Spectrophotometric determination of arsenic in soil samples using 2-(5-bromo-2-pyridylazo)-5-di-ethylaminophenol (Br-PADAP)

Um novo método, simples e sensível para a determinação de arsênio em solo é proposto neste trabalho. Este método é baseado na redução de prata (I) e ferro (III) pela arsina seguida da reação de complexação do ferro (II) com o reagente espectrofotométrico 2-(5-bromo-2-piridilazo)-5-di-etilaminofenol (Br-PADAP). A determinação de arsênio apresentou uma sensitividade de Sandell de 3.1x10^-4 cm^-2, foi linear na faixa de 0.1 µg ml^-1 to 2.0 µg ml^-1 (r₅₆₀ = 0.9995), apresentou uma absortividade molar de 2.45x10⁵ l mol^-1 cm^-1 e um limite de detecção de 1.4 ng ml^-1 (3s) estes dados foram obtidos para 10 ml de amostra. A seletividade foi melhorada com o uso de EDTA com agente mascarante. O método proposto foi aplicado na determinação do arsênio na presença de outros íons e em amostras de solo. Os resultados revelaram que antimônio (III), mercúrio (II), germânio (IV), platina (IV) interferem na análise em todas as proporções analisadas. As interferências podem ser facilmente removidas pelo uso do EDTA. A precisão e a exatidão deram resultados satisfatórios, com desvio padrão relativo abaixo de 5%. As recuperações de arsênio em solo variaram de 95,55 a 102,70% com uma média de 99,63%. Estes resultados demonstraram que o método proposto é aplicável para a análise do arsênio em diferentes amostras de solo.

Síntese, caracterização e estudo de atividade biológica de complexos de prata(I) contendo ligantes baseados na 1,10-fenantrolina e tiouréia

Pós-graduação em Química - IQ

Novos complexos de 'PD'(II): síntese, caracterização e efeito dos ligantes na citotoxicidade e interação com DNA

Pós-graduação em Química - IQ

Espécies metalo-supramoleculares discretas polinucleares: sínteses e caracterização

Pós-graduação em Química - IQ

Novel europium and gadolinium complexes with methaneseleninate as ligand: Synthesis, characterization and spectroscopic study

The methaneseleninate and 1,10-phenanthroline were used as ligands in the synthesis of new lanthanide complexes. The photostability, emission quantum yield (q) and quantum efficiency (eta) of the D-5(0) emitting level of the Eu3+ ion were determined. An energy level diagram was used to establish the most relevant channels involved in the ligand-to-metal intramolecular energy transfer process. The nephelauxetic effect was investigated to assess the covalency of the ligand-metal chemical bond. The values of the experimental 4f-4f intensity parameters, suggest that this ion is in a chemical environment less polarisable than in the case of complexes with beta-diketonates as ligands. (C) 2011 Elsevier B.V. All rights reserved.

Modified CUPRAC spectrophotometric quantification of total polyphenol content in beer samples using Cu(II)/neocuproine complexes

Cu(II)/neocuproine (2,9-dimethyl-1,10-phenanthroline) complexes were utilized for spectrophotometric determination of total polyphenol content in beers. This procedure is based on the reduction of Cu(II) by polyphenols in hydroethanolic medium (pH 7.0) in the presence of neocuproine, yielding Cu(I)/complexes with maximum absorption at 454 nm. The sensitivity of the proposed method was compared with the AOAC method using tannic and gallic acid as standards. The average apparent molar absorptivity, in L cm(-1) mol(-1), of tannic acid (3.50 +/- 0.20) x 10(5) and gallic acid (5.12 +/- 0.21) x 10(4), was twice as high for the proposed method. A lower limit of detection (LOD) (2.9 x 10(-1) mg L-1) was found when tannic acid was used in the proposed method. Additionally, less interference from the most common additives in beers was noticed. Total content of polyphenols was analyzed in 17 Brazilian samples. Results ranged from 35.5 to 556 mg L-1 of tannic acid, with higher values for recovery rates (45.4-118%, mean 85.0%) than for gallic acid. Although tannic acid is a mixture of polygalloyl glucoses, the total polyphenol content found in the samples suggests that tannic acid should be used as a standard. This is the first attempt to use this particular copper complex to quantify total polyphenol content in beer samples. (C) 2012 Elsevier Inc. All rights reserved.

A Donor-Acceptor Tetrathiafulvalene Ligand Complexed to Iron(II): Synthesis, Electrochemistry, and Spectroscopy of Fe(phen)(2)(TTF-dppz)(PF6)(2)

The synthesis and photophysical properties of the complex Fe(phen)(2)(TTF-dppz)(2+) (TTF-dppz = 4',5'-bis-(propylthio)tetrathiafulvenylidipyrido3,2-a:2',3'-c-phenazine, phen = 1,10-phenanthroline) are described. In this complex, excitation into the metal ligand charge transfer bands results in the population of a high-spin state of iron(II), with a decay lifetime of approximately 1.5 ns, in dichloromethane, at room temperature. An intraligand charge transfer state can also be obtained and has a lifetime of 38 ps. A mechanism for the different states reached is proposed based on transient absorption spectroscopy.

Synthesis and testing of photoaffinity probes for the site-selectivechemical modifications of the 5-HT3 receptor

The 5-HT3 receptor (5-HT3R) is an important ion channel responsible for the transmission of nerve impulses in the central nervous system.1 It is difficult to characterize transmembrane dynamic receptors with classical structural biology approaches like crystallization and x-ray. The use of photoaffinity probes is an alternative approach to identify regions in the protein that are important for the binding of small molecules. Therefore we synthesized a small library of photoaffinity probes by conjugating photophores via various linkers to granisetron which is a known antagonist of the 5-HT3R. We were able to obtain several compounds with diverse linker lengths and different photolabile moieties that show nanomolar binding affinities for the orthosteric binding site. Furthermore we established a stable h5-HT3R expressing cell line and a purification protocol to yield the receptor in a high purity. Currently we are investigating the photo crosslinking of these ligands with the 5-HT3R.

Intraoperative monopolar mapping during 5-ALA-guided resections of glioblastomas adjacent to motor eloquent areas: evaluation of resection rates and neurological outcome.

OBJECT Resection of glioblastoma adjacent to motor cortex or subcortical motor pathways carries a high risk of both incomplete resection and postoperative motor deficits. Although the strategy of maximum safe resection is widely accepted, the rates of complete resection of enhancing tumor (CRET) and the exact causes for motor deficits (mechanical vs vascular) are not always known. The authors report the results of their concept of combining monopolar mapping and 5-aminolevulinic acid (5-ALA)-guided surgery in patients with glioblastoma adjacent to eloquent tissue. METHODS The authors prospectively studied 72 consecutive patients who underwent 5-ALA-guided surgery for a glioblastoma adjacent to the corticospinal tract (CST; < 10 mm) with continuous dynamic monopolar motor mapping (short-train interstimulus interval 4.0 msec, pulse duration 500 μsec) coupled to an acoustic motor evoked potential (MEP) alarm. The extent of resection was determined based on early (< 48 hours) postoperative MRI findings. Motor function was assessed 1 day after surgery, at discharge, and at 3 months. RESULTS Five patients were excluded because of nonadherence to protocol; thus, 67 patients were evaluated. The lowest motor threshold reached during individual surgery was as follows (motor threshold, number of patients): > 20 mA, n = 8; 11-20 mA, n = 13; 6-10 mA, n = 10; 4-5 mA, n = 13; and 1-3 mA, n = 23. Motor deterioration at postsurgical Day 1 and at discharge occurred in 30% (n = 20) and 10% (n = 7) of patients, respectively. At 3 months, 3 patients (4%) had a persisting postoperative motor deficit, 2 caused by vascular injury and 1 by mechanical injury. The rates of intra- and postoperative seizures were 1% and 0%, respectively. Complete resection of enhancing tumor was achieved in 73% of patients (49/67) despite proximity to the CST. CONCLUSIONS A rather high rate of CRET can be achieved in glioblastomas in motor eloquent areas via a combination of 5-ALA for tumor identification and intraoperative mapping for distinguishing between presumed and actual motor eloquent tissues. Continuous dynamic mapping was found to be a very ergonomic technique that localizes the motor tissue early and reliably.

Light-independent degradation of stromal proteins in intact chloroplasts isolated from Pisum sativum L. leaves: requirement for divalent cations

Intact chloroplasts were isolated from mature pea (Pisum sativum L.) leaves in order to study the degradation of several stromal proteins in organello. Changes in the abundances of ribulose-1,5-bisphosphate carboxylase/oxygenase (EC 4.1.1.39), phosphoribulokinase (EC 2.7.1.19), glutamine synthetase (EC 6.3.1.2) and ferredoxin-dependent glutamine:α-ketoglutarate aminotransferase (glutamate synthase; EC 1.4.7.1) were detected by sodium dodecyl sulfate-polyacrylamide gel electrophoresis followed by Coomassie-staining of the gels or immunoblotting using specific antibodies for the different enzymes. Degradation of several stromal proteins was strongly stimulated when intact chloroplasts were incubated in the light in the presence of dithiothreitol. Since free radicals may artificially accumulate in the chloroplast under such conditions and interfere with the stability of stromal proteins, the general relevance of these processes remains questionable. In the absence of light, proteolysis proceeded slowly in isolated chloroplasts and was not stimulated by dithiothreitol. Inhibition by ethylenediaminetetraacetic acid (EDTA), 1,10-phenanthroline or excess zinc ions as well as the requirement for divalent cations suggested that a zinc-containing metalloprotease participated in this process. Furthermore, light-independent degradation of ribulose-1,5-bisphosphate carboxylase/oxygenase and phosphoribulokinase was enhanced in chloroplasts isolated from leaves in which senescence was accelerated by nitrogen starvation. Our results indicate that light-independent stromal protein degradation in intact chloroplasts may be analogous to proteolysis that occurs in intact leaves during senescence.

Glassy objects from DSDP Hole 5-32 in the northeastern Pacific Ocean

Small glassy spheres, ellipsoids, teardrops, cylinders and dumbbells occur in large numbers in Tertiary deep sea clays cored in the northeastern Pacific by the Deep Sea Drilling Project. These objects morphologically resemble microtektites, but have the composition of an oceanic tholeiite. On the basis of their composition and stratigraphic relationship it is considered that they are of volcanic origin and most likely have been formed in deep water by submarine volcanic processes.

Relación entre capacidades físicas, Indice de Masa Corporal (IMC) y la discriminación dentro de la clase de educación física en alumnos de 10 y 11 años, en cuatro colegios de Chillan, Chile

Objetivo: verificar relación entre IMC, capacidades físicas y discriminación en clase de Educación Física, alumnos entre 10 a 11 años, 4 colegios de Chillán, Chile. Metodología: medir flexibilidad, velocidad y resistencia; calcular IMC; posteriormente contestar cuestionario de auto percepción frente a sus pares en relación a discriminación en clases de Educación Física. Población: 178 sujetos; muestra: 44 indicaron discriminación. Resultados: IMC: 72,6 por ciento de la muestra, que sienten discriminación, no presentan niveles de obesidad. Velocidad: 47,7 por ciento sujetos discriminados se encuentran sobre el promedio; demuestra que la velocidad es un factor que influye en la discriminación debido a que menos de la mitad de los alumnos discriminados se encuentran sobre el nivel de aprobación. Resistencia: 75 por ciento superior y 25 por ciento bajo el promedio lo que demuestra que la resistencia no es un factor determinante en la discriminación. Flexibilidad: 11 por ciento de los sujetos bajo el promedio y un 89 por ciento sobre el nivel de aprobación; se indica que la flexibilidad no es un factor determinarte en la discriminación. Los resultados indicaron que la relación de IMC y las capacidades físicas, en base a la discriminación en la clase de Educación Física, existe relación entre ambas, pero con resultados diferentes, ya que el índice de masa corporal en sujetos que presentan el rango de bajo peso y son discriminados, tienen mejor capacidad física que en alumnos de rango normal, riesgo de obesidad y obesidad

Relación entre capacidades físicas, Indice de Masa Corporal (IMC) y la discriminación dentro de la clase de educación física en alumnos de 10 y 11 años, en cuatro colegios de Chillan, Chile

Objetivo: verificar relación entre IMC, capacidades físicas y discriminación en clase de Educación Física, alumnos entre 10 a 11 años, 4 colegios de Chillán, Chile. Metodología: medir flexibilidad, velocidad y resistencia; calcular IMC; posteriormente contestar cuestionario de auto percepción frente a sus pares en relación a discriminación en clases de Educación Física. Población: 178 sujetos; muestra: 44 indicaron discriminación. Resultados: IMC: 72,6 por ciento de la muestra, que sienten discriminación, no presentan niveles de obesidad. Velocidad: 47,7 por ciento sujetos discriminados se encuentran sobre el promedio; demuestra que la velocidad es un factor que influye en la discriminación debido a que menos de la mitad de los alumnos discriminados se encuentran sobre el nivel de aprobación. Resistencia: 75 por ciento superior y 25 por ciento bajo el promedio lo que demuestra que la resistencia no es un factor determinante en la discriminación. Flexibilidad: 11 por ciento de los sujetos bajo el promedio y un 89 por ciento sobre el nivel de aprobación; se indica que la flexibilidad no es un factor determinarte en la discriminación. Los resultados indicaron que la relación de IMC y las capacidades físicas, en base a la discriminación en la clase de Educación Física, existe relación entre ambas, pero con resultados diferentes, ya que el índice de masa corporal en sujetos que presentan el rango de bajo peso y son discriminados, tienen mejor capacidad física que en alumnos de rango normal, riesgo de obesidad y obesidad

Relación entre capacidades físicas, Indice de Masa Corporal (IMC) y la discriminación dentro de la clase de educación física en alumnos de 10 y 11 años, en cuatro colegios de Chillan, Chile

Objetivo: verificar relación entre IMC, capacidades físicas y discriminación en clase de Educación Física, alumnos entre 10 a 11 años, 4 colegios de Chillán, Chile. Metodología: medir flexibilidad, velocidad y resistencia; calcular IMC; posteriormente contestar cuestionario de auto percepción frente a sus pares en relación a discriminación en clases de Educación Física. Población: 178 sujetos; muestra: 44 indicaron discriminación. Resultados: IMC: 72,6 por ciento de la muestra, que sienten discriminación, no presentan niveles de obesidad. Velocidad: 47,7 por ciento sujetos discriminados se encuentran sobre el promedio; demuestra que la velocidad es un factor que influye en la discriminación debido a que menos de la mitad de los alumnos discriminados se encuentran sobre el nivel de aprobación. Resistencia: 75 por ciento superior y 25 por ciento bajo el promedio lo que demuestra que la resistencia no es un factor determinante en la discriminación. Flexibilidad: 11 por ciento de los sujetos bajo el promedio y un 89 por ciento sobre el nivel de aprobación; se indica que la flexibilidad no es un factor determinarte en la discriminación. Los resultados indicaron que la relación de IMC y las capacidades físicas, en base a la discriminación en la clase de Educación Física, existe relación entre ambas, pero con resultados diferentes, ya que el índice de masa corporal en sujetos que presentan el rango de bajo peso y son discriminados, tienen mejor capacidad física que en alumnos de rango normal, riesgo de obesidad y obesidad