A thermal behaviour study of solid-state cinnamates of the latter trivalent lanthanides and yttrium(III)

Some new compounds of cinnamic acid with the latter trivalent lanthanides and yttrium(III) were synthesized in the solid state. The compounds have the general formula LnL3, where Ln represents trivalent Eu to Lu or Y ions and L is the cinnamate anion (C6H5-CH=CH-COO-). Thermogravimetry (TG), derivative thermogravimetry (DTG), differential scanning calorimetry (DSC), infrared absorption spectra and X-ray diffraction powder patterns were used to characterize and to study the thermal behaviour of these compounds. © 2002 Elsevier Science B.V. All rights reserved.

Spectroscopic properties of Tm3+ doped fluoroindate glass

Optical absorption and fluorescence were investigated in Tm3+ doped fluoroindate glass. The spectroscopic parameters for transitions in the 4f11 configuration were determined. The fluorescence study revealed the origin of the frequency upconversion process as well as allowed to quantify the interaction between Tm3+ ions.

Dynamics of energy transfer and frequency upconversion in Tm3+ doped fluoroindate glass

The spectroscopic properties of Tm3+-doped fluoroindate glasses (FIG) were described by single wavelength pumping in the red region. The Judd-Ofelt (J-O) theory was used to obtain the quantum efficiency of the 4f-4f transitions and other spectroscopic parameters. The dynamics of the fluorescence was investigated and energy transfer (ET) processes among Tm3+ ions were studied. The results indicate that a two-step one-photon absorption process is responsible for the ultraviolet upconversion (UC) emissions, and dipole-dipole interaction provides the main contribution for ET rate is equal to the decay rate of noninteracting among active ions.

Physico-chemical properties of MTA and a novel experimental cement

Aim: To evaluate the release of calcium ions, pH and conductivity of a new experimental dental cement (EC) and to compare them with those of mineral trioxide aggregate (MTA-Angelus). Methodology: Five samples of each cement were prepared using plastic tubes 1 mm in diameter and 10 mm long. Each sample was sealed in a test tube containing 10 mL deionized water which was analysed after 24, 48, 72, 96, 192, 240 and 360 h for pH, electrical conductivity and calcium release. The concentration of calcium ions was obtained through atomic absorption spectroscopy technique. The data were analysed statistically using the analysis of variance (ANOVA) and the Student's test (t-test). Results: The pH of the storage solutions was not affected by the material and the interaction of material with time (P > 0.05). However, the time of immersion was significant (P < 0.01) for both materials. For the electric conductivity and calcium release, the interaction of material with time was statistically significant (P < 0.01), indicating that EC and MTA-Angelus did not behave in a similar manner. Conclusions: The experimental cement released calcium and increased the pH of the storage solutions in a similar manner to MTA-Angelus. However, EC showed significantly higher calcium release than commercial MTA-Angelus after 24 h. © 2005 International Endodontic Journal.

Densification of Mn-doped tin oxide films by conventional heating and microwave heating treatment

Mn(II) doped SnO2 thin films used for shielding fluoride glasses against corrosion were investigated by x-ray absorption spectroscopy (EXAFS and XANE)S at the Sn and Mn K-edges. The effect of firing treatment on the densification of the films was studied. It has been evidenced a partial change of Mn valence from 2.3 to 2.6 upon heating which is attributed to a change of ratios of two Mn sites: grafted divalent Mn ions at the surface of SnO 2 nanocrystallites and trivalent Mn ions embedded into a substitutional solid solution with Sn. © Physica Scripta 2005.

Correlation between local structure and ionic conductivity of potassium-doped siloxane poly(propyleneoxyde) ormolytes

The local order around K for K(CF3SO3) doped Siloxane-Poly(propyleneoxide) hybrids at different doping concentration was investigated by x-ray absorption spectroscopy (EXAFS and XANES) at the potassium K-edge. The results indicate that the use of HCl as hydrolytic catalyst for gelation induces the precipitation of KCl. The ionic conductivity is strongly related to the presence of oxygen atoms as first neighbours around potassium and to the amount of KCl precipitate. © Physica Scripta 2005.

Transferênce de metais pesados, flúor e radionuclídeos para solos agrícolas na bacia do rio Corumbataí (SP)

The use of phosphate fertilizers and amendments in sugar cane crops may increase the concentration of some elements in soils, from where they would become available for plants (principally in acid soils) and transferred to me human food chain. This paper reports the transference of heavy metals (Cd, Cr, Cu, Ni, Pb and Zn), fluorine and radionuclides ( 238U, 234U, 226Ra, 232Th and 40K) from phosphate fertilizers and amendments to agricultural soils at Corumbatal River basin (SP). The products utilized and colleted in sugar cane crops at Corumbatai River basin are: phosphate fertilizers NPK 5:25:25 (two samples), limestones (three samples), phosphogypsum (two samples) and KCl (two samples). The heavy metals were determined by atomic absorption spectrometry (AAS), fluorine by potentiometry and radionuclides by alpha and gamma spectrometry. Heavy metals (17.8, 31.2, 75.2, 69.5, 138.8, 114.9 and 342.9 g/ha of Cd, Cr, Cu, Ni, Pb, Zn and F, respectively) and radionuclides (0.47, 0.16, 0.17 and 6.33 Bq/kg of soil to 238U, 226Ra, 232Th and 40K, respectively) incorporated in phosphate fertilizers and amendments are annually added in the sugar cane crops, but if utilized in accordance with the recommended rates, they do not raise the concentration levels in soils up to hazards values.

Ten years of NO2 comparisons between ground-based SAOZ and satellite instruments (GOME, SCIAMACHY, OMI)

SAOZ (Systeme d'Analyse par Observations Zenithales) is a ground-based UV-Visible zenith-sky spectrometer installed between 1988 and 1995 at a number of NDSC stations at various latitudes on the globe. The instrument is providing ozone and NO2 vertical columns at sunrise and sunset using the Differential Optical Absorption Spectroscopy (DOAS) technique in the visible spectral range. The ERS-2 GOME Ozone Monitoring Experiment (GOME) in 1995 was the first satellite mission to provide a global picture of atmospheric NO 2 with reasonable spatial and temporal resolution. It was then followed by SCanning ImAging spectroMeter for Atmospheric ChartographY (SCIAMACHY) onboard ENVISAT in 2002, and Ozone Monitoring Instrument (OMI) onboard EOS-AURA in 2004, with a similar capacity to monitor total NO 2. All these instruments are nadir viewing mapping spectrometers, applying the DOAS technique in the visible for deriving the NO2 total column. Here we present the results of NO2 long-term comparisons between GOME and SAOZ for the whole period of GOME operation since 1995 at all latitudes - tropics, mid-latitudes and polar regions - in both hemispheres. Comparisons are also shown with the most recently available SCIAMACHY and OMI data in 2004-2005. Overall, the daytime satellite measurements (around noon) are found consistent with sunrise ground-based data, with an average smaller difference at the tropics and mid-latitudes than in the polar areas in the summer. The agreement is even improved after correcting for the NO2 photochemical change between sunrise and the satellite overpass using a box model. However, some seasonal dependence of the difference between ground-based and satellite total NO2 still remains, related to the accuracy of photochemical simulations and the set of NO2 air mass factors used in the retrievals of both systems.

Iron determination by FAAS in fish feed and feces after ultrasound-assisted extraction

This paper proposes a method to determine iron in samples of fish feed and feces using ultrasound in the extraction of the analyte and in subsequent quantification by flame atomic absorption spectrometry. Using HCl 0.10 mol L -1 as the extraction solution, the optimal conditions of extraction were found to be: granulometry of the sample <60 μm; a sonication time of five cycles of 10 s and sonication power of 136 W. The method was applied in studies of the availability of iron in four food sources used in the diet of Nile Tilapia. The results obtained with the proposed extraction method allowed us to calculate the coefficients of apparent digestibility of iron in the food sources, which was not possible when using results obtained from samples mineralized by acid digestion. © Springer Science+Business Media, LLC 2008.

CdMoO 4 synthesized by a microwave-assisted hydrothermal method and their photoluminescence and photocatality properties

In this work CdMoO 4 nanoparticles were obtained under hydrothermal conditions using microwave radiation (2.45 GHz) (MH) at 100°C for different times. These powders were analyzed by X-ray diffraction (XRD), Field-emisson gum scanning electron microscopy (FEG-SEM), Ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements. XRD pattern confirmed that the pure CdMoO 4 phases were obtained. FEG-SEM powders present large-scale and homogeneous particles with microspheres-like morphology. UV-vis results were employed to determine the optical band gap these materials. Also, it showed existence of photoluminescence (PL) emission in the green wavelength range of 540-546 nm. Photocatalytic activity of CdMoO 4 nanocrystals was examined by monitoring the degradation of rhodamine B dye.

Microwave-assisted hydrothermal synthesis of ZnO powders with different reagents

In this work, zinc oxide powders were synthesized by microwave-assisted hydrothermal method in basic medium. These powders were analyzed by X-ray diffraction (XRD), Field-emisson gum scanning electron microscopy (FEG-SEM), Ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements. XRD pattern confirmed that the pure ZnO phases were obtained after MH processing performed at 130°C/ 1h. FEG-SEM micrographs reveals that these nanostructures are made up of ZnO plates. UV-vis results were employed to determine the optical band gap these materials. Also, it showed existence of photoluminescence (PL) in the different zinc powders. An orange PL emission when excited by 350 nm wavelength at room temperature was observad in the different powders.

Incorporation of dithiooxamide as a complexing agent into cellulose for the removal and pre-concentration of Cu(II) and Cd(II) ions from natural water samples

The present study describes the incorporation of a complexing agent, dithiooxamide, into microcrystalline cellulose for use in the pre-concentration of Cu(II) and Cd(II) ions from aqueous samples. The FTIR spectrum of the adsorbent exhibited an absorption band in the region of 800 cm-1, which confirmed the binding of the silylating agent to the matrix. Elemental analysis indicated the amount of 0.150 mmol g-1 of the complexing agent. The adsorption data were fit to the modified Langmuir equation, and the maximum amount of metal species extracted from the solution, Ns, was determined to be 0.058 and 0.072 mmol g-1 for Cu(II) and Cd(II), respectively. The covering fraction φ, which was 0.39 and 0.48 for Cu(II) and Cd(II), respectively, was used to estimate a 1:2 (metal:ligand) ratio in the formed complex, and a binding model was proposed based on this information. The adsorbent was applied in the pre-concentration of natural water samples and exhibited an enrichment factor of approximately 50-fold for the species studied, which enabled its use in the analysis of trace metals in aqueous samples. The system was validated by the analysis of certified standard (1643e), and the adsorbent was stable for more than 20 cycles, thus enabling its safe reutilization. © 2012 Elsevier B.V. All rights reserved.

A study of the precursors and photoactivity of nanostructures of Ti oxides synthesized by the alkaline hydrothermal method

The present study describes the synthesis, characterization and photocatalytic potential of Ti oxide nanostructures of various morphologies and crystalline phases that were synthesized from 4 different precursors by the alkaline hydrothermal method. The materials were characterized by mainly X-ray diffraction (XRD), Raman spectroscopy, scanning and transmission electron microscopy (SEM and TEM), thermogravimetric analysis (TGA) and X-ray absorption spectroscopy (XAS). Also, photocatalytic potential was assessed by rhodamine B photodegradation. The materials obtained from peroxytitanium complexes (PTCs) exhibited a strong dependence on the concentration of KOH ([KOH]) used for synthesis. The pre-formed sheets of the PTCs were critical to the formation of nanostructures such as nanoribbons, and they were also compatible with the rolling up process, which can be utilized to form structures such as nanorods, nanowires or nanotubes. In the rhodamine photodegradation tests, TiO2 anatase nanostructures with six-coor inated Ti were more effective than the titanate ones (five-coordinated), despite having a smaller surface area and fewer OH groups. The lower photoactivity of the titanates was attributed to the presence of five-coordinated titanium species (TiO5), which may act as electron-hole recombination centers. Furthermore, the material with a mixture of TiO2/titanate was shown to be promising for photocatalytic applications. © 2013 by American Scientific Publishers.

Altering the adsorptive and electronic properties of Pt through poly(vinyl alcohol) adsorption

In the present paper we investigated the effect of adsorbed PVA on Pt electrodes on classic electrochemical processes such as hydrogen UPD, oxygen reduction and CO electro-oxidation. Upon adsorption PVA blocks roughly 50% of the hydrogen sites and can not be removed from the Pt surface through cycling in the potential range of 0.05-1.0 V vs. RHE. Potentiodynamic experiments under controlled hydrodynamic conditions provided by rotating disk electrode experiments showed a negative impact of the adsorbed PVA on the oxygen reduction reaction (ORR). Cyclic-voltammetry results revealed that not even CO was able to remove PVA from the Pt surface. Regarding the oxidation of CO, the adsorbed polymer positively shifted the CO oxidation peak potential, therefore higher potentials are required to free the Pt surface from CO poisoning. In situ Fourier transform infrared spectroscopy evidenced that the presence of PVA shifted the linearly bound CO frequency toward higher wavenumbers, a process found to be independent of the Pt surface orientation. In situ electrochemical X-ray absorption spectroscopy results showed that PVA also impacted the electronic properties of platinum by decreasing the occupancy of the Pt conducting 5d band. Our findings clearly support the efforts toward understanding the nature of the interaction between polymers and metallic surfaces as well as the impact on technological applications (e.g. in PEMFCs). © 2013 Elsevier Ltd. All rights reserved.

Thermal denaturation and aggregation of hemoglobin of Glossoscolex paulistus in acid and neutral media

The thermal denaturation and aggregation of the HbGp, in the oxy- and cyanomet-forms, was investigated by DSC, AUC, DLS, optical absorption and CD, in the pH range from 5.0 to 7.0. Oxy-HbGp has a denaturation process partially reversible and dependent on the temperature. DSC melting curve is characterized by a single peak with Tc value of 333.4±0.2K for oxy-HbGp, while two peaks with Tc values of 332.2±0.1 and 338.4±0.2K are observed for cyanomet-HbGp, at pH 7.0. In acidic pH oxy- and cyanomet-HbGp are more stable showing higher Tc values and aggregation. AUC data show that, HbGp, at pH 7.0, upon denaturation, remains undissociated at 323K, presenting oligomeric dissociation at 333 (12±3% of tetramer and 88±5% of whole HbGp) and 343K (70±5% of monomer and 30±2% of trimer). DLS data show that the lag period before aggregation is dependent on the temperature and HbGp concentration. Optical absorption and CD results show that the increase of temperature leads to the oxy-HbGp oxidation and aggregation, above 331K, in acidic pH. CD data, for HbGp, present a greater thermal stability in acid medium than at neutral pH, with similar Tc values for both oxidation forms. Our data are consistent with previous studies and represents an advance in understanding the thermal stability of oligomeric HbGp structure. © 2012 Elsevier B.V.