Evaluation of intramolecular energy transfer process in the lanthanide(III) bis- and tris-(TTA) complexes: Photoluminescent and triboluminescent behavior

This work reports the energy transfer mechanism process of [Eu(TTA)(2)(NO(3))(TPPO)(2)] (bis-TTA complex) and [Eu(TTA)(3)(TPPO)(2)] (tris-TTA complex) based on experimental and theoretical spectroscopic properties, where TTA = 2-thienoyltrifluoroacetone and TPPO = triphenylphosphine oxide. These complexes were synthesized and characterized by elemental analyses, infrared spectroscopy and thermogavimetric analysis. The theoretical complexes geometry data by using Sparkle model for the calculation of lanthanide complexes (SMLC) is in agreement with the crystalline structure determined by single-crystal X-ray diffraction analysis. The emission spectra for [Gd(TTA)(3)(TPPO)(2)] and [Gd(TTA)(2) (NO(3))(TPPO)(2)] complexes are associated to T -> S(0) transitions centered on coordinated TTA ligands. Experimental luminescent properties of the bis-TTA complex have been quantified through emission intensity parameters Omega(lambda)(lambda = 2 and 4), spontaneous emission rates (A(rad)), luminescence lifetime (tau), emission quantum efficiency (eta) and emission quantum yield (q), which were compared with those for tris-TTA complex. The experimental data showed that the intensity parameter value for bis-TTA complex is twice smaller than the one for tris-TTA complex, indicating the less polarizable chemical environment in the system containing nitrate ion. A good agreement between the theoretical and experimental quantum yields for both Eu(Ill) complexes was obtained. The triboluminescence (TL) of the [Eu(TTA)(2)(NO(3))(TPPO)(2)] complexes are discussed in terms of ligand-to-metal energy transfer. (c) 2007 Elsevier B.V. All fights reserved.

Simultaneous analysis of five antidepressant drugs using direct injection of biofluids in a capillary restricted-access media-liquid chromatography-tandem mass spectrometry system

Direct analysis, with minimal sample pretreatment, of antidepressant drugs, fluoxetine, imipramine, desipramine, amitriptyline, and nortriptyline in biofluids was developed with a total run time of 8 min. The setup consists of two HPLC pumps, injection valve, capillary RAM-ADS-C18 pre-column and a capillary analytical C 18 column connected by means of a six-port valve in backflush mode. Detection was performed with ESI-MS/MS and only 1 mu m of sample was injected. Validation was adequately carried out using FLU-d(5) as internal standard. Calibration curves were constructed under a linear range of 1-250 ng mL(-1) in plasma, being the limit of quantification (LOQ), determined as 1 ng mL(-1), for all the analytes. With the described approach it was possible to reach a quantified mass sensitivity of 0.3 pg for each analyte (equivalent to 1.1-1.3 fmol), translating to a lower sample consumption (in the order of 103 less sample than using conventional methods). (C) 2008 Elsevier B.V. All rights reserved.

A restricted curriculum for second language learners : a self-fulfilling teacher strategy?

The focus of this article is on relations between classroom interaction, curricular knowledge and student engagement in diverse classrooms. It is based on a study with ethnographic perspective in which two primary school classes in Sweden were followed for three years. The analysis draws on Halliday's Systemic Functional Linguistics. The results indicate that language use in the classrooms is on a basic everyday level and that high teacher control results in low-demanding tasks and low engagement among students. Interaction in the classrooms mainly consists of short talk-turns with fragmented language, frequent repairs and interruptions, while writing and reading consists of single words and short sentences. Although the classroom atmosphere is friendly and inclusive, second language students are denied necessary opportunities to develop curricular knowledge and Swedish at the advanced level, which they will need higher up in the school system. The restricted curriculum that these students are offered in school thus restricts their opportunities to school success. Thus, I argue for a more reflective and critical approach regarding language use in classrooms.

Photochemical Generation and Intramolecular Chemistry of β-Alkoxycarbenes

The photolytic phenanthrene-based precursors for both β-methoxycarbene and β-ethoxycarbene were synthesized with and without a deuterium label attached to the a carbon. The incorporation of this deuterium label allowed distinction between a 1, 2-H shift and a 1, 2-O shift pathway to the respective alkyl vinyl ether, without the influence of a primary kinetic isotope effect. Photolyses of these precursors gave rearrangement products of the expected β-alkoxycarbenes. In the case of β-methoxycarbene, no methyl vinyl ether was observed due to its volatility. However, the appearance of aldehyde peaks in the NMR spectra, from an apparent further rearrangement to acetaldehyde through an enol intermediate, indicated that a 1,2-H shift had occurred. Ethyl vinyl ether was isolated following the photolysis of the β-ethoxycarbene precursor. Quantification of the two pathways showed less than 2% undergoing an ethoxy shift to the ethyl vinyl ether. Yield experiments on this photolysis demonstrated a maximum yield of β-ethoxycarbene as 43%, though this decreased as the experiment continued. Computational work on the β-ethoxycarbene system indicates that the triplet scate is more stable than the singlet. In addition, the activation energy to the 1.2-H shift pathway is remarkably low and is clearly consistent with the observed overwhelming preference for this pathway in the experiment.

Síntese de novas bases de tröger, fluorescentes via transferência protônica intramolecular no estado excitado (ESIPT)

Neste trabalho, realizou-se a síntese e a caracterização de quatro novas bases de Tröger. Estes compostos pertencem à classe de heterociclos 2-hidroxifenibenzazóis, que caracterizam-se por apresentar uma forte emissão de fluorescência, devido à reação de transferência protônica intramolecular no estado excitado -ESIPT- por eles sofrrida quando excitados por luz ultravioleta. Os heterociclos sintetizadosapesentam ligações de hidrogênio intramolecular entrte o nitrogênio azólico e a hidroxila fenólica e um granded deslocamento de Stokes, características tíicas de compostos que sofrem a ESIPT. As bases de Tröger, que são quirais, são bem conhecidas como receptores moleculares devido a concavidade que estas moléculas apresentam, Os compostos obtidos são os primeiro exmeplos de bases de Tröger fluorescentes, via ESIP, na literatura, por isso, despertam grande interesse na síntese de sondas biológicas moleculares fluorescentes. A partir da resolução quiral das bases de Tröger, estas potencialmente podem vir a ser utilizadas como indutores quirais e/ou par ao reconhecimento enantiosseletivo do DNA. A resolução quiral foi feita para uma das bases de Tröger sintetizadas.

Espalhamento de luz estático e dinâmico em polímeros do tipo polimetacrilato, fluorescentes por transferência protônica intramolecular no estado eletrônico excitado (TPIEE)

As técnicas de espalhamento de luz estático e dinâmico foram utilizadas para a caracterização dos copolímeros de PMMA-benzazolas e do PMMA, em clorofórmio e THF nos regimes diluído e semi-diluído. Os copolímeros foram obtidos pela polimerização do metil-metacrilato na presença dos corantes orgânicos do tipo benzazolas, que caracterizam-se por apresentar uma intensa emissão de fluorescência através de um mecanismo de transferência protônica intramolecular no estado eletrônico excitado. Através da técnica de espalhamento de luz estático foram obtidos parâmetros macromoleculares como a massa molar ponderal média, o raio de giro e o segundo coeficiente virial, bem como o módulo osmótico reduzido e o parâmetro g, relacionado com a arquitetura do polímero em solução. Estes parâmetros indicam que os copolímeros e o PMMA em solução diluída comportam-se como cadeias lineares flexíveis e apresentam-se como esferas homogêneas em solução. Através da espectroscopia de correlação de fótons foram obtidas funções normalizadas de correlação temporal de intensidade correspondentes a um único processo dinâmico tanto para o PMMA como para os copolímeros em regime diluído, independentemente do solvente utilizado. Esta dinâmica corresponde à difusão das cadeias poliméricas em solução. Para as soluções em regime semi-diluído (5£c£30 g·L-1), as funções de correlação temporal de intensidade apresentaram um único decaimento exponencial correspondente a difusão cooperativa dos entrelaçamento das cadeias poliméricas em solução pode ser observado em ambos os solventes. O tempo de relaxação ( t) obtido sugere que o copolímero apresenta, neste regime de diluição, uma dinâmica diferente daquela observada para o PMMA. Portanto, a incorporação da benzazola na cadeia polimérica afeta a dinâmica do polímero tanto em THF como em clorofórmio. Para soluções contendo PMMA e o Copolímero 6 na concentração de 60 g·L-1 em THF observou-se o aparecimento de um segundo movimento, mais lento, nas funções normalizadas de correlação temporal de intensidade, sugerindo a formação de uma estrutura contínua em solução. O mesmo não ocorre utilizando-se clorofórmio como solvente.

General equilibrium model with restricted participation in financial markets

The paper analyses a general equilibrium model with financiaI markets in which households may face restrictions in trading financiaI assets such as borrowing constraints and collateral (restricted participation model). However, markets are not assumed to be incomplete. We consider a standard general equilibrium model with H > 1 households, 2 periods and S states of nature in the second period. We show that generically the set of equilibrium allocations ia indeterminate, provided the existence of at least one nominal asset and one household for who some restriction is binding. Suppose there are C > 1 commodities in each state of nature and assets pays in units of some commodity. In this case for each household with binding restrictions it is possible to reduce the set of feasible assets trading and obtain a new equilibrium that utility improve alI those households. There is however an upper bound on the number of households to be improved related to the number of states of nature and the number of commodities. In particular, if the number of households ia smaller than the number of states of nature it is possible to Pareto improve any equilibrium by reducing the feasible choice set for each household.

Geostatistical analysis of the spatial distribution of Rotylenchulus reniformis on cotton cultivated under crop rotation

The spatial distribution of Rotylenchulus reniformis on cotton cultivated in crop rotation with sorghum-peanut-velvetbean was studied using geostatistics. The experimental field, which had been continuously cropped with cotton for 20 years, comprised two 32 x 48 m-grids, each divided in sixty-four 4 x 6 in sampling plots. For all crops, 300 cm(3) soil samples were taken at the center of each plot at crop germination (Pi) and again at harvest (Pf), from which the numbers of nematodes were determined. The results revealed that the spatial distribution of R. reniformis was highly aggregated and with the aid of geostatistical techniques the nematode intensities were mapped and the risk areas accurately identified. Consequently, geostatistics is here considered a useful tool for planning nematode control strategies, particularly in precision agriculture.

Intercropping corn and kudzu in a rotation system with soybean

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Qualitative-feed-restricted heavy swine: meat quality and morpho-histochemical characteristics of muscle fibers

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Soil water retention and s index after crop rotation and chiseling

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Soybean root growth and yield in rotation with cover crops under chiseling and no-till

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Phosphorus and potassium balance in soil under crop rotation and fertilization

The use of crop rotation and manure application can provide sustainability for an agricultural production system by improving soil quality and increasing nutrient use efficiency. This study aimed to evaluate the effect of mineral, organic and mineral+organic fertilization on grain yield and on soil phosphorus and potassium balance, in two crop systems under no-till, with and without rotation of cover crops. The experiment was carried out from 2006 to 2008 on a clayey Rhodic Hapludox in Marechal Candido Rondon, Parana State, Brazil. The cropping sequence in the rotation system involving cover crops was black oat + hairy vetch + forage turnip/corn/pigeon pea/wheat/mucuna + brachiaria + sunn hemp, and in the succession system was wheat/corn/wheat/soybean. Organic and mineral+organic fertilizations consisted of the application of solely manure and manure combined with mineral fertilizer, respectively. Soil P and K balances were calculated after the second year of the experiment, up to a depth of 0.40 m. First year corn yields were higher in the crop succession system accompanied by mineral fertilization. In the second year, wheat and soybean yield did not vary between crop systems and nutrient sources, demonstrating the residual effect of crop rotation and manure use. Crop rotation with cover crops resulted in an increase in soil K levels by promoting the recycling of this nutrient in the soil. In both crop systems, the application of mineral and organic fertilizers - either in isolation or in combination - resulted in a negative soil P and K balance in the short term. This represents a threat to the sustainability of the agricultural production system in the long term, due to the depletion of soil nutrient reserves.