Matéria orgânica do solo e emissão de C-CO2 em diferentes manejos e cultivos agrícolas

O manejo do solo deve ser realizado de tal forma que garanta a produção sustentável ao longo dos anos. Dentre as técnicas empregas, o manejo agroecológico e o plantio direto favorecem a manutenção da cobertura do solo e o aporte de matéria orgânica. Partindo da hipótese de que o maior aporte de resíduos culturais aumenta o conteúdo e estoque de matéria orgânica no solo, bem como reduz a emissão de C-CO2, o objetivo geral da pesquisa foi avaliar o impacto do manejo na matéria orgânica do solo e na emissão de C-CO2, nos períodos secos e chuvosos em diferentes cultivos agrícolas. O capítulo 1 foi desenvolvido na comunidade de Feliz Lembrança, Alegre–ES, onde foram avaliados sistemas de manejo em pastagem (PAST), café a pleno sol (PS) e café em sistema agroflorestal (SAF) e uma mata nativa (MN). O capítulo 2 foi desenvolvido no Incaper de Domingos Martins, onde se avaliou tratamentos de plantio direto de hortaliças sob palhada de gramínea (PD-G), leguminosa (PD-L), consórcio gramínea/leguminosa (PD-GL) e convencional utilizando enxada rotativa no pré-plantio (PC)em um delineamento de blocos casualizados. Amostras de solos em diferentes camadas foram coletadas para caracterização química e da matéria orgânica. Foram realizadas medições de emissão de C-CO2, temperatura do solo, umidade do solo e C biomassa microbiana do solo in situ. Foi utilizada análise de variância multivariada, vinculada a teste de aleatorização e aplicação de contrastes ortogonais no capítulo 1 e análise de variância aplicando teste F e teste de médias no capítulo 2. O SAF apresentou maior conteúdo de C orgânico total (19,8 g/kg) na camada de 0 a 5 cm e a PAST em subsuperfície. O menor estoque de C e N e os maiores valores de quociente metabólico foram encontrados no PS. O SAF reduziu a emissão de C-CO2 em 1,93 Mg ha-1 ano-1 em relação ao PS. O C orgânico total variou de 34,94 a 50,48 g/kg no PD-GL enquanto no sistema PC essa variação foi de 27,11 a 43,74 g/kg no perfil amostrado. A emissão média anual foi de 15,89 Mg C-CO2 ha-1 ano-1para a PD-G enquanto o PD-GL foi de 13,77; PD-L de 13,09 e PC de 11,20 Mg C-CO2 ha-1 ano-1. No PC, o balanço de C foi negativo (-2,15Mg ha-1), além de apresentar as menores médias anuais de umidade do solo e C biomassa microbiana e maior Qmet anual. Sistemas com contínuo e diversificado aporte de matéria orgânica promovem redução na emissão de C-CO2, bem como atuam no sequestro de C atmosférico.

Prova de hemaglutinação passiva para a evidenciação da toxina do C. diphtherias na lesão diftérica

Foi demonstrada a presença da toxina do C. diphtheriae, através de prova de hemaglutinação passiva, usando-se hemácias sensibilizadas com antitoxina diftérica, na lesão da garganta de 47,7% dos casos suspeitos de difteria examinados no presente trabalho. De 53,0% dos mesmos pacientes pôde ser isolado bacilo diftérico toxígeno. A prova de hemaglutinação passiva foi a única positiva em 13,0% dos casos e a cultura, a única positiva em 18,9%. Em 42 crianças normais ou portadoras de faringite ou amigdalite sem nenhuma característica clínica de difteria, a prova de hemaglutinação passiva foi negativa. O processo descrito, de execução muito simples, pode acusar o resultado em menos de 2 horas e oferece grande possibilidade de aplicação vantajosa no diagnóstico da difteria.

Deuterium NMR Study of Orientational Order in Cellulosic Network Microfibers

Deuterium NMR was used to investigate the orientational order in a composite cellulosic formed by liquid crystalline acetoxypropylcellulose (A PC) and demented nematic 4'-penty1-4-cyanobiphenyl (5CB-4 alpha d(2)) with the per centage of 85% A PC by weight Three forms of the composite including electro spun microfibers, thin film and bulk samples were analyzed The NMR results initially suggest two distinct scenarios, one whet e the 503-alpha d(2), is confined to small droplets with dimensions smaller than the magnetic coherence length and the other where the 503-alpha d(2) molecules arc aligned with the A PC network chains Polarized optical microscopy (POW from thin film samples along with all the NMR results show the presence of 5CB-alpha d(2) droplets in the composite systems with a nematic wetting layer at the APC-5CB-alpha d(2) interface that experiences and order disorder transition driven by the polymer network N-I transition The characterization of the APC network I-N transition shows a pronounced subcritical behavior within a heterogeneity scenario.

Avaliação dos níveis séricos das vitaminas A, E, C e B2, de carotenóides e zinco, em idosos hospitalizados

Foram verificados os níveis séricos de zinco, carotenóides e vitaminas A, E, C, B2 em todos os idosos (n = 202) internados nas diversas enfermarias do hospital estudado, no período de fevereiro de 1986 a outubro de 1988. Foram estudados 130 homens e 72 mulheres que apresentaram média de idade de 67,8 anos, com variação entre 60 a 88. A percentagem de níveis séricos deficitários foi de 59,5 para o zinco, 56,5% para a vitamina C, 34,5% para a vitamina B2, 26% para a vitamina E, 13,2% para a vitamina A e 6,8% para os carotenóides. Os idosos portadores de leucoses, magaesôfogo, doença pulmonar obstrutiva crônica e insuficiência cardíaca congestiva constituíram-se no grupo de pacientes com grande prevalência de estado deficitário de zinco e das vitaminas estudadas, resultados que mostram a importância de se investigar as deficiências desses micronutrientes e dão subsídios para a abordagem terapêutica mais racional do paciente idoso internado.

Molybdenum Complexes Bearing the Tris(1-pyrazolyl)methanesulfonate Ligand: Synthesis, Characterization and Electrochemical Behaviour

The tris(1-pyrazolyl)methanesulfonate lithium salt Li(Tpms) [Tpms = SO3C(pz)(3)-] reacts with [Mo(CO)(6)] in NCMe heated at reflux to yield Li[Mo(Tpms)(CO)(3)] (1), which, upon crystallization from thf, forms the coordination polymer [Mo(Tpms)(CO)(2)(mu-CO)Li(thf)(2)](n) (2). Reaction of 1 with I-2, HBF4 or AgBF4 yields [Mo(Tpms)I(CO)(3)] (3), (Mo(Tpms)-H(CO)(3)] (5) or (Mo(Tpms)O-2](2)(mu-O) (7), respectively. The high-oxidation-state dinuclear complexes [{Mo(Tpms)O(mu-O)}(2)] (4) and [{Mo(tpms)OCl)(2)](mu-O) (6) are formed upon exposure to air of solutions of 3 and 5, respectively. Compounds 1-7, which appear to be the first tris(pyrazolyl)methanesulfonate complexes of molybdenum to be reported, were characterized by IR, H-1 and C-13 NMR spectroscopy, ESI-MS, elemental analysis, cyclic voltammetry and, in the cases of Li(Tpms) and compounds 2, 4.2CH(3)CN, 6.6CHCl(3) and 7, by X-ray diffraction analyses. Li(Tpms) forms a 1D polymeric structure (i.e., [Li(tpms)](n)} with Tpms as a tetradentate N2O2 chelating ligand that bridges two Li cations with distorted tetrahedral coordination. Compound 2 is a 1D coordination polymer in which Tpms acts as a bridging tetradentate N3O ligand and each Li(thf)(2)(+) moiety is coordinated by one bridging CO ligand and by the sulfonyl group of a contiguous monomeric unit. In 4, 6 and 7, the Tpms ligand is a tridentate chelator either in the NNO (in 4) or in the NNN (in 6 and 7) fashion. Complexes 1, 3 and 5 exhibit, by cyclic voltammetry, a single-electron oxidation at oxidation potential values that indicate that the Tpms ligand has an electron-donor character weaker than that of cyclopentadienyl.

Spontaneous leptonic CP violation and nonzero theta(13)

We consider a simple extension of the Standard Model by adding two Higgs triplets and a complex scalar singlet to its particle content. In this framework, the CP symmetry is spontaneously broken at high energies by the complex vacuum expectation value of the scalar singlet. Such a breaking leads to leptonic CP violation at low energies. The model also exhibits an A(4) X Z(4) flavor symmetry which, after being spontaneously broken at a high-energy scale, yields a tribimaximal pattern in the lepton sector. We consider small perturbations around the tribimaximal vacuum alignment condition in order to generate nonzero values of theta(13), as required by the latest neutrino oscillation data. It is shown that the value of theta(13) recently measured by the Daya Bay Reactor Neutrino Experiment can be accommodated in our framework together with large Dirac-type CP violation. We also address the viability of leptogenesis in our model through the out-of-equilibrium decays of the Higgs triplets. In particular, the CP asymmetries in the triplet decays into two leptons are computed and it is shown that the effective leptogenesis and low-energy CP-violating phases are directly linked.

Complexes of copper(II) with 3-(ortho-substituted phenylhydrazo)pentane-2,4-diones: syntheses,properties and catalytic activity for cyclohexane oxidation

Reactions of copper(II) with 3-phenylhydrazopentane-2,4-diones X-2-C6H4-NHN = C{C(= O)CH3}(2) bearing a substituent in the ortho-position [X = OH (H2L1) 1, AsO3H2 (H3L2) 2, Cl (HL3) 3, SO3H (H2L4) 4, COOCH3 (HL5) 5, COOH (H2L6) 6, NO2 (HL7) 7 or H (HL8) 8] lead to a variety of complexes including the monomeric [CuL4(H2O)(2)]center dot H2O 10, [CuL4(H2O)(2)] 11 and [Cu(HL4)(2)(H2O)(4)] 12, the dimeric [Cu-2(H2O)(2)(mu-HL2)(2)] 9 and the polymeric [Cu(mu-L-6)](n)] 13 ones, often bearing two fused six-membered metallacycles. Complexes 10-12 can interconvert, depending on pH and temperature, whereas the Cu(II) reactions with 4 in the presence of cyanoguanidine or imidazole (im) afford the monomeric compound [Cu(H2O)(4){NCNC(NH2)(2)}(2)](HL4)(2)center dot 6H(2)O 14 and the heteroligand polymer [Cu(mu-L-4)(im)](n) 15, respectively. The compounds were characterized by single crystal X-ray diffraction (complexes), electrochemical and thermogravimetric studies, as well as elemental analysis, IR, H-1 and C-13 NMR spectroscopies (diones) and ESI-MS. The effects of the substituents in 1-8 on the HOMO-LUMO gap and the relative stability of the model compounds [Cu(OH)(L-8)(H2O)]center dot H2O, [Cu(L-1)(H2O)(2)]center dot H2O and [Cu(L-4)(H2O)(2)]center dot H2O are discussed on the basis of DFT calculations that show the stabilization follows the order: two fused 6-membered > two fused 6-membered/5-membered > one 6-membered metallacycles. Complexes 9, 10, 12 and 13 act as catalyst precursors for the peroxidative oxidation (with H2O2) of cyclohexane to cyclohexanol and cyclohexanone, in MeCN/H2O (total yields of ca. 20% with TONs up to 566), under mild conditions.

Coordination Chemistry of the (eta(6)-p-Cymene)ruthenium(II) Fragment with Bis-, Tris-, andTetrakis(pyrazol-1-yl)borate Ligands: Synthesis, Structural, Electrochemical, and CatalyticDiastereoselective Nitroaldol Reaction Studies

Novel [Ru(eta(6)-p-cymene)(kappa(2)-L)X] and [Ru(eta(6)-p-cymene)(kappa(3)-L)]X center dot nH(2)O complexes (L = bis-, tris-, or tetrakis-pyrazolylborate; X = Cl, N-3, PF6, or CF3SO3) are prepared by treatment of [Ru(eta(6)-p-cymene)Cl-2](2) with poly-(pyrazolyl)borate derivatives [M(L)] (L in general; in detail L = Ph(2)Bp = diphenylbis-(pyrazol-1-yl)borate; L = Tp = hydrotris(pyrazol-1-yl)borate; L = pzTp = tetrakis(pyrazol-1-yl)borate; L = Tp(4Bo) = hydrotris(indazol-1-yl)borate, L = T-p4Bo,T-5Me = (5-methylindazol-1-yl)borate; L = Tp(Bn,4Ph) = hydrotris(3-benzyl-4-phenylpyrazol-1-yl)borate; M = Na, K, or TI) and characterized by analytical and spectral data (IR, ESIMS, H-1 and C-13 NMR). The structures of [Ru(eta(6)-p-cymene)(Ph(2)Bp)Cl] (1) and [Ru(eta(6)-p-cymene)(Tp)Cl] (3) have been established by single-crystal X-ray diffraction analysis. Electrochemical studies allowed comparing the electron-donor characters of Tp and related ligands and estimating the corresponding values of the Lever E-L ligand parameter. The complexes [Ru(eta(6)-p-cymene)-(kappa(2)-L)X] and [Ru(eta(6)-p-cymene)(kappa(3)-L)]X center dot nH(2)O act as catalyst precursors for the diastereoselective nitroaldol reaction of benzaldehyde and nitroethane to the corresponding beta-nitroalkanol (up to 82% yield, at room temperature) with diastereoselectivity toward the formation of the threo isomer.

Prevalencia de hepatitis B, hepatitis C y sífilis en trabajadoras sexuales de Venezuela

OBJETIVO: En Venezuela las trabajadoras sexuales reciben un control sanitario para la sífilis y el virus de inmunodeficiencia humana (VIH). Sin embargo, otras importantes infecciones de transmisión sexual no son evaluadas. Así, se realizó este estudio con el objetivo de determinar el nivel socio-cultural de un grupo de trabajadores sexuales y su relación con la sero-presencia de marcadores de Hepatitis C y Hepatitis B, en adición a la evaluación de rutina. MÉTODOS: Se evaluaron 212 trabajadoras sexuales, que acudieron al control sanitario en el servicio de infecciones de transmisión sexual, de la ciudad de Los Teques, Venezuela. Fueron entrevistadas en cuanto a edad, nivel educativo, uso de anticonceptivos y del condón. Se les tomó una muestra de sangre para determinar sífilis, antígeno de superficie de hepatitis B (HBsAg) y la presencia de anticuerpos contra el core de hepatitis B (anti-HBc), virus de hepatitis C (anti-HC) y VIH. Los datos fueron evaluados estadísticamente por Chi-cuadrado y correlación de Pearson. RESULTADOS: La prevalencia fue de 2,4% para sífilis, 0,5% para anti-HC, 3,8% para HBsAg y 13,8% para anti-HBc. Un aumento en la prevalencia de marcadores de hepatitis B se correlacionó con un bajo nivel educativo (p<0,05) e incremento en la edad (p<0,05). No se encontró ningún caso positivo de VIH. La encuesta reveló que el 38,5% de las trabajadoras sexuales nunca utilizan el condón y un 25,6% de ellas no utiliza ningún tipo de método anticonceptivo. CONCLUSIONES: Es necesario implementar planes de inmunización de hepatitis B en este grupo de mujeres, así como campañas de educación sobre la importancia del uso del condón para disminuir la probabilidad de contraer infecciones de transmisión sexual.

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.

Fatores de risco para infecção pelo HIV em pacientes com o vírus da hepatite C

OBJETIVO: Os vírus da imunodeficiência humana e o vírus da hepatite C apresentam fatores de transmissão em comum. Atualmente, há alta freqüência da co-infecção, principalmente em indivíduos usuários de drogas injetáveis e com história de transfusões. O objetivo do estudo foi avaliar os fatores de risco para infecção pelo HIV em pacientes infectados pelo vírus da hepatite C. MÉTODOS: Trata-se de estudo epidemiológico do tipo caso-controle, realizado com 118 pacientes (casos) infectados pelos vírus HIV e vírus da hepatite C e 233 pacientes (controles) infectados somente pelo vírus da hepatite C. Entre janeiro de 1999 a novembro de 2001, os pacientes foram submetidos a questionário sobre características sociodemográficas, profissionais, e principais fatores de risco para infecção pelos vírus. Após descritas e comparadas, as variáveis foram submetidas à análise univariada, e em seguida à análise de regressão logística para variáveis selecionadas pelo teste da razão da máxima verossimilhança. RESULTADOS: A co-infecção está associada ao sexo feminino (OR=2,89; IC 95%: 1,16-7,08), aos estados civis separado/viúvo (OR=3,91; IC 95%: 1,34-11,35), ao uso pregresso ou atual de drogas ilícitas (OR=3,96; IC 95%: 1,55-0,13) e ao hábito de compartilhar canudos ou seringas (OR=10,28; IC 95%: 4,00-6,42). CONCLUSÕES: Em pacientes infectados pelo vírus da hepatite C, o sexo feminino é fator de risco para a infecção pelo HIV quando ajustado à variável compartilhar canudos ou seringas. Os estados civis separado/viúvo, uso de drogas ilícitas e hábito de compartilhar canudos ou seringas são, também, fatores associados ao risco para esta co-infecção.

Synthesis of new 1,8-dihydroxy-9h-xanthen-9-ones

XXVth European Colloquium on Heterocyclic Chemistry, Reading, UK, 13 – 17 Agosto de 2012.

Synthesis, structure and electrochemical behaviour of Na, Mg-II, Mn-II, Cd-II and Ni-II complexes of 3-(2-carboxyphenylhydrazone)pentane-2,4-dione

Mononuclear manganese(II) [Mn(kappa O-HL)(2)(CH3OH)(4)] (4), nickel(II) [Ni(kappa O-2, kappa N-L)(H2O)(3)] (5), cadmium(II) [Cd(kappa O-2-HL)(2)(CH3OH)(3)] (7), tetranuclear zinc(II) [Zn-4(mu-OH)(2)(1 kappa O:2 kappa O-HL)(4)(kappa O-HL)(2)(H2O)(4)] (6) and polynuclear aqua sodium(I) [Na(H2O)(2)(mu-H2O)(2)](n)(HL)(n) (2) and magnesium(II) [Mg(OH)(H2O)(mu-H2O)(2)](n)(-HL)(n) (3) complexes were synthesized using 3-(2-carboxyphenyl-hydrazone)pentane-2,4-dione (H2L, 1) as a ligand precursor. The complexes were characterized by single crystal X-ray diffraction, elemental analysis, IR, H-1 and C-13 NMR (for 2, 3, 6 and 7) spectroscopies. Mono- or dianionic deprotonated derivatives of H2L display different coordination modes and lead to topologies and nuclearities of the complexes depending on metal ions and conditions used for the syntheses. Extensive intermolecular H-bonds form supramolecular arrangements in 1D chains (4 and 6), 1D chains of the organic anion and 2D networks of the metal-aqua aggregates (2 and 3), 2D networks (7) or even 3D frameworks (5). Electrochemical studies, by cyclic voltammetry and controlled potential electrolysis, show ligand centred redox processes as corroborated by theoretical DFT calculations in terms of LUMO and HOMO compositions. (C) 2012 Elsevier Ltd. All rights reserved.

Cobalt and Zinc Compounds Bearing 1,10-Phenanthroline-5,6-dione or 1,3,5-Triaza-7-phosphaadamantane Derivatives - Synthesis, Characterization, Cytotoxicity, and Cell Selectivity Studies

The compounds [mPTA][CoCl4] (1, mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane cation), [CoCl(H2O)(DION)(2)][BF4] (2, DION = 1,10-phenanthroline-5,6-dione), [Zn(DION)(2)]Cl-2 (3) and [ZnCl(O-PTA=O)(DION)][BF4] (4) were synthesized by reaction of CoCl2 with [mPTA]I or DION and ZnCl2 with DION or 1,3,5-triaza-7-phosphaadamantane-7-oxide (PTA=O) and DION, respectively. All complexes are water soluble and have been characterized by IR, far-IR, H-1, C-13 and P-31{H-1} NMR spectroscopy, ESI-MS, elemental analyses and single-crystal X-ray diffraction structural analysis (for 1). They were screened against the human tumour cell lines HCT116, HepG2 and MCF7. Complexes 2 and 3 exhibit the highest in vitro cytotoxicity and show lower cytotoxic activities in normal human fibroblast cell line than in HCT116 tumour cell line, which demonstrates their slight specificity for this type of tumour cell.

Synthesis, characterization, electrochemical behavior and in vitro protein tyrosine kinase inhibitory activity of the cymene-halogenobenzohydroxamato [Ru(eta(6)-cymene)(bha)Cl] complexes

The ruthenium(II)-cymene complexes [Ru(eta(6)-cymene)(bha)Cl] with substituted halogenobenzohydroxamato (bha) ligands (substituents = 4-F, 4-Cl, 4-Br, 2,4-F-2, 3,4-F-2, 2,5-F-2, 2,6-F-2) have been synthesized and characterized by elemental analysis, IR, H-1 NMR, C-13 NMR, cyclic voltammetry and controlled-potential electrolysis, and density functional theory (DFT) studies. The compositions of their frontier molecular orbitals (MOs) were established by DFT calculations, and the oxidation and reduction potentials are shown to follow the orders of the estimated vertical ionization potential and electron affinity, respectively. The electrochemical E-L Lever parameter is estimated for the first time for the various bha ligands, which can thus be ordered according to their electron-donor character. All complexes exhibit very strong protein tyrosine kinase (PTK) inhibitory activity, even much higher than that of genistein, the clinically used PTK inhibitory drug. The complex containing the 2,4-difluorobenzohydroxamato ligand is the most active one, and the dependences of the PTK activity of the complexes and of their redox potentials on the ring substituents are discussed. (C) 2012 Elsevier B.V. All rights reserved.