericamente aplicadas em situações similares, dada a impossibilidade de se estudarem soluções tipo que não resultariam, face à complexidade e diversidade das variáveis envolvidas.

Effects of health decentralization, financing and governance in Mexico

OBJECTIVE: To identify the effects of decentralization on health financing and governance policies in Mexico from the perspective of users and providers. METHODS: A cross-sectional study was carried out in four states that were selected according to geopolitical and administrative criteria. Four indicators were assessed: changes and effects on governance, financing sources and funds, the final destination of resources, and fund allocation mechanisms. Data collection was performed using in-depth interviews with health system key personnel and community leaders, consensus techniques and document analyses. The interviews were transcribed and analyzed by thematic segmentation. RESULTS: The results show different effectiveness levels for the four states regarding changes in financing policies and community participation. Effects on health financing after decentralization were identified in each state, including: greater participation of municipal and state governments in health expenditure, increased financial participation of households, greater community participation in low-income states, duality and confusion in the new mechanisms for coordination among the three government levels, absence of an accountability system, lack of human resources and technical skills to implement, monitor and evaluate changes in financing. CONCLUSIONS: In general, positive and negative effects of decentralization on health financing and governance were identified. The effects mentioned by health service providers and users were related to a diversification of financing sources, a greater margin for decisions around the use and final destination of financial resources and normative development for the use of resources. At the community level, direct financial contributions were mentioned, as well as in-kind contributions, particularly in the form of community work.

A Hexanuclear Mixed-Valence Oxovanadium(IV,V) Complex as a Highly Efficient Alkane Oxidation Catalyst

The new hexanuclear mixed-valence vanadium complex [V3O3(OEt)(ashz)(2)(mu-OEt)](2) (1) with an N,O-donor ligand is reported. It acts as a highly efficient catalyst toward alkane oxidations by aqueous H2O2. Remarkably, high turnover numbers up to 25000 with product yields of up to 27% (based on alkane) stand for one of the most active systems for such reactions.

A eficiência na gestão de projectos em Portugal - Reflexão sobre o incumprimento dos objectivos fixados e sua consequências na viabilidade dos empreendimentos

Trabalho desenvolvido para a apresentação em Provas Públicas para atribuição do título de Especialista em Engenharia e Gestão Industrial

Efficiency Measures in the Agricultural Sector: The Beginning

Copyright © 2013 Springer Netherlands.

Animal Grazing System Efficiency

Copyright © 2013 Springer Netherlands.

Azorean Agriculture Efficiency by PAR

Copyright © 2013 Springer Netherlands.

Sustainable Tourism and Agriculture Multifunctionality by PAR: A Variable Selection Approach

Copyright © 2013 Springer Netherlands.

Efficiency Assessment: Final Remarks

Copyright © 2013 Springer Netherlands.

Efficiency Measures in the Agricultural Sector: With Applications

Copyright 2013 Springer Netherlands.

Superefficiency and Multiplier Adjustment in Data Envelopment Analysis

Copyright © 2013 Springer Netherlands.

Multiplier adjustment in data envelopment analysis

V Congreso de Eficiencia y Productividad EFIUCO, Córdoba, 19-20 Mayo 2011.

Relação existente entre as exportações e as restrições financeiras das empresas industriais do setor têxtil

Dissertação de Mestrado em Finanças Empresariais