A prospective, randomized, pragmatic, health outcomes trial evaluating the incorporation of hylan G-F 20 into the treatment paradigm for patients with knee osteoarthritis (Part 1 of 2): clinical results

Objective: First, to assess the clinical effectiveness of hylan G-F 20 in an appropriate care treatment regimen (as defined by the American College of Rheumatology (ACR) 1995 guidelines) as measured by validated disease-specific outcomes and health-related quality of life endpoints for patients with osteoarthritis (OA) of the knee. Second, to utilize the measures of effectiveness and costs in an economic evaluation (see accompanying manuscript). Design: A total of 255 patients with OA of the knee were enrolled by rheumatologists or orthopedic surgeons into a prospective, randomized, open-label, 1-year, multi-centred trial, conducted in Canada. Patients were randomized to 'Appropriate care with hylan G-F 20' (AC+H) or 'Appropriate care without hylan G-F 20' (AC). Data were collected at clinic visits (baseline, 12 months) and by telephone (1, 2, 4, 6, 8, 10, and 12 months). Results: The AC+H group was superior to the AC group for all primary (% reduction in mean Western Ontario and McMaster Universities Osteoarthritis Index (WOMAC) pain scale: 38% vs 13%, P=0.0001) and secondary effectiveness outcome measures. These differences were all statistically significant and exceeded the 20% difference between groups seta priori by the investigators as the minimum clinically important difference. Health-related quality of life improvements in the AC+H group were statistically superior for the WOMAC pain, stiffness and physical function (all P

Multiple ciguatoxins present in Indian Ocean reef fish

Optimised gradient reversed-phase high-performance liquid chromatography electrospray ionisation mass spectrometry (LC/MS) methods, in combination with a [H-3]-brevetoxin binding assay (RLB), revealed multiple ciguatoxins in a partially purified extract of a highly toxic Lutjanus sebae (red emperor) from the Indian Ocean. Two major ciguatoxins of 1140.6 Da (I-CTX-1 and -2) and two minor ciguatoxins of 1156.6 Da (I-CTX-3 and -4) were identified. Accurate mass analysis revealed that I-CTX-1 and -2 and Caribbean C-CTX-1 had indistinguishable masses (1140.6316 Da, at 0.44 ppm resolution). Toxicity estimated from LC/MS/RLB responses indicated that I-CTX-1 and -2 were both similar to 60% the potency of Pacific ciguatoxin-1 (P-CTX-1). In contrast to ciguatoxins of the Pacific where the more oxidised ciguatoxins are more potent, I-CTX-3 and -4 were similar to 20% of P-CTX-1 potency. Interconversion in dilute acid or on storage, typical of spiroketal and hemiketal functionality found in P-CTXs and C-CTXs, respectively, was not observed to occur between I-CTX-1 and -2. The ratio of CTX-1 and -2 varied depending on the fish extract being analysed. These results suggest that I-CTX-1 and -2 may arise from separate dinoflagellate precursors that may be oxidatively biotransformed to I-CTX-3 and -4 in fish. (C) 2002 Published by Elsevier Science Ltd.

Effect of soil composition and dissolved organic matter on pesticide sorption

The effect of the solid and dissolved organic matter fractions, mineral composition and ionic strength of the soil solution on the sorption behaviour of pesticides were studied. A number of soils, chosen so as to have different clay mineral and organic carbon content, were used to study the sorption of the pesticides atrazine (6-chloro-N-2-ethyl-N-4-isopropyl-1,3,5-triazine-2,4-diamine), 2,4-D ((2,4-dichlorophenoxy) acetic acid), isoproturon (3-(4-isopropylphenyl)1,1-dimethylurea) and paraquat (1,1'-dimethyl-4,4'-bipyridinium) in the presence of low and high levels of dissolved organic carbon and different background electrolytes. The sorption behaviour of atrazine, isoproturon and paraquat was dominated by the solid state soil components and the presence of dissolved organic matter had little effect. The sorption of 2,4-D was slightly affected by the soluble organic matter in the soil. However, this effect may be due to competition for adsorption sites between the pesticide and the soluble organic matter rather than due to a positive interaction between the pesticide and the soluble fraction of soil organic matter. It is concluded that the major factor governing the sorption of these pesticides is the solid state organic fraction with the clay mineral content also making a significant contribution. The dissolved organic carbon fraction of the total organic carbon in the soil and the ionic strength of the soil solution appear to have little or no effect on the sorption/transport characteristics of these pesticides over the range of concentrations studied. (C) 2002 Elsevier Science B.V. All rights reserved.

Spatial and temporal changes in multiple hormone groups during lateral bud release shortly following apex decapitation of chickpea (Cicer arietinum) seedlings

Although the co-ordination of promotive root-sourced cytokinin (CK) and inhibitory shoot apex-sourced auxin (IAA) is central to all current models on lateral bud dormancy release, control by those hormones alone has appeared inadequate in many studies. Thus it was hypothesized that the IAA : CK model is the central control but that it must be considered within the relevant timeframe leading to lateral bud release and against a backdrop of interactions with other hormone groups. Therefore, IAA and a wide survey of cytokinins (CKs), were examined along with abscisic acid (ABA) and polyamines (PAs) in released buds, tissue surrounding buds and xylem sap at 1 and 4 h after apex removal, when lateral buds of chickpea are known to break dormancy. Three potential lateral bud growth inhibitors, IAA, ABA and cis-zeatin 9-riboside (ZR), declined sharply in the released buds and xylem following decapitation. This is in contrast to potential dormancy breaking CKs like trans-ZR and trans-zeantin 9-riboside 5'phosphate (ZRMP), which represented the strongest correlative changes by increasing 3.5-fold in xylem sap and 22-fold in buds. PAs had not changed significantly in buds or other tissues after 4 h, so they were not directly involved in the breaking of bud dormancy. Results from the xylem and surrounding tissues indicated that bud CK increases resulted from a combination synthesis in the bud and selective loading of CK nucleotides into the xylem from the root.

2-quinolyl- and 1-isoquinolylnitrenes: Ring expansion and ring opening in heteroarylnitrenes

Argon matrix photolysis of tetrazolo[1,5-a]quinoline 8 and tetrazolo[5,1-a]isoquinoline 7 causes nitrogen elimination and ring expansion to 1,3-diazabenzo[d]cyclohepta-1,2,4,6-tetraene 13. The photolysis of tetrazolo[5,1-a]isoquinoline 7 also causes ring opening to o-cyanophenylketenimine 22. Mechanisms of ring opening of heteroarylnitrenes are discussed.

4?? Encontro Nacional de Educa????o a Distancia para a Rede de Escolas de Governo

IV Encontro Nacional de Educa????o ?? Dist??ncia para a Rede de Escolas de Governo, realizado em Fortaleza-CE, no per??odo de 16 a 18 de novembro de 2011.

Ácidos húmicos extraídos do lodo de esgoto sanitário e seus efeitos em plantas

O lodo de esgoto possui alto teor de matéria orgânica porém, também estão presentes diferentes poluentes e patógenos. Desta forma, neste trabalho foi extraído ácido húmico (AH) o qual é um composto resultante do fracionamento de substâncias húmicas que compreendem um grupo de compostos de carbono gerados na decomposição de resíduos orgânicos que sofrem ressíntese formando o húmus. O ácido húmico promove diversos benefícios nos vegetais, como crescimento, elongação celular, tolerância a estresses e aumento da permeabilidade da membrana plasmática. Com base nestas características, o presente trabalho teve como objetivo avaliar os efeitos citogenéticos (ensaio Allium cepa), fisiológicos, anatômicos e bioquímicos do ácido húmico do lodo de esgoto sanitário. Foi realizada caracterização elementar do material para a definição das doses. Após 20 dias de tratamento, foram realizadas coletas do material e, posteriormente, analisadas. A caracterização química do AH indicou-o como bom condicionador para culturas apresentando elevadas taxas de C, H e N. Não foi observado efeito de toxicidade, citotoxicidade, genotoxicidade e mutagenicidade do AH. Foi verificado aumento expressivo de todos os pigmentos fotossintéticos vegetais nas concentrações mais altas (2 mM C L-1 e 4 mM C L-1). Houve aumento da expressão da ATPAse em todos os tratamentos e das enzimas do estresse oxidativo (CAT, SOD, APX, GST) em diferentes concentrações. A integração destas análises permitiu concluir que o ácido húmico do lodo de esgoto pode ser utilizado como adubo orgânico, pois foi observado benefícios no vegetal tais como maior crescimento vegetal e aumento da atividade nas enzimas do estresse oxidativo.

The influence of light spectra, UV-A, and growth regulators on the in vitro seed germination of Senecio cineraria DC.

This study was carried out to investigate the effects of light spectra, additional UV-A, and different growth regulators on the in vitro germination of Senecio cineraria DC. Seeds were surface-sterilized and inoculated in MS medium to evaluate the following light spectra: white, white plus UV-A, blue, green, red or darkness. The maximum germinability was obtained using MS0 medium under white light (30%) and MS + 0.3 mg L-1 GA3 in the absence of light (30.5%). S. cineraria seeds were indifferent to light. Blue and green lights inhibited germination. Different concentrations of gibberellic acid (GA3) (0.1; 0.4; 0.6; 0.8; 1.0 and 2.0 mg L-1) and indole-3-acetic acid IAA (0.1; 0.3 and 1.0 mg L-1) were evaluated under white light and darkness. No concentration of GA3 enhanced seed germination percentage under white light. However, when the seeds were maintained in darkness, GA3 improved germination responses in all tested concentrations, except at 1.0 mg L-1. Under white light, these concentrations also increased the germination time and reduced germination rate. Germination rate, under light or darkness, was lower using IAA compared with GA3.

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.

Concentrações sangüíneas de metais pesados e praguicidas organoclorados em crianças de 1 a 10 anos

Foi realizado estudo em 6 bairros do Município de Cubatão, SP, Brasil, situados às margens dos principais rios do município, com uma amostragem de 251 crianças de 1 a 10 anos de idade. Foram verificadas as concentrações sangüíneas de praguicidas organoclorados em 242 crianças, sendo que 73 crianças (30%) apresentaram concentrações de p-p'DDE (média = 0,85 ± 2,13 µg/l.), e em 47 crianças (19%) foi encontrado HCH total (média = 0,28 ± 0,79 µg/l.). Verificou-se também a concentração sangüínea de chumbo e mercúrio, sendo que se obteve a plumbemia média de 17,8 ± 5,8 µg/dl. e concentração média de mercúrio de 9,1 ± 6,4 µg/l. Crianças consumidoras de organismos aquáticos de origem exclusiva dos rios de Cubatão apresentaram teores médios de mercúrio (média = 14,7 ±7,1 µg/l.) significativamente maiores (p < 0,04) em comparação às crianças não consumidoras de organismos aquáticos de qualquer origem (média = 10,0 ± 6,5 µg/l.).

Antifungal activity of Imidazolidin-4-ones of the antimalarial primaquine

The 5-Isopropyl-3-[4-(6-methoxy-quinolin-8-ylamino)-pentyl]-2,2-dimethyl-imidazolidin-4-one (ValPQacet) was sinthesized through acylation of the anti-malarial primaquine with α-valine and subsequent reaction of the resulting -aminoamide with propanone (Sheme 1).Imidazolidin-4-ones of the anti malarial primaquine are being sinthesized to develop new variants in order to improve more effective treatments against malaria . Recently it has been observed that primaquine derivates could have effect in a new kind of yeast . To study the fungicidal activity against Candida albicans, Candida tropicalis, Issatchenkia orientalis, Sacharomyces cerevisae, the ValPQacet was put in the form of the hydrochloride salt. The minimal inhibitory concentration (MIC) could be determined for all yeast in the concentration range assayed. Also was determined MIC’s of primaquine hydrochloride salt for all yeast, and this shows that the parent drug is less active than our compound. Further studies are being performed to determine viability and cellular injury with this drugs.

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.

Modelação do transporte e dispersão de um marcador corado no Rio Febros

O rio Febros é um pequeno curso de água, situado no concelho de Vila Nova de Gaia, com cerca de 15 km de extensão, cuja bacia hidrográfica ocupa uma área de aproximadamente 35,4 km2. Nasce em Seixezelo e desagua na margem esquerda do Rio Douro no Cais do Esteiro, em Avintes. Em Maio de 2008, um acidente de viação teve como consequência o derrame de cerca de quatro toneladas de ácido clorídrico que rapidamente convergiu às águas do rio. Apenas um dia depois, o pH desceu para três e muitos foram os peixes que morreram. A solução adoptada para evitar o desaire foi introduzir milhares de litros de água de modo a diluir o ácido presente, ao longo de todo o curso de água. Tal facto não evitou a destruição de parte de um ecossistema, que ainda nos dias de hoje se encontra em recuperação. De forma a avaliar-se o impacto destas possíveis perturbações sejam estas de origem antropogénica ou natural é necessário possuir conhecimentos dos processos químicos tais como a advecção, a mistura devida à dispersão e a transferência de massa ar/água. Estes processos irão determinar o movimento e destino das substâncias que poderão ser descarregadas no rio. Para tal, recorrer-se-á ao estudo hidrogeométrico do curso de água assim como ao estudo do comportamento de um marcador, simulando uma possível descarga. A rodamina WT será o marcador a ser utilizado devido à panóplia de características ambientalmente favoráveis. Os estudos de campo com este corante, realizados em sequência de descarga previamente estudada, fornecem uma das melhores fontes de informação para verificação e validação de modelos hidráulicos utilizados em estudos de qualidade de águas e protecção ambiental. Escolheram-se dois pontos de descarga no Febros, um em Casal Drijo e outro no Parque Biológico de Gaia, possuindo cada um deles, a jusante, duas estações de monitorização. Pelo modelo ADE os valores obtidos para o coeficiente de dispersão longitudinal para as estações Pontão d’ Alheira, Pinheiral, Menesas e Giestas foram, respectivamente, 0,3622; 0,5468; 1,6832 e 1,7504 m2/s. Para a mesma sequência de estações, os valores da velocidade de escoamento obtidos neste trabalho experimental foram de 0,0633; 0,0684; 0,1548 e 0,1645 m/s. Quanto ao modelo TS, os valores obtidos para o coeficiente de dispersão longitudinal para as estações Pontão d’ Alheira, Pinheiral, Menesas e Giestas foram, respectivamente, 0,2339; 0,1618; 0,5057e 1,1320 m2/s. Para a mesma sequência de estações, os valores da velocidade de escoamento obtidos neste trabalho experimental foram de 0,0652; 0,0775; 0,1891 e 0,1676 m/s. Os resultados foram ajustados por um método directo, o método dos momentos, e por dois métodos indirectos, os modelos ADE e TS. O melhor ajuste corresponde ao modelo TS onde os valores do coeficiente de dispersão longitudinal e da velocidade de escoamento são aqueles que melhor se aproximam da realidade. Quanto ao método dos momentos, o valor estimado para a velocidade é de 0,162 m/s e para o coeficiente de dispersão longitudinal de 9,769 m2/s. Não obstante, a compreensão da hidrodinâmica do rio e das suas características, bem como a adequação de modelos matemáticos no tratamento de resultados formam uma estratégia de protecção ambiental inerente a futuros impactos que possam suceder.

Biomimetic sensors of molecularly-imprinted polymers for chlorpromazine determination

A new man-tailored biomimetic sensor for Chlorpromazine host-guest interactions and potentiometric transduction is presented. The artificial host was imprinted within methacrylic acid, 2-vinyl pyridine and 2-acrylamido-2-methyl-1-propanesulfonic acid based polymers. Molecularly imprinted particles were dispersed in 2-nitrophenyloctyl ether and entrapped in a poly(vinyl chloride) matrix. Slopes and detection limits ranged 51–67 mV/decade and 0.46–3.9 μg/mL, respectively, in steady state conditions. Sensors were independent fromthe pHof test solutionswithin 2.0–5.5.Good selectivitywas observed towards oxytetracycline, doxytetracycline, ciprofloxacin, enrofloxacin, nalidixic acid, sulfadiazine, trimethoprim, glycine, hydroxylamine, cysteine and creatinine. Analytical features in flowing media were evaluated on a double-channel manifold, with a carrier solution of 5.0×10−2 mol/L phosphate buffer. Near-Nernstian response was observed over the concentration range 1.0×10−4 to 1.0×10−2 mol/L. Average slopes were about 48 mV/decade. The sensors were successfully applied to field monitoring of CPZ in fish samples, offering the advantages of simplicity, accuracy, automation feasibility and applicability to complex samples.

Tetranuclear COPPER(II) complexes with macrocyclic and open-chain disiloxane ligands as catalyst precursors for hydrocarboxylation and oxidation of alkanes and 1-phenylethanol

Two new tetranuclear complexes [Cu-4(mu-O)(L-1)-Cl-4] and [Cu-4(mu(4)-O)(L-2)(2)Cl-4] (2), where H2L1 is a macrocyclic ligand resulting from [2+2] condensation of 2,6-diformy1-4-methylphanol (DFF) and 1,3-bis(aminopropy1)tetramethyldisiloxane, and HL2 is a 1:2 condensation product: of DFF with trimethylsilyl p-aminobenzoate, have been prepared. The structures of the products were established by Xray diffraction. The complexes have been characterised by FTIR, UV/Vis spectroscopy, ES1 mass-spectrometry and magnetic susceptibility measurements. The latter revealed that the letrftriuclear complexes can be descr bed as two ferromagnetically coupled dinuclear units, in which the two copper(II) ions interact antiferromacinetically. The ccimpi.iunds act as homogeneous catalyst precursors for a number of single-pot reactions, including (I) hydrocarbaxylation, with CO, H2O and K2S2O8, of a variety of linear and cyclic (n = 5-8) alkanes into the corresponding Cn+1 carboxylic acids, (ii) peroxidative oxidation of cyclohexane, and (iii) solvent-free microwave-assisted oxidation of 1-phenyletha.nol.