Lanthanide-Containing Light-Emitting Organic-Inorganic Hybrids: A Bet on the Future

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

Transparent Er3+-activated lead fluorogermanate glass ceramics

Transparent glass ceramics containing β-PbF2:Er 3+ nanocrystals were obtained through appropriate thermal treatments of a glass of molar composition 60PbGeO3-10PbF2-30CdF 2 doped with 0.5 mol% Er3+. Their optical properties, as well as upconversion processes among erbium ions in the glass and glass ceramic matrix were studied. From absorption spectra, Judd-Ofelt parameters and radiative transition rates for several excited levels were calculated. Emission spectra in the visible and NIR regions were collected, and stimulated emission cross sections were obtained by McCumber theory for the 4F 13/2→4I15/2 transition at 1.5 μm. Red and green upconversion emissions were measured in glass and glass ceramics upon excitation at 980 nm; lifetimes were measured in order to assess the upconversion mechanisms.

Giant enhancement of phonon-assisted one-photon excited frequency upconversion in a Nd3+-doped tellurite glass

Changing the sample's temperature from 200 K to 535 K, we observed 670-fold enhancement of a phonon-assisted upconversion emission at ≈754 nm obtained from a Nd3+-doped tellurite glass excited by 5 ns laser pulses at 805 nm. A rate-equation model, including the relevant energy levels and temperature dependent transition rates, is proposed to describe the process. The results fit well with the data when one considers the nonradiative transitions contributing for the 754 nm luminescence are promoted by an effective phonon mode with energy of 700 cm-1. © 2013 American Institute of Physics.

Nonmesonic weak decay dynamics from proton spectra of Lambda-hypernuclei

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

Transition metal rates in latosol twice treated with sewage sludge

A reciclagem agrícola do lodo de esgoto tem provocado o acúmulo de metais pesados no solo e na água, podendo atingir níveis tóxicos e causar danos às plantas cultivadas, aos animais e ao homem, por meio da cadeia trófica. Neste intuito foi desenvolvido o presente experimento, em condições de campo, entre 2000 e 2002, onde foram avaliados os efeitos da aplicação de lodo de esgoto por dois anos, sobre a extração de metais de transição (essenciais e não) pelo extrator DTPA em um Latossolo Vermelho distrófico (LVd) de textura média. As concentrações dos elementos metálicos: Mn, Fe, Cd, Ni, Co, Pb e Cr não foram detectados pelo método da absorção atômica na solução obtida com o extrator DTPA. A aplicação de lodo de esgoto causou inicialmente pequena elevação no pH do solo, posteriormente a diminuição do mesmo, e manteve-se próximo ao original. Foi possível concluir que, com a aplicação consecutiva do lodo, os teores extraíveis de Fe e Mn nas amostras de solos aumentaram gradativamente nos dois anos agrícolas, com as doses do lodo de esgoto aplicado, época de amostragens, e foram superiores ao tratamento testemunha. O extrator apresentou capacidade restrita para avaliação da fitodisponibilidade dos metais pesados decorrentes das baixas concentrações nas amostras de solo.

Configuration-dependent diffusion can shift the kinetic transition state and barrier height of protein folding

We show that diffusion can play an important role in protein-folding kinetics. We explicitly calculate the diffusion coefficient of protein folding in a lattice model. We found that diffusion typically is configuration- or reaction coordinate-dependent. The diffusion coefficient is found to be decreasing with respect to the progression of folding toward the native state, which is caused by the collapse to a compact state constraining the configurational space for exploration. The configuration- or position-dependent diffusion coefficient has a significant contribution to the kinetics in addition to the thermodynamic free-energy barrier. It effectively changes (increases in this case) the kinetic barrier height as well as the position of the corresponding transition state and therefore modifies the folding kinetic rates as well as the kinetic routes. The resulting folding time, by considering both kinetic diffusion and the thermodynamic folding free-energy profile, thus is slower than the estimation from the thermodynamic free-energy barrier with constant diffusion but is consistent with the results from kinetic simulations. The configuration- or coordinate-dependent diffusion is especially important with respect to fast folding, when there is a small or no free-energy barrier and kinetics is controlled by diffusion. Including the configurational dependence will challenge the transition state theory of protein folding. The classical transition state theory will have to be modified to be consistent. The more detailed folding mechanistic studies involving phi value analysis based on the classical transition state theory also will have to be modified quantitatively.

Study of the thermal behavior of the transition phase of Co(II)-diclofenac compound by non-isothermal method

The Co(II)-diclofenac complex was evaluated by simultaneous thermogravimetry-differential thermal analysis (TG-DTA) and differential scanning calorimetry (DSC). The DTA curve profile shows one exothermic peak because of the transition phase of the compound between 170 and 180 A degrees C, which was confirmed by X-ray powder diffractometry. The transition phase behavior was studied by DSC curves at several heating rates of a sample mass between 1 and 10 mg in nitrogen atmosphere and in a crucible with and without a lid. Thus, the kinetic parameters were evaluated using an isoconversional non-linear fitting proposed by Capela and Ribeiro. The results show that the activation energy and pre-exponential factor for the transition phase is dependant on the different experimental conditions. Nevertheless, these results indicate that the kinetic compensation effect shows a relationship between them.

Ingestive behavior and performance of female lambs grazing on Marandu palisadegrass under different stocking rates

The ingestive behavior and performance of female lambs grazing on Marandu pasture submitted to different stocking rates during the rainy and transition season were evaluated. The experimental area with 4,500 m² was divided into 45 paddocks of 100 m². Twenty-seven Santa Ines female lambs (purebred) with 4 months age and 22 kg of initial body weight were distributed in a completely randomized design, with nine replicates. Lambs were divided into 9 groups with the same initial weight and submitted to three stocking rates: 2, 3 and 4 lambs/paddock, which corresponded to 40, 60 and 80 lambs/ha, respectively. Each group of animals had a module of five paddocks, managed on intermittent grazing system, with 7 days of occupation and 28 d of rest. Increase on time grazing and reduction on time ruminating and resting were observed as stocking rates increased. There was 14% raise in time grazing and 41% decline on time resting by lambs subjected to the highest stocking rate compared with those in the lower stocking rate. The number of animals/ha promoted linear effect on average daily gain, which was higher for animals in the lowest stocking rate of 90 g/d. For gain per area, the best result was obtained with 60 animals/ha featuring an average value of 426 kg/ha.

Liming in the transition to no-till under a wheat-soybean rotation

Soil and subsoil aluminium toxicity has been one of the main limiting factors for soybean and wheat yields in tropical soils. Usually liming is the most effective way to deal with soil acidity and Al toxicity, but in no-till systems the soil is not disturbed making it impossible to incorporate lime in the arable layer, and lime has been usually applied on the soil surface. In this paper soybean and wheat responses to lime applied on the soil surface and/or incorporated in the soil arable layer were evaluated during the transition from conventional tillage to a no-till system. The experiment was conducted for 3 years in Parana, Brazil, using a wheat-soybean rotation. Lime rates ranging from 0.0 to 9.0 t ha(-1) were incorporated down to 20 cm and 4.5 t ha(-1) were spread or not on the soil surface. Soil samples were taken down to 60 cm, 39 months after the first lime application. Soil chemical characteristics were affected by lime application down to 60 cm deep in the profile. Soybean responded to lime irrespective of application method, but the highest accumulated yield was obtained when lime was incorporated into the arable layer. For wheat, the more sensitive the cultivar, the greater was the response to lime. During the introduction of a no-till system, lime must be incorporated into the arable layer when the wheat cultivar is Al-sensitive. (C) 2007 Elsevier B.V. All rights reserved.

Phase transition in poly(vinylidene fluoride) investigated with micro-Raman spectroscopy

The phase transition from the non-polar a-phase to the polar beta-phase of poly(vinylidene fluoride) (PVDF) has been investigated using micro-Raman spectroscopy, which is advantageous because it is a nondestructive technique. Films of alpha-PVDF were subjected to stretching under controlled rates at 80 degrees C, while the transition to P-PVDF was monitored by the decrease in the Raman band at 794 cm(-1) characteristic of the a-phase, along with the concomitant increase in the 839 cm-1 band characteristic of the P-phase. The alpha ->beta transition in our PVDF samples could be achieved even for the sample stretched to twice (2 X -stretched) the initial length and it did not depend on the stretching rate in the range between 2.0 and 7.0 mm/min. These conclusions were corroborated by differential scanning calorimetry (DSC) and X-ray diffraction experiments for PVDF samples processed under the same conditions as in the Raman scattering measurements. Poling with negative corona discharge was found to affect the a-PVDF morphology, improving the Raman bands related to this crystalline phase. This effect is minimized for films stretched to higher ratios. Significantly, corona-induced effects could not be observed with the other experimental techniques, i.e., X-ray diffraction and infrared spectroscopy.

The investigation of alpha -> beta phase transition in poly(vinylidene fluoride) (PVDF)

The phase transition from the non-polar a-phase to the polar beta-phase of poly(vinylidene fluoride) (PVDF) has been investigated using micro-Raman spectroscopy, which is advantageous for being a non-destructive technique. Films of alpha-PVDF were subjected to stretching under controlled rates and at 80 degrees C, the transition to beta-PVDF being monitored by the decrease in the Raman band at 794 cm(-1) characteristic of the a-phase, with the concomitant increase in the 839 cm(-1) band characteristic of the beta-phase. Poling with negative corona discharge was found to affect the alpha-PVDF morphology improving the Raman bands related to this crystalline phase. This effect is minimized for films stretched to higher ratios. Significantly, corona-induced effects could not be observed with the other experimental techniques, viz. X-ray diffraction and infrared spectroscopy.

Sedimentation rates of tripton in Jurumirim Reservoir (São Paulo, Brazil)

Sedimentation rates of particulate material and some physicochemical parameters of water were determined in October, January, April and July 1990-91 at seven stations in the Jurumirim Reservoir (São Paulo, Brazil), three located in the Paranapanema arm, three in the Taquari arm and one near the dam. Higher sedimentation rates of tripton were found in the Paranapanema arm, followed by those from the Taquari arm and the dam. Suspended matter (2.5-48.7 mg · 1-1) and chlorophyll-a (0.7-8.1 mg · m-3) concentrations in the Paranapanema arm were in general higher resulting in lower water transparency (0.3-1.7m) than in the Taquari arm. Temporal and spatial variations in the tripton sedimentation rates were mainly influenced by allochthonous input at the stations near the river mouth. The settling fluxes at station near the dam of the reservoir were affected rather by a small autochthonous production (65 g C ass m-2 ;yr-1), indicated by a higher organic content (64-87%). Therefore, sedimentation rates measured by bottom traps were affected by sediment ressuspension especially at isothermal conditions. With respect to sedimentation, the riverine, the transition and the lacustrine zones commonly found in reservoires could be distinguished. The extent of the riverine zone in each arm of the Jurumirim Reservoir depends on the seasonal change of allochthonous input.

The investigation of α→β phase transition in poly(vinylidene fluoride) (PVDF)

The phase transition from the non-polar α-phase to the polar β-phase of poly(vinylidene fluoride) (PVDF) has been investigated using micro-Raman spectroscopy, which is advantageous for being a non-destructive technique. Films of α-PVDF were subjected to stretching under controlled rates and at 80°C, the transition to β-PVDF being monitored by the decrease in the Raman band at 794 cm-1 characteristic of the α-phase, with the concomitant increase in the 839 cm-1 band characteristic of the β-phase. Poling with negative corona discharge was found to affect the a-PVDF morphology improving the Raman bands related to this crystalline phase. This effect is minimized for films stretched to higher ratios. Significantly, corona-induced effects could not be observed with the other experimental techniques, viz. X-ray diffraction and infrared spectroscopy.