Energy transfer processes in Yb(3+)-Tm(3+) co-doped sodium alumino-phosphate glasses with improved 1.8 mu m emission

Sodium alumino-phosphate glasses co-doped with Yb(3+) and Tm(3+) ions have been prepared with notably low OH(-) content, and characterized from the viewpoint of their spectroscopic properties. In these glasses, Yb(3+) acts as an efficient sensitizer of excitation energy at 0.98 mu m - which can be provided by high power and low cost diode lasers, and subsequently undergoes non-resonant energy transfer to Tm(3+) ions ((2)F(5/2), (3)H(6) --> (2)F(7/2), (3)H(5)). Through this process, the emitting level (3)F(4) is rapidly populated, generating improved emission at 1.8 mu m ((3)F(4) --> (3)H(6)). In order to guarantee the efficiency of such favorable energy transfer, energy losses via multiphonon decay, Yb-Yb radiative trapping, and non- radiative transfer to OH(-) groups were evaluated, and minimized when possible. The dipole - dipole energy transfer microscopic parameters corresponding to Yb(3+) --> Tm(3+), Yb(3+) --> Yb(3+) and Tm(3+) --> Tm(3+) transfers, calculated by the Forster-Dexter model, are C(Yb-Tm) = 2.9 x 10(-40) cm(6) s(-1), C(Yb-Yb) = 42 x 10(-40) cm(6) s(-1) and C(Tm-Tm) = 43 x 10(-40) cm(6) s(-1), respectively.

Structural-electronic aspects related to the near-infrared light emission of Fe-doped silicon films

The need of efficient (fast and low consumption) optoelectronic devices has always been the driving force behind the investigation of materials with new or improved properties. To be commercially attractive, however, these materials should be compatible with our current micro-electronics industry and/or telecommunications system. Silicon-based compounds, with their matured processing technology and natural abundance, partially comply with such requirements-as long as they emit light. Motivated by these issues, this work reports on the optical properties of amorphous Si films doped with Fe. The films were prepared by sputtering a Si+Fe target and were investigated by different spectroscopic techniques. According to the experimental results, both the Fe concentration and the thermal annealing of the samples induce changes in their atomic structure and optical-electronic properties. In fact, after thermal annealing at similar to 750 degrees C, the samples partially crystallize with the development of Si and/or beta-FeSi(2) crystallites. In such a case, certain samples present light emission at similar to 1500 nm that depends on the presence of beta-FeSi(2) crystallites and is very sensitive to the annealing conditions. The most likely reasons for the light emission (or absence of it) in the considered Fe-doped Si samples are presented and discussed in view of their main structural-electronic characteristics. (C) 2011 Elsevier Ltd. All rights reserved.

Erbium and Ytterbium Codoped Titanoniobophosphate Glasses for Ion-Exchange-Based Planar Waveguides

This work presents the optical properties of erbium-doped and erbium/ytterbium codoped Na(2)O-Al(2)O(3)-TiO(2)-Nb(2)O(5)-P(2)O(5) glass systems and also the characterization of planar waveguides obtained by typical thermally assisted Ag+<-> Na+ ion-exchange process. The glass systems allow the preparation of single mode and multimode planar waveguides presenting a strong and relatively broad emission at 1536 nm. The emission signal in the infrared region is intensified for silver-containing samples when compared with free-silver samples. The emission signal intensification may be attributed to a nonplasmonic energy transfer from silver species to Er3+ ions as no bands related to surface plasmon resonance (SPR) of silver nanoparticles were observed.

Absorption and emission properties of LBL PPV films deposited on ITO electrodes

In this work we studied the properties of absorption and emission line shape of layer-by-layer (LBL) poly(p-phenylene vinylene) (PPV) on indium-tin oxide (ITO) electrode. To minimize the PPV thermal conversion effects during the polymer processing, we used a less aggressive leaving group in the precursor polymer; minimizing electrode degradation. LBL ITO/PPV films showed the same absorption and emission line shape compared with LBL PPV films deposited on non-metallic substrates (glass). With this analysis we indirectly observe the decrease in the ITO degradation. Atomic force microscopy (AFM) technique was used to analyze quantitatively the microscopic morphology of the film surface. Results indicated that the substrate topology is not affected, to a large extent, by the use of dodecylbenzensulfonate (DBS) ion. (C) 2008 Elsevier B.V. All rights reserved.

Tryptophan oxidation by singlet molecular oxygen [O-2 ((1)Delta(g))]: Mechanistic studies using O-18-labeled hydroperoxides, mass spectrometry, and light emission measurements

Proteins have been considered important targets for reactive oxygen species. Indeed, tryptophan (W) has been shown to be a highly susceptible amino acid to many oxidizing agents, including singlet molecular oxygen [O-2 ((1)Delta(g))]. In this study, two cis- and trans-tryptophan hydroperoxide (WOOH) isomers were completely characterized by HPLC/mass spectrometry and NMR analyses as the major W-oxidation photoproducts. These photoproducts underwent thermal decay into the corresponding alcohols. Additionally, WOOHs were shown to decompose under heating or basification, leading to the formation of N-formylkynurenine (FMK). Using O-18-labeled hydroperoxides ((WOOH)-O-18-O-18), it was possible to confirm the formation of two oxygen-labeled FMK molecules derived from (WOOH)-O-18-O-18 decomposition. This result demonstrates that both oxygen atoms in FMK are derived from the hydroperoxide group. In addition, these reactions are chemiluminescent (CL), indicating a dioxetane cleavage pathway. This mechanism was confirmed since the CL spectrum of the WOOH decomposition matched the FMK fluorescence spectrum, unequivocally identifying FMK as the emitting species.

Cholesterol Hydroperoxides Generate Singlet Molecular Oxygen [O(2) ((1)Delta(g))]: Near-IR Emission, (18)O-Labeled Hydroperoxides, and Mass Spectrometry

In mammalian membranes, cholesterol is concentrated in lipid rafts. The generation of cholesterol hydroperoxides (ChOOHs) and their decomposition products induces various types of cell damage. The decomposition of some organic hydroperoxides into peroxyl radicals is known to be a potential source of singlet molecular oxygen [O(2) ((1)Delta(g))] in biological systems. We report herein on evidence of the generation of O(2) ((1)Delta(g)) from ChOOH isomers in solution or in liposomes containing ChOOHs, which involves a cyclic mechanism from a linear tetraoxide intermediate originally proposed by Russell. Characteristic light emission at 1270 nm, corresponding to O(2) ((1)Delta(g)) monomolecular decay, was observed for each ChOOH isomer or in liposomes containing ChOOHs. Moreover, the presence of O(2) ((1)Delta(g)) was unequivocally demonstrated using the direct spectral characterization of near-infrared light emission. Using (18)O-labeled cholesterol hydroperoxide (Ch(18)O(18)OH), we observed the formation of (18)O-labeled O(2) ((1)Delta(g)) [(18)O(2) ((1)Delta(g))] by the chemical trapping of (18)O(2) ((1)Delta(g)) with 9,10-diphenylanthracene (DPA) and detected the corresponding (18)O-labeled DPA endoperoxide (DPA(18)O(18)O) and the (18)O-labeled products of the Russell mechanism using high-performance liquid chromatography coupled to tandem mass spectrometry. Photoemission properties and chemical trapping clearly demonstrate that the decomposition of Ch(18)O(18)OH generates (18)O(2) ((1)Delta(g)), which is consistent with the Russell mechanism and points to the involvement of O(2) ((1)Delta(g)) in cholesterol hydroperoxide-mediated cytotoxicity.

Vision in click beetles (Coleoptera: Elateridae): pigments and spectral correspondence between visual sensitivity and species bioluminescence emission

Among lampyrids, intraspecific sexual communication is facilitated by spectral correspondence between visual sensitivity and bioluminescence emission from the single lantern in the tail. Could a similar strategy be utilized by the elaterids (click beetles), which have one ventral abdominal and two dorsal prothoracic lanterns? Spectral sensitivity [S(lambda)] and bioluminescence were investigated in four Brazilian click beetle species Fulgeochlizus bruchii, Pyrearinus termitilluminans, Pyrophorus punctatissimus and P. divergens, representing three genera. In addition, in situ microspectrophotometric absorption spectra were obtained for visual and screening pigments in P. punctatissimus and P. divergens species. In all species, the electroretinographic S(lambda) functions showed broad peaks in the green with a shoulder in the near-ultraviolet, suggesting the presence of short- and long-wavelength receptors in the compound eyes. The long-wavelength receptor in Pyrophorus species is mediated by a P540 rhodopsin in conjunction with a species-specific screening pigment. A correspondence was found between green to yellow bioluminescence emissions and its broad S(lambda) maximum in each of the four species. It is hypothesized that in elaterids, bioluminescence of the abdominal lantern is an optical signal for intraspecifc sexual communication, while the signals from the prothoracic lanterns serve to warn predators and may also provide illumination in flight.

2-Aminopurine non-radiative decay and emission in aqueous solution: A theoretical study

The minimum energy path along the lowest-lying pi pi* excited state of 2-aminopurine was calculated to elucidate the mechanisms of radiationless decay and emission in water. The sequential Monte Carlo quantum mechanics approach with a multiconfigurational and perturbative description of the wave function was employed to compute the minimum, transition state, and conical intersection. It was found that the barrier in the potential energy surface to access the conical intersection funnel increases in aqueous environment, making the system prone to enlarge the emission yield. These results rationalize the observed enhancement of emission in 2-aminopurine upon increasing of the solvent polarity. (c) 2008 Elsevier B.V. All rights reserved.

A method for Ca, Fe, Ga, Na, Si and Zn determination in alumina by inductively coupled plasma optical emission spectrometry after aluminum precipitation

In this present work a method for the determination of Ca, Fe, Ga, Na, Si and Zn in alumina (Al(2)O(3)) by inductively coupled plasma optical emission spectrometry (ICP OES) with axial viewing is presented. Preliminary studies revealed intense aluminum spectral interference over the majority of elements and reaction between aluminum and quartz to form aluminosilicate, reducing drastically the lifetime of the torch. To overcome these problems alumina samples (250 mg) were dissolved with 5 mL HCl + 1.5 mLH(2)SO(4) + 1.5 mL H(2)O in a microwave oven. After complete dissolution the volume was completed to 20 mL and aluminum was precipitated as Al(OH)(3) with NH(3) (by bubbling NH(3) into the solution up to a pH similar to 8, for 10 min). The use of internal standards (Fe/Be, Ga/Dy, Zn/In and Na/Sc) was essential to obtain precise and accurate results. The reliability of the proposed method was checked by analysis of alumina certified reference material (Alumina Reduction Grade-699, NIST). The found concentrations (0.037%w(-1) CaO, 0.013% w w(-1) Fe(2)O(3), 0.012%w w(-1)Ga(2)O(3), 0.49% w w(-1) Na(2)O, 0.014% w w(-1) SiO(2) and 0.013% w w(-1) ZnO) presented no statistical differences compared to the certified values at a 95% confidence level. (C) 2011 Elsevier B.V. All rights reserved.

Uncertainties In Future Projections Of Extreme Rainfall: The Role Of Climate Model, Emission Scenario And Randomness

Climate change has resulted in substantial variations in annual extreme rainfall quantiles in different durations and return periods. Predicting the future changes in extreme rainfall quantiles is essential for various water resources design, assessment, and decision making purposes. Current Predictions of future rainfall extremes, however, exhibit large uncertainties. According to extreme value theory, rainfall extremes are rather random variables, with changing distributions around different return periods; therefore there are uncertainties even under current climate conditions. Regarding future condition, our large-scale knowledge is obtained using global climate models, forced with certain emission scenarios. There are widely known deficiencies with climate models, particularly with respect to precipitation projections. There is also recognition of the limitations of emission scenarios in representing the future global change. Apart from these large-scale uncertainties, the downscaling methods also add uncertainty into estimates of future extreme rainfall when they convert the larger-scale projections into local scale. The aim of this research is to address these uncertainties in future projections of extreme rainfall of different durations and return periods. We plugged 3 emission scenarios with 2 global climate models and used LARS-WG, a well-known weather generator, to stochastically downscale daily climate models’ projections for the city of Saskatoon, Canada, by 2100. The downscaled projections were further disaggregated into hourly resolution using our new stochastic and non-parametric rainfall disaggregator. The extreme rainfall quantiles can be consequently identified for different durations (1-hour, 2-hour, 4-hour, 6-hour, 12-hour, 18-hour and 24-hour) and return periods (2-year, 10-year, 25-year, 50-year, 100-year) using Generalized Extreme Value (GEV) distribution. By providing multiple realizations of future rainfall, we attempt to measure the extent of total predictive uncertainty, which is contributed by climate models, emission scenarios, and downscaling/disaggregation procedures. The results show different proportions of these contributors in different durations and return periods.

A simple analysis of the U.S. emission permits auctions

We examine a stylized version of EPA auctions when agents know the list of values of sellers and buyers. Sellers and buyers behave strategically. We show that there are two types of equilibria: inefficient equilibria where no goods are traded and efficient equilibria where alI exchange occurs at a uniform price. We also provide examples of the EPA auction game under incomplete information when the uniform price equilibrium holds and when it does not hold. When the uniform price equilibrium holds, sellers shade their bids up and buyers shade their bids down. In the example where the uniform price equilibrium does not hold, both buyers and sellers shade their bids down in an equilibrium.

Al-based anodic oxide films structure observation using field emission gun scanning electron microscopy

In the present work, the anodic oxide films of Al, Al-Cu 4.5% and Al-Si 6.5% alloys are formed using direct and pulse current. In the case of Al-Cu and Al-Si alloys, the electrolyte used contains sulfuric acid and oxalic acid, meanwhile for Al the electrolyte contains sulfuric acid only. Al-Cu alloy was submitted to a heat treatment in order to decrease the effect of inter metallic phase theta upon the anodic film structure. Fractured samples were observed using a field emission gun scanning electron microscope JSM-6330F at (LME)/Brazilian Synchrotron Light Laboratory (LNLS), Campinas, SP, Brazil. The oxide film images enable evaluation of the pore size and form with a resolution similar to the transmission electron microscope (TEM) resolution. It is also observed that the anodizing process using pulse current produces an irregular structure of pore walls, and by direct cur-rent it is produced a rectilinear pore wall. (c) 2005 Elsevier B.V. All rights reserved.

Spatial variability of soil CO2 emission in a sugarcane area characterized by secondary information

Soil CO2 emission (FCO2) is governed by the inherent properties of the soil, such as bulk density (BD). Mapping of FCO2 allows the evaluation and identification of areas with different accumulation potential of carbon. However, FCO2 mapping over larger areas is not feasible due to the period required for evaluation. This study aimed to assess the quality of FCO2 spatial estimates using values of BD as secondary information. FCO2 and BD were evaluated on a regular sampling grid of 60 m × 60 m comprising 141 points, which was established on a sugarcane area. Four scenarios were defined according to the proportion of the number of sampling points of FCO2 to those of BD. For these scenarios, 67 (F67), 87 (F87), 107 (F107) and 127 (F127) FCO2 sampling points were used in addition to 127 BD sampling points used as supplementary information. The use of additional information from the BD provided an increase in the accuracy of the estimates only in the F107, F67 and F87 scenarios, respectively. The F87 scenario, with the approximate ratio between the FCO2 and BD of 1.00:1.50, presented the best relative improvement in the quality of estimates, thereby indicating that the BD should be sampled at a density 1.5 time greater than that applied for the FCO2. This procedure avoided problems related to the high temporal variability associated with FCO2, which enabled the mapping of this variable to be elaborated in large areas.

Soil CO2 emission as related to incorporation of sugarcane crop residues and aggregate breaking after rotary tiller

O preparo do solo é um dos processos que aceleram a decomposição da matéria orgânica, transferindo carbono para atmosfera, principalmente na forma de CO2. Neste trabalho, investigou-se o efeito do preparo com enxada rotativa sobre as emissões de CO2 do solo durante 02 semanas após o preparo do solo, incluindo-se a presença de resíduos vegetais sobre a superfície. As emissões foram avaliadas por 15 dias após preparo em 3 parcelas: 1) sem preparo e sem palha superficial (SPs); 2) preparo com enxada rotativa sem a presença de palha na superfície (ERs), e 3) preparo com enxada rotativa com a presença de palha superficial (ERc). As emissões provenientes da ERc foram superiores às demais (0,777 g CO2 m-2 h-1), sendo as menores emissões registradas na parcela SPs (0,414 g CO2 m-2 h-1). As emissões totais indicaram que a diferença de C-CO2 emitida à atmosfera corresponde a 3% do total de carbono adicional presente na palha, na parcela ERc, quando comparado à parcela ERs. O aumento da emissão da parcela SPs para ERs foi acompanhado de uma modificação na distribuição do tamanho de agregados, especialmente aqueles com diâmetro médio inferior a 2 mm. O aumento da emissão da parcela ERs para ERc esteve relacionado a uma diminuição da massa de palha na superfície, com fragmentação e incorporação da mesma no interior do solo. Quando se analisa a correlação linear entre emissão de CO2 versus temperatura e umidade do solo, somente a emissão da ERc foi significativamente correlacionada (p<0,05) à umidade do solo.