Photopatternable di-ureasil-zirconium oxocluster organic-inorganic hybrids as cost effective integrated optical substrates

Organic-inorganic hybrids containing methacrylic acid (McOH, CH(2)= C(CH(3))COOH)) modified zirconium tetrapropoxide, Zr(OPr(n))(4), classed as di-ureasil-zirconium oxo-cluster hybrids, have been prepared and structurally characterized by X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), Fourier transform infrared (FT-IR) and Raman (FT-Raman) spectroscopies, Si and C nuclear magnetic resonance (NMR), and atomic force microscopy (AFM). XRD and SAXS results have pointed out the presence of Si- and Zr-based nanobuilding blocks (NBBs) dispersed into the organic phase. Inter-NBBs correlation distances have been estimated for the pure di-ureasil and a model compound obtained. by hydrolysis/condensation of Zr(OPr(n))(4):McOH (molar ratio 1: 1): d(Si) approximate to 26 +/- 1 angstrom and d(Zr) approximate to 16 +/- 1 angstrom, respectively. In the case of the di-ureasil-zirconium oxo-cluster hybrids, these distances depend on the Zr relative molar percentage (rel. mol. Zr %) (d(Si) ranges from 18 to 25 angstrom and d(Zr) from 14 to 23 angstrom, as the rel. mol. Zr % increases from 5 to 75), suggesting that the Si- and Zr-based clusters are interconstrained. Complementary data from FT-IR, FT-Raman, (29)Si and (13)C NMR, and AFM support to a structural model where McOH-modified Zr-based NBBs (Zr-OMc) are present over the whole range of composition. At low Zr-OMc contents (rel. mol. Zr % <30) the clusters are well-dispersed within the di-ureasil host, whereas segregation occurs at the 0.1 mu m scale at high Zr-OMc concentration (rel. mol. Zr % = 50). No Zr-O-Si heterocondensation has been discerned. Monomode waveguides, diffractions gratings, and Fabry-Perot cavities have been written through the exposure of the hybrid monoliths to UV light. FT-Raman has shown that the chemical process that takes place under illumination is the polymerization of the methacrylate groups of the Zr-OMc NBBs. The guidance region in patterned channels is a Gaussian section located below the exposed surface with typical dimensions of 320 mu m wide and 88 mu m deep. The effective refractive index is 1.5162 (maximum index contrast on the order of 1 x 10(-4)) and the reflection coeficient of the Fabry-Perot cavity (formed by a grating patterned into a 0.278 cm channel) is 0.042 with a free spectral range value of 35.6 GHz.

Self-supported bacterial cellulose/boehmite organic-inorganic hybrid films

Self-supported organic-inorganic hybrid transparent films have been prepared from bacterial cellulose and boehmite. SEM results indicate that the BC membranes are covered by Boehmite and XRD patterns suggest structural changes on cellulose due to Boehmite addition. Thermal stability is accessed through TG curves and is dependent on Boehmite content. Transparency, as evaluated by UV-Vis absorption, increases with increasing content of boehmite suggesting application of these materials as transparent substrates for opto-electronic devices.

Transparent bacterial cellulose-boehmite-epoxi-siloxane nanocomposites

Organic-inorganic composite membranes were prepared from membranes of the bio-polymer bacterial cellulose (BC) and organic-inorganic sal composed of nanoparticulate boehmite and epoxi modified siloxane. Bacterial cellulose membranes are obtained in a highly hydrated state (1% cellulose and 99% cellulose) from cultures of Gluconacetobacter xylinus and could be used in the never-dried or in the dried state. Depending on the use of dried or never-dried BC membranes two main kinds of composites were obtained. In the first one dried BC membranes coated with the hybrid sol have lead to transparent membranes displaying a hi-phase structure where the two components could be easily distinguished, with individual structures preserved. A decrease was observed for tensile strength (50.5 MPa) and Young's Modulus (2.8 GPa) when compared to pure BC membrane (112.5 MPa and 12.7 GPa). Elongation at break was observed to increase (2.5% against 1.5% observed for BC). When never-dried BC membranes were used transparent membranes were also obtained, however an improvement was observed for mechanical properties (tensile strength - 116 MPa and Young's Modulus - 13.7 GPa). A lower value was obtained for the elongation at break (1.3%). In the last case the interaction between the two-phases lead to changes in the cellulose crystallinity as shown by X rays diffraction results. Multifunctional transparent membranes displaying the cellulose structure in one side and the boehmite-siloxane structure at the opposite face could find special applications in opto-electronics or biomedical areas taking advantage of the different chemical nature of the two components. (C) 2012 Elsevier Ltd. All rights reserved.

Hybrid Materials Based on Smectite Clays and Nutraceutical Anthocyanins from the Acai Fruit

Hybrid materials were prepared by combining clay mineral (montmorillonite SWy-2 and saponite SapCa-1) and dyes extracted from the acai (Euterpe oleracea Mart.) fruit, which contains mainly anthocyanins from the 3-glucoside class, to increase the stability of the dye and facilitate its handling and storage. Clay minerals are common ingredients in therapeutic and pharmaceutical products and acai phytochemicals show disease prevention properties. The extract of the acai fruit was mixed with water suspensions of layered silicates in different proportions. The dyeclay hybrids presented incorporated organic material in amounts up to 24 wt.-%. X ray diffractometry and vibrational (FTIR and Raman) and electronic spectroscopic data showed that flavylium cations were successfully intercalated between the inorganic layers. Mass-coupled thermogravimetric analysis (TGA-MS) data showed a significant gain in the thermostability of the organic species in relation to anthocyanins in the extract. MS curves related to CO2 release (m/z = 44) are ascendant above 200 degrees C when the dye cations are confined to the inorganic structure. The radical scavenging activity of the hybrid materials was monitored by electron paramagnetic resonance (EPR) toward the stable radical DPPH (1,1-diphenyl-2-picrylhydrazyl) and compared to the activity of the acai extract. In addition to the fact that interaction with clay minerals improves the stability of the acai dyes against heat, their properties as radical scavengers are preserved after intercalation. The improvement in the properties of the nutraceutical species by intercalation by using biocompatible inorganic structures can be valuable for human therapy.

Size distributions and temporal variations of biological aerosol particles in the Amazon rainforest characterized by microscopy and real-time UV-APS fluorescence techniques during AMAZE-08

As a part of the AMAZE-08 campaign during the wet season in the rainforest of central Amazonia, an ultraviolet aerodynamic particle sizer (UV-APS) was operated for continuous measurements of fluorescent biological aerosol particles (FBAP). In the coarse particle size range (> 1 mu m) the campaign median and quartiles of FBAP number and mass concentration were 7.3x10(4) m(-3) (4.0-13.2x10(4) m(-3)) and 0.72 mu g m(-3) (0.42-1.19 mu g m(-3)), respectively, accounting for 24% (11-41%) of total particle number and 47% (25-65%) of total particle mass. During the five-week campaign in February-March 2008 the concentration of coarse-mode Saharan dust particles was highly variable. In contrast, FBAP concentrations remained fairly constant over the course of weeks and had a consistent daily pattern, peaking several hours before sunrise, suggesting observed FBAP was dominated by nocturnal spore emission. This conclusion was supported by the consistent FBAP number size distribution peaking at 2.3 mu m, also attributed to fungal spores and mixed biological particles by scanning electron microscopy (SEM), light microscopy and biochemical staining. A second primary biological aerosol particle (PBAP) mode between 0.5 and 1.0 mu m was also observed by SEM, but exhibited little fluorescence and no true fungal staining. This mode may have consisted of single bacterial cells, brochosomes, various fragments of biological material, and small Chromalveolata (Chromista) spores. Particles liquid-coated with mixed organic-inorganic material constituted a large fraction of observations, and these coatings contained salts likely from primary biological origin. We provide key support for the suggestion that real-time laser-induce fluorescence (LIF) techniques using 355 nm excitation provide size-resolved concentrations of FBAP as a lower limit for the atmospheric abundance of biological particles in a pristine environment. We also show some limitations of using the instrument for ambient monitoring of weakly fluorescent particles < 2 mu m. Our measurements confirm that primary biological particles, fungal spores in particular, are an important fraction of supermicron aerosol in the Amazon and that may contribute significantly to hydrological cycling, especially when coated by mixed inorganic material.

Surfactant-assisted intercalation of high molecular weight poly(ethylene oxide) into vanadyl phosphate di-hydrate

A high molecular weight poly(ethylene oxide)/layered vanadyl phosphate di-hydrate intercalation compound was synthesized via the surfactant-assisted approach. Results confirmed that surfactant molecules were replaced with the polymer, while the lamellar structure of the matrix was retained, and that the material presents high specific surface area. In addition, intercalation produced a more thermally stable polymer as evidenced by thermal analysis. (C) 2011 Elsevier Ltd. All rights reserved.

Effect of the vanadium(V) concentration on the spectroscopic properties of nanosized europium-doped yttrium phosphates

Nanosized rare earth phosphovanadate phosphors (Y(P,V)O-4:Eu3+) have been prepared by applying the organic-inorganic polymeric precursors methodology. Luminescent powders with tetragonal structure and different vanadate concentrations (0%, 1%, 5%, 10%, 20%, 50%, and 100%, with regard to the phosphate content) were then obtained for evaluation of their structural and spectroscopic properties. The solids were characterized by scanning electron microscopy, X-ray diffractometry, vibrational spectroscopy (Raman and infrared), and electronic spectroscopy (emission, excitation, luminescence lifetimes, chromaticity, quantum efficiencies, and Judd-Ofelt intensity parameters). The solids exhibited very intense D-5(0) -> F-7(J) Eu3+ transitions, and it was possible to control the luminescent characteristics, such as excitation maximum, lifetime and emission colour, through the vanadium(V) concentration. The observed luminescent properties correlated to the characteristics of the chemical environments around the Eu3+ ions with respect to the composition of the phosphovanadates. The Eu3+ luminescence spectroscopy results indicated that the presence of larger vanadium(V) amounts in the phosphate host lattice led to more covalent and polarizable chemical environments. So, besides allowing for control of the luminescent properties of the solids, the variation in the vanadate concentration in the obtained YPO4:Eu3+ phosphors enabled the establishment of a strict correlation between the observable spectroscopic features and the chemical characteristics of the powders.

Preparação e caracterização de materiais híbridos celulose/NbOPO4.nH2O a partir de celulose branqueada de bagaço de cana-de-açúcar

Este trabalho descreve a preparação e caracterização do híbrido celulose/fosfato de nióbio hidratado (Cel/NbOPO4.nH2O) utilizando como material de partida a celulose branqueada de bagaço de cana-de-açúcar e o nióbio metálico. O híbrido foi preparado por dois métodos: denominados métodos I e II. O método I consistiu na dissolução do nióbio metálico em solução de ácido fluorídrico/nítrico (100:10), com tempo de contato de 16 horas entre a celulose branqueada do bagaço de cana-de-açúcar e a solução ácida. Adicionou-se a essa solução ácido fosfórico para precipitação do material. O método II foi semelhante, com proporções diferentes da solução ácida fluorídrico/nítrico (160/100), sem tempo de contato da celulose com a solução ácida. Os métodos I e II utilizaram as seguintes proporções de cel/ Nb2O5.nH2O: (10:10);(10:6) e (10:2). Os materiais preparados pelos métodos I e II foram caracterizados por difração de raios X (DRX), termogravimetria (TG/DTG) e microscopia eletrônica de varredura (MEV). Observou-se aumento do índice do grau de cristalinidade e mudanças na morfologia dos materiais preparados.

A systematic study of transfection efficiency and cytotoxicity in HeLa cells using iron oxide nanoparticles prepared with organic and inorganic bases

Magnetic iron oxide nanoparticles (magnetite) (MNPs) were prepared using different organic and inorganic bases. Strong inorganic base (KOH) and organic bases (NH4OH and 1,4-diazabicyclo[2.2.2]octane (DABCO)) were used in the syntheses of the MNPs. The MNPs were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM). Fourier transform infrared spectroscopy (FT-IR) and magnetization measurements. MNPs prepared with strong inorganic base yielded an average size of 100 nm, whereas the average size of the MNPs prepared with the organic bases was 150 nm. The main competitive phase for MNPs prepared with the strong inorganic and organic bases was maghemite; however, syntheses with KOH yielded a pure magnetite phase. The transfection study performed with the MNPs revealed that the highest transfection rate was obtained with the MNPs prepared with KOH (74%). The correlation between the magnetic parameters and the transfection ratio without transfection agents indicated that MNPs prepared with KOH were a better vector for possible applications of these MNPs in biomedicine. HeLa cells incubated with MNP-KOH at 10 mu g/mL for 24 and 48 h exhibited a decrease in population in comparison with the control cells and it was presumably related to the toxicity of the MNPs. However, the cells incubated with MNP-KOH at 50 and 100 mu g/mL presented a very small difference in the viability between the cell populations studied at 24 and 48 h. These data illustrate the viability of HeLa cells treated with MNP-KOH and suggest the potential use of these MNPs in biomedical applications. (C) 2012 Elsevier B.V. All rights reserved.

Organic and inorganic sources of zinc, copper and selenium in diets for dairy cows: intake, blood metabolic profile, milk yield and composition

The present study was carried out with the objective of evaluating the effects of feeding dairy cows with organic or inorganic sources of zinc (Zn), copper (Cu) and selenium (Se) on blood concentrations of these minerals, blood metabolic profiles, nutrient intake and milk yield and composition. Nineteen Holstein cows were selected and randomly assigned to two groups for receiving organic (n = 9) or inorganic (n = 10) sources of Zn, Cu and Se from 60 days before the expected date of calving to 80 days of lactation. Samples of feed, orts and milk were collected for analysis. Body condition score (BCS) was determined and blood samples were collected for analysis of Zn, Cu and Se concentrations, as well as for metabolic profile. Supplying organic or inorganic sources of Zn, Cu, and Se did not affect dry matter and nutrient intake, blood metabolic profile, milk yield and composition, plasma concentration of these minerals, and BCS or change the BCS in cows from 60 days before the expected date of calving to 80 days of lactation. An effect of time was observed on all feed intake variables, plasma concentrations of Zn and Se, milk yield, milk protein content, BCS and change in BCS.

Supplementation of diets for Santa Ines sheep with organic and inorganic zinc sources

This research was conducted with objective to evaluate the effect of different zinc (Zn) sources and doses in the diet for Santa Ines sheep. Forty lambs at weaning, with 18.4 kg of body weight were supplemented with three different sources of zinc (zinc oxide (ZnO), zinc amino acid and zinc proteinate) and three doses of zinc (200, 400 and 600 mg/kg DM) added to the basal diet. At every 28 days, animals were weighted and blood samples were collected for analyses of zinc (Zn), alkaline phosphatase and immunoglobulin G (IgG) and M (IgM). At the end of experiment, liver samples were collected for determination of the hepatic zinc levels. Zinc was analyzed with atomic absorption spectrophotometer, while phosphatase alkaline and immunoglobulins G and M were analyzed using Laborlab and Bioclin kits, respectively. There was no effect of diets on phosphatase alkaline levels and hepatic zinc, but there was difference in the plasmatic zinc levels and IgG and IgM levels. Based on the accumulation of hepatic zinc, the estimate of the zinc bioavailability, through the regression equation, showed that supplementation with organic and inorganic sources of zinc did not differ in the diet of Santa Ines sheep.

Influence of allochthonous organic matter on bacterioplankton biomass and activity in a eutrophic, sub-tropical estuary

Heterotrophic bacterial and phytoplankton biomass, production, specific growth rates, and growth efficiencies were studied in the Northern region of the Cananeia-Iguape estuarine system, which has recently experienced an intense eutrophication due to anthropogenic causes. Two surveys were carried out during spring and neap tide periods of the dry season of 2005 and the rainy season of 2006. This region receives large freshwater inputs with organic seston and phosphate concentrations that reach as high as 1.0 mg l(-1) and 20.0 mu M, respectively. Strong decreasing gradients of seston and dissolved inorganic nutrients were observed from the river/estuary boundary to the estuary/coastal interface. Gradients were also observed in phytoplankton and bacterial production rates. The production rates of phytoplankton were 5.6-fold higher (mean 8.5 mu g Cl(-1) h(-1)) during the dry season. Primary production rates (PP) positively correlated with salinity and euphoric depth, indicating that phytoplankton productivity was light-limited. On the other hand, bacterial biomass (BB) and production rates (BP) were 1.9- and 3.7-fold higher, respectively, during the rainy season, with mean values of up to 40.4 mu g Cl(-1) and 7.9 mu g Cl(-1) h-1, respectively. Despite such a high BP, bacterial abundance remained <2 x 106 cells ml(-1), indicating that bacterial production and removal were coupled. Mean specific growth rates ranged between 0.9 and 5.5 d(-1). BP was inversely correlated with salinity and positively correlated with temperature, organic matter, exopolymer particles, and particulate-attached bacteria; this last accounted for as much as 89.6% of the total abundance. During the rainy season, BP was generally much higher than PP, and values of BP/PP > 20 were registered during high freshwater input, suggesting that under these conditions, bacterial activity was predominantly supported by allochthonous inputs of organic carbon. In addition, BB probably represented the main pathway for the synthesis of high-quality (low C:N) biomass that may have been available to the heterotrophic components of the plankton food web, particularly nanoheterotrophs. (C) 2008 Elsevier Ltd. All rights reserved.

Interference of inorganic ions on phenol degradation by the Fenton reaction

The addition of Cu2+ ions to the classical Fenton reaction (Fe2+ plus H2O2 at pH 3) is found to accelerate the degradation of organic compounds. This synergic effect causes an approximately 15 % additional reduction of the total organic carbon (TOC), representing an overall improvement of the efficiency of the mineralization of phenol. Although Fe2+ exhibits a high initial rate of degradation, the degradation is not complete due to the formation of compounds refractory to the hydroxyl radical. The interference of copper ions on the degradation of phenol by the Fenton reaction was investigated. In the presence of Cu2+, the degradation is slower, but results in a greater reduction of TOC at the end of the reaction (t = 120 min). In the final stages of the reaction, when the Fe3+ in the solution is complexed in the form of ferrioxalate, the copper ions assume the role of the main catalyst of the degradation.

Use of levoglucosan, potassium, and water-soluble organic carbon to characterize the origins of biomass-burning aerosols

Three chemical species related to biomass burning, levoglucosan, potassium and water-soluble organic carbon (WSOC), were measured in aerosol samples collected in a rural area on the outskirts of the municipality of Ourinhos (Sao Paulo State, Brazil). This region is representative of the rural interior of the State, where the economy is based on agro-industrial production, and the most important crop is sugar cane. The manual harvesting process requires that the cane be first burned to remove excess foliage, leading to large emissions of particulate materials to the atmosphere. Most of the levoglucosan (68-89%) was present in small particles (<1.5 mu m), and its concentration in total aerosol ranged from 25 to 1186 ng m(-3). The highest values were found at night, when most of the biomass burning occurs. In contrast, WSOC showed no diurnal pattern, with an average concentration of 5.38 +/- 2.97 mu g m(-3) (n = 27). A significant linear correlation between levoglucosan and WSOC (r = 0.54; n = 26; p < 0.0001) confirmed that biomass burning was in fact an important source of WSOC in the study region. A moderate (but significant) linear correlation between levoglucosan and potassium concentrations (r = 0.62; n = 40; p < 0.0001) was indicative of the influence of other sources of potassium in the study region, such as soil resuspension and fertilizers. When only the fine particles (<1.5 pm; typical of biomass burning) were considered, the linear coefficient increased to 0.91 (n = 9). In this case, the average levoglucosan/K+ ratio was 0.24, which may be typical of biomass burning in the study region. This ratio is about 5 times lower than that previously found for Amazon aerosol collected during the day, when flaming combustion prevails. This suggests that the levoglucosan/K+ ratio may be especially helpful for characterization of the type of vegetation burned (such as crops or forest), when biomass-burning is the dominant source of potassium. The relatively high concentrations of WSOC (and inorganic ions) suggest an important influence on the formation of cloud condensation nuclei, which is likely to affect cloud formation and precipitation patterns. (C) 2012 Elsevier Ltd. All rights reserved.

Tb3+-> Eu3+ Energy Transfer in Mixed-Lanthanide-Organic Frameworks

In this work, we report a theoretical and experimental investigation of the energy transfer mechanism in two isotypical 2D coordination polymers, (infinity)[(Tb1-xEux)(DPA)(HDPA)], where H(2)DPA is pyridine 2,6-dicarboxylic acid and x = 0.05 or 0.50. Emission spectra of (infinity)[(Tb0.95Eu0.05)(DPA)(HDPA)] and (infinity)[(Tb0.5Eu0.5)(DPA)(HDPA)], (I) and (2), show that the high quenching effect on Tb3+ emission caused by Eu3+ ion indicates an efficient Tb3+-> Eu3+ energy transfer (ET). The k(ET) of Tb3+-> Eu3+ ET and rise rates (k(r)) of Eu3+ as a function of temperature for (1) are on the same order of magnitude, indicating that the sensitization of the Eu3+5D0 level is highly fed by ET from the D-5(4) level of Tb3+ ion. The eta(ET) and R-0 values vary in the 67-79% and 7.15 to 7.93 angstrom ranges. Hence, Tb3+ is enabled to transfer efficiently to Eu3+ that can occupy the possible sites at 6.32 and 6.75 angstrom. For (2), the ET processes occur on average with eta(ET) and R-0 of 97% and 31 angstrom, respectively. Consequently, Tb3+ ion is enabled to transfer energy to Eu3+ localized at different layers. The theoretical model developed by Malta was implemented aiming to insert more insights about the dominant mechanisms involved in the ET between lanthanides ions. Calculated single Tb3+-> Eu3+ ETs are three orders of magnitude inferior to those experimentally; however, it can be explained by the theoretical model that does not consider the role of phonon assistance in the Ln(3+)-> Ln(3+) ET processes. In addition, the Tb3+-> Eu3+ ET processes are predominantly governed by dipole-dipole (d-d) and dipole-quadrupole (d-q) mechanisms.