1,4-Diamino-2-butanone, a wide-spectrum microbicide, yields reactive species by metal-catalyzed oxidation

The alpha-aminoketone 1,4-diamino-2-butanone (DAB), a putrescine analogue, is highly toxic to various microorganisms, including Trypanosoma cruzi. However, little is known about the molecular mechanisms underlying DAB`s cytotoxic properties. We report here that DAB (pK(a) 7.5 and 9.5) undergoes aerobic oxidation in phosphate buffer, pH 7.4, at 37 degrees C, catalyzed by Fe(II) and Cu(II) ions yielding NH(4)(+) ion, H(2)O(2), and 4-amino-2-oxobutanal (oxoDAB). OxoDAB, like methylglyoxal and other alpha-oxoaldehydes, is expected to cause protein aggregation and nucleobase lesions. Propagation of DAB oxidation by superoxide radical was confirmed by the inhibitory effect of added SOD (50 U ml(-1)) and stimulatory effect of xanthine/xanthine oxidase, a source of superoxide radical. EPR spin trapping studies with 5,5-dimethyl-1-pyrroline-1-oxide (DMPO) revealed an adduct attributable to DMPO-HO(center dot), and those with alpha-(4-pyridyl-1-oxide)-N-tert-butylnitrone or 3,5-dibromo-4-nitrosobenzenesulfonic acid, a six-line adduct assignable to a DAB(center dot) resonant enoyl radical adduct. Added horse spleen ferritin (HoSF) and bovine apo-transferrin underwent oxidative changes in tryptophan residues in the presence of 1.0-10 mM DAB. Iron release from HoSF was observed as well. Assays performed with fluorescein-encapsulated liposomes of cardiolipin and phosphatidylcholine (20:80) incubated with DAB resulted in extensive lipid peroxidation and consequent vesicle permeabilization. DAB (0-10 mM) administration to cultured LLC-MK2 epithelial cells caused a decline in cell viability, which was inhibited by preaddition of either catalase (4.5 mu M) or aminoguanidine (25 mM). Our findings support the hypothesis that DAB toxicity to several pathogenic microorganisms previously described may involve not only reported inhibition of polyamine metabolism but also DAB pro-oxidant activity. (C) 2011 Elsevier Inc. All rights reserved.

The use of a gold disc microelectrode for the determination of copper in human sweat

A novel approach of using a gold disc microelectrode to analyze sweat samples for copper ions by anodic square wave stripping voltammetry (SW stripping voltammetry) is described Sweat was collected from the lower back of four subjects after physical exercise and the sample volume required for the determinations was 100 mu L. Under the optimized conditions the calibration plot was linear over the range 1-100 mu mol L(-1) Cu(II) with a limit of detection of 0 25 mu mol L(-1) The precision was evaluated by carrying out five replicate measurements in a 1 mu mol L(-1) Cu(II) solution and the standard deviation was found to be 1 5% Measurements were performed by inserting the microelectrode into sweat drops and Cu(II) concentrations in the analyzed samples ranged from 09 to 28 mu mol L(-1) Values obtained by the proposed voltammetric method agreed well with those found using graphite furnace atomic absorption spectroscopy (GFAAS) (C) 2010 Elsevier B V All rights reserved

Supramolecular assemblies of a new class of nonplanar cationic metalloporphyrins and anionic metallophthalocyanines

The heteroaggregation behavior between a new class of nonplanar cationic beta-octabrominated meso-alkylpyridinium zinc(II)-porphyrins (beta-Br(8)(ZnP)) and anionic tetrasulfonated metallophthalocyanines (MTSPc, M = Ni(II) and Cu(II)) has been studied by UV-Vis electronic spectroscopy, in dimethylsulfoxide (DMSO) solution. The heteroaggregate stoichiometry and the association constants were determined by means of Job plots. Dimers and unexpected trimers, taking into account the existence of axially coordinated DMSO molecules to the central metal in both beta-Br(8)(ZnP) and MTSPc complexes, are formed in solution. The spectroscopic properties of the heteroaggregates are markedly different from those observed in the correspondent planar cationic derivatives, the heteroaggregates showing major changes predominantly in the beta-Br(8)(ZnP) Soret band region and minor effects in the MTSPc Q bands. The observed changes in the Soret band region (red/blue shifts, decrease in the absorption intensities) depend on the nature of the alkyl substituent attached to the meso-pyridinium group. The greater versatility of the nonplanar porphyrins accommodating the meso-substituents in out-of-plane and in-plane conformations is proposed to explain the observed stoichiometries and the differences on the heteroaggregates spectroscopic properties for each beta-Br(8)(ZnP) compound. The likely conformations assumed by the meso-substituents in these beta-Br(8)(ZnP) compounds and its spectroscopic characteristics are in accordance with the participation of the substituents as the main factor on the extent of the observed red-shifted spectra in nonplanar porphyrins. The obtained association constants (K(IP)) for the dimers and trimers are lower than those previously found for the similar planar cationic porphyrin systems, due to the lack of extensive pi-pi interactions and to the less effective approximation between the ionic groups, resulting in loosened heteroaggregates, particularly for the trimeric systems. Furthermore, the experimental results suggest that the NiTSPc is more distorted in DMSO solution than the CuTSPc derivative, favoring the interaction with the nonplanar beta-Br(8)(ZnP) compounds. (C) 2007 Elsevier B.V. All rights reserved.

Raman, IR, UV-vis and EPR characterization of two copper dioxolene complexes derived from L-dopa and dopamine

The anionic complexes [Cu(L(1-))(3)](1-), L(-) = dopasemiquinone or L-dopasemiqui none, were prepared and characterized. The complexes are stable in aqueous solution showing intense absorption bands at ca. 605 nm for Cu(II)-L-dopasemiquinone and at ca. 595 nm for Cu(II)-dopasemiquinone in the UV-vis spectra, that can be assigned to intraligand transitions. Noradrenaline and adrenaline, under the same reaction conditions, did not yield Cu-complexes, despite the bands in the UV region showing that noradrenaline and adrenaline were oxidized during the process. The complexes display a resonance Raman effect, and the most enhanced bands involve ring modes and particularly the vCC + vCO stretching mode at ca. 1384 cm(-1). The free radical nature of the ligands and the oxidation state of the Cu(II) were confirmed by the EPR spectra that display absorptions assigned to organic radicals with g= 2.0005 and g = 2.0923, and for Cu(II) with g = 2.008 and g = 2.0897 for L-dopasemiquinone and dopasemiquinone, respectively. The possibility that dopamine and L-dopa can form stable and aqueous-soluble copper complexes at neutral pH, whereas noradrenaline and adrenaline cannot, may be important in understanding how Cu(II)-dopamine crosses the cellular membrane as proposed in the literature to explain the role of copper in Wilson disease. (c) 2008 Elsevier B.V. All rights reserved.

Evaluation of a carbon paste electrode modified with organofunctionalised SBA-15 nanostructured silica in the simultaneous determination of divalent lead, copper and mercury ions

The performance of a carbon paste electrode (CPE) modified with SBA-15 nanostructured silica organofunctionalised with 2-benzothiazolethiol in the simultaneous determination of Pb(II), Cu(II) and Hg(II) ions in natural water and sugar cane spirit (cachaca) is described. Pb(II), Cu(II) and Hg(II) were pre-concentrated on the surface of the modified electrode by complexing with 2-benzothiazolethiol and reduced at a negative potential (-0.80 V). Then the reduced products were oxidised by DPASV procedure. The fact that three stripping peaks appeared on the voltammograms at the potentials of -0.48 V (Pb2+), -0.03 V (Cu2+) and +0.36 V (Hg2+) in relation to the SCE, demonstrates the possibility of simultaneous determination of Pb2+, Cu2+ and Hg2+. The best results were obtained under the following optimised conditions: 100 mV pulse amplitude, 3 min accumulation time, 25 mV s(-1) scan rate in phosphate solution pH 3.0. Using such parameters, calibration graphs were linear in the concentration ranges of 3.00-70.0 x 10(-7) mol L-1 (Pb2+), 8.00-100.0 X 10(-7) mol L-1 (Cu2+) and 2.00-10.0 x 10(-6) mol L-1 (Hg2+). Detection limits of 4.0 x 10(-8) mol L-1 (Pb2+), 2.0 x 10(-7) mol L-1 (Cu2+) and 4.0 x 10(-7) mol L-1 (Hg2+) were obtained at the signal noise ratio (SNR) of 3. The results indicate that this electrode is sensitive and effective for simultaneous determination of Pb2+, Cu2+ and Hg2+ in the analysed samples. (C) 2008 Published by Elsevier B.V.

Microbial distribution in the root canal system after periapical lesion induction using different methods

The aim of this study was to evaluate the microbial distribution in the root canal system after periapical lesion induction in dogs' teeth using different methods. Fifty-two root canals were assigned to 4 groups (n=13). Groups I and II: root canals were exposed to the oral cavity for 180 days; groups III and IV: root canals were exposed for 7 days and then the coronal openings were sealed for 53 days. The root apices of groups I and III were perforated, while those of groups II and IV remained intact. After the experimental periods, the animals were euthanized and the anatomic pieces containing the roots were processed and stained with the Brown & Brenn method to assess the presence and distribution of microorganisms. The incidence of microorganisms at different sites of the roots and periapical lesions was analyzed statistically by the chi-square test at 5% significance level. All groups presented microorganisms in the entire root canal system. A larger number of microorganisms was observed on the root canal walls, apical delta and dentinal tubules (p<0.05), followed by cementum and cemental resorption areas. In spite of the different periods of exposure to the oral environment, the methods used for induction of periapical periodontitis yielded similar distribution of microorganisms in the root canal system.

Microleakage in conservative cavities varying the preparation method and surface treatment

OBJECTIVE: To assess microleakage in conservative class V cavities prepared with aluminum-oxide air abrasion or turbine and restored with self-etching or etch-and-rinse adhesive systems. Materials and Methods: Forty premolars were randomly assigned to 4 groups (I and II: air abrasion; III and IV: turbine) and class V cavities were prepared on the buccal surfaces. Conditioning approaches were: groups I/III - 37% phosphoric acid; groups II/IV - self-priming etchant (Tyrian-SPE). Cavities were restored with One Step Plus/Filtek Z250. After finishing, specimens were thermocycled, immersed in 50% silver nitrate, and serially sectioned. Microleakage at the occlusal and cervical interfaces was measured in mm and calculated by a software. Data were subjected to ANOVA and Tukey's test (α=0.05). RESULTS: Marginal seal provided by air abrasion was similar to high-speed handpiece, except for group I. There was SIGNIFICANT difference between enamel and dentin/cementum margins for to group I and II: air abrasion. The etch-and-rinse adhesive system promoted a better marginal seal. At enamel and dentin/cementum margins, the highest microleakage values were found in cavities treated with the self-etching adhesive system. At dentin/cementum margins, high-speed handpiece preparations associated with etch-and-rinse system provided the least dye penetration. CONCLUSION: Marginal seal of cavities prepared with aluminum-oxide air abrasion was different from that of conventionally prepared cavities, and the etch-and-rinse system promoted higher marginal seal at both enamel and dentin margins.

Qualidade da carne de suínos de três linhagens genéticas comerciais em diferentes pesos de abate

O objetivo deste trabalho foi determinar as características de qualidade da carne de suínos de diferentes linhagens genéticas, em diferentes pesos de abate. Neste estudo foram utilizados 88 suínos por linhagem, fêmeas e machos castrados, com idade e peso médio iniciais de 74 dias e 30kg, respectivamente, pertencentes a três linhagens genéticas distintas, designadas de AgroceresPic, Dalland e Seghers. A etapa experimental foi dividida em quatro fases (Crescimento I, Crescimento II, Terminação I e Terminação II). Ao final de cada etapa, foram abatidos 60 animais (10 por linhagem/sexo), para as análises de qualidade da carne. O pH e a temperatura foram determinados a 1 e 24 horas post mortem. Foram retiradas amostras para as determinações de cor, perda de água por exsudação (PAE), perda de água por cocção (PAC) e força de Cisalhamento. As amostras provenientes das carcaças dos animais da linhagem AgroceresPic e Dalland apresentaram valores médios de PAE superiores aos da linhagem Seghers. Os valores médios de PAC foram diferentes entre as diferentes fases. Na fase Crescimento II, as carnes provenientes das carcaças das fêmeas Dalland foram mais duras, ou seja, com maiores valores de força de cisalhamento, que as carnes dos machos. Entretanto, na linhagem Seghers, as carnes dos machos foram mais duras. Observou-se diferença de L* entre os sexos da linhagem AgroceresPic nas fases Terminação I e II e, na linhagem Dalland, na Terminação II. As linhagens Dalland e Seghers apresentaram carnes com resultados superiores de a*, parâmetro característico da cor vermelha (a*>0). Pode-se concluir, portanto, que as características de qualidade da carne de suínos (pH, perda de água por exsudação, cor e maciez) podem variar entre grupos genéticos, entre sexos e entre diferentes pesos ao abate.

Características de carcaça de suínos de três linhagens genéticas em diferentes idades ao abate

O objetivo deste trabalho foi estudar as características da carcaça de suínos de diferentes linhagens genéticas, em diferentes idades ao abate. Foram utilizados 88 suínos por linhagem, fêmeas e machos castrados, com idade e peso médio iniciais de 74 dias e 30kg, respectivamente, pertencentes a três linhagens genéticas distintas, designadas de AgroceresPic, Dalland e Seghers. A etapa experimental foi dividida em quatro fases (Crescimento I, Crescimento II, Terminação I e Terminação II). Ao final de cada etapa, foram abatidos 60 animais (10 por linhagem/sexo), para as caracterizações: Peso (PCQ) e Rendimento de Carcaça Quente (RCQ), Área de Olho de Lombo (AOL) e Espessura de Toucinho (ET). Na análise dos resultados foi utilizado um delineamento inteiramente casualizado com desdobramento dos graus de liberdade em esquema fatorial 4 x 3 x 2, sendo quatro idades ao abate (90, 119, 150 e 186 dias), três linhagens (AgroceresPic, Dalland e Seghers) e dois sexos (fêmea e macho castrado), com 10 repetições por tratamento, sendo utilizado o pacote PROC MIXED do Softwear SAS. Os valores médios de peso vivo apresentaram diferença entre as linhagens e interação entre fase e linhagem (P<0,05). Os valores médios das demais variáveis estudadas apresentaram diferença e a interação (P<0,05) entre fase, linhagem e sexo, sendo que de maneira geral as principais diferenças ocorreram a partir da fase de Terminação I, em que as fêmeas das linhagens AgroceresPic e Dalland apresentaram melhores resultados (P<0,05) de RCQ (80,4 e 80,7%, respectivamente) em comparação com os machos (78,8 e 78,7%, respectivamente) e além disso as fêmeas Dalland apresentaram valores superiores (P<0,01) de AOL e ET (45,7cm² e 11,4mm x 38,3cm² e 18,3mm). Conclui-se que as linhagens genéticas avaliadas apresentaram características de carcaça muito interessantes para o mercado atual e que as fêmeas suínas podem ser utilizadas em programas que visem o abate de animais mais pesados.

Avaliação audiológica pré-cirurgia otológica de indivíduos com fissura labiopalatina operada

OBJETIVO: descrever as características audiológicas de indivíduos com fissura labiopalatina operada (FLP) e indicação de cirurgia otológica, comparando os grupos quanto ao tipo e grau da perda auditiva, bem como a curva timpanométrica. MÉTODOS: análise de 150 prontuários, ambos os gêneros, idade igual ou superior a 4 anos, FLP e indicação de cirurgia otológica, divididos em 3 grupos: I - Tubo de ventilação (TV), II - Timpanoplastia e III - Timpanomastoidectomia, analisando aspectos quanto a entrevista audiológica, audiometria tonal limiar e imitanciometria. RESULTADOS: o grupo I apresentou porcentagem maior de cirurgia bilateral (86%), o que não ocorreu nos demais grupos. Na entrevista audiológica, 83% apresentou algum tipo de queixa auditiva, sendo a mais frequente a perda auditiva (64%) com p<0,05 entre os grupos I e II; I e III. O tipo de perda auditiva de maior ocorrência foi condutivo bilateral (56%) seguido de unilateral (35%), com p<0,05 entre os grupos I e II; I e III. A perda de grau leve unilateral foi a de maior ocorrência (41%), seguida de grau leve a moderada bilateral (20%), com p<0,05 entre os três grupos. A curva timpanométrica mais frequente foi a do tipo B bilateral (39%) com p<0,05 entre os três grupos. CONCLUSÃO: a maioria dos indivíduos apresentou algum tipo de queixa na entrevista audiológica e alterações na audiometria tonal limiar e imitanciometria. A maioria dessas alterações foi compatível com problemas de orelha média, com perda auditiva do tipo condutiva, de grau leve e bilateral, independentemente da indicação cirúrgica.

Influência do treinamento físico aeróbio no transporte mitocondrial de ácidos graxos de cadeia longa no músculo esquelético: papel do complexo carnitina palmitoil transferase

O ácido graxo (AG) é uma importante fonte de energia para o músculo esquelético. Durante o exercício sua mobilização é aumentada para suprir as necessidades da musculatura ativa. Acredita-se que diversos pontos de regulação atuem no controle da oxidação dos AG, sendo o principal a atividade do complexo carnitina palmitoil transferase (CPT), entre os quais três componentes estão envolvidos: a CPT I, a CPT II e carnitina acilcarnitina translocase. A função da CPT I durante o exercício físico é controlar a entrada de AG para o interior da mitocôndria, para posterior oxidação do AG e produção de energia. Em resposta ao treinamento físico há um aumento na atividade e expressão da CPT I no músculo esquelético. Devido sua grande importância no metabolismo de lipídios, os mecanismos que controlam sua atividade e sua expressão gênica são revisados no presente estudo. Reguladores da expressão gênica de proteínas envolvidas no metabolismo de lipídios no músculo esquelético, os receptores ativados por proliferadores de peroxissomas (PPAR) alfa e beta, são discutidos com um enfoque na resposta ao treinamento físico.

As técnicas NASVD e MNF e sua aplicação na redução de ruídos em dados gamaespectrométricos

A desintegração radioativa é um processo aleatório e a estimativa de todas as medidas associadas é governada por leis estatísticas. Os perfis de taxas de contagem são sempre "ruidosos" quando utilizados períodos curtos como um segundo para cada medida. Os filtros utilizados e posteriormente as correções feitas no processamento atual de dados gamaespectrométricos não são suficientes para remover ou diminuir, consideravelmente, o ruído oriundo do espectro. Dois métodos estatísticos que atuam diretamente nos dados coletados, isto é, nos espectros, vêm sendo sugeridos na literatura para remover e minimizar estes ruídos remanescentes o Noise-Adjusted Singular Value Decomposition - NASVD e Maximum Noise Fraction - MNF. Estes métodos produzem uma redução no ruído de forma significativa. Neste trabalho eles foram implementados dentro do ambiente de processamento do software Oasis Montaj e aplicados na área compreendida pelos blocos I e II do levantamento aerogeofísico que recobre a porção oeste da Província Mineral do Tapajós, entre os Estados do Pará e Amazonas. Os dados filtrados e não-filtrados com as técnicas de NASVD e MNF foram processados com os parâmetros e constantes fornecidos pela empresa Lasa Engenharia e Prospecções S.A., sendo estes comparados. Os resultados da comparação entre perfis e mapas apresentaram-se de forma promissora, pois houve um ganho na resolução dos produtos.

Evaluation of the diffusion capacity of calcium hydroxide pastes through the dentinal tubules

This study aimed to evaluate the diffusion capacity of calcium hydroxide pastes with different vehicles through dentinal tubules. The study was conducted on 60 extracted single-rooted human teeth whose crowns had been removed. The root canals were instrumented and divided into 4 groups according to the vehicle of the calcium hydroxide paste: Group I - distilled water; Group II - propylene glycol; Group III - 0.2% chlorhexidine; Group IV - 2% chlorhexidine. After placement of the root canal dressings, the teeth were sealed and placed in flasks containing deionized water. After 1, 2, 7, 15, 30, 45 and 60 days, the pH of the water was measured to determine the diffusion of calcium hydroxide through the dentinal tubules. The data were recorded and statistically compared by the Tukey test. The results showed that all pastes presented a similar diffusion capacity through dentin. Group IV did not present difference compared to group I. Group II presented difference compared to the other groups, as did Group III. In conclusion, groups I and IV presented a better diffusion capacity through dentin than groups II and III; 2% chlorhexidine can be used as a vehicle in calcium hydroxide pastes.

Thermal behavior and decomposition kinetics of rifampicin polymorphs under isothermal and non-isothermal conditions

The thermal behavior of two polymorphic forms of rifampicin was studied by DSC and TG/DTG. The thermoanalytical results clearly showed the differences between the two crystalline forms. Polymorph I was the most thermally stable form, the DSC curve showed no fusion for this species and the thermal decomposition process occurred around 245 ºC. The DSC curve of polymorph II showed two consecutive events, an endothermic event (Tpeak = 193.9 ºC) and one exothermic event (Tpeak = 209.4 ºC), due to a melting process followed by recrystallization, which was attributed to the conversion of form II to form I. Isothermal and non-isothermal thermogravimetric methods were used to determine the kinetic parameters of the thermal decomposition process. For non-isothermal experiments, the activation energy (Ea) was derived from the plot of Log β vs 1/T, yielding values for polymorph form I and II of 154 and 123 kJ mol-1, respectively. In the isothermal experiments, the Ea was obtained from the plot of lnt vs 1/T at a constant conversion level. The mean values found for form I and form II were 137 and 144 kJ mol-1, respectively.

Desenvolvimento dos ovários da lagosta Panulirus echinatus (Crustacea: Palinuridae) baseados nas análises macroscópica, microscópica e relação gonadossomática (RGS)

Os estádios de desenvolvimento dos ovários da lagosta Panulirus echinatus Smith, 1869 foram caracterizados com base nos aspectos macroscópicos, microscópicos e na relação gonadossomática (RGS). Através de amostragem mensal (novembro/1999 a outubro/2000) foram capturadas 711 fêmeas, empregando-se redes de espera de fundo. Retirou-se a região dorsal da carapaça para avaliação dos ovários. Estes foram dissecados, pesados, fixados em solução de Bouin e submetidos aos procedimentos histológicos. A análise microscópica dos ovários foi avaliada pela presença de células germinativas nas diferentes fases de desenvolvimento. Esta análise quando associada a macroscopia (mudança de cor e volume das gônadas no cefalotórax) e a relação gonadossomática (RGS) possibilitou a caracterização de cinco estádios de desenvolvimento: imaturo (I), em desenvolvimento (II), pré-maturação (III), maduro (IV) e pós-desova (V). As análises estatísticas confirmaram que a RGS pode ser utilizada como indicadora dos estádios de maturidade.