New layered double hydroxides intercalated with substituted pyrroles. 2. 3-(Pyrrol-1-yl)-propanoate and 7-(pyrrol-1-yl)-heptanoate LDHs

We report the synthesis and characterization of organic-inorganic hybrid materials: Zn-2-Al-LDHs (layered double hydroxides) containing 3-(1H-pyrrol-1-yl)-propanoate and 7-(1H-pyrrol-l-yl)-heptanoate as the interlayer anions. The LDHs were synthesized by the co-precipitation method at constant pH followed by hydrothermal treatment for 72 h. The materials were characterized by PXRD, C-13 CP-MAS NMR, TGA, and ESR. The basal spacing found by PXRD technique is coincident with the formation of bilayers of the intercalated anions. The solid state C-13 NMR showed that the interlayered anions remain identical after intercalation. ESR data suggest that the monomers connect each other in a limited number of guests when a thermal treatment is applied. The inorganic LDH sheets delay the temperature of degradation of the monomers. (c) 2006 Elsevier Ltd. All rights reserved.

Characterization of humic acids from a Brazilian Oxisol under different tillage systems by EPR, C-13 NMR, FTIR and fluorescence spectroscopy

The importance of soil organic matter functions is well known, but structural information, chemical composition and changes induced by anthropogenic factors such as tillage practices are still being researched. In the present paper were characterized Brazilian humic acids (HAs) from an Oxisol under different treatments: conventional tillage/maize-bare fallow (CT1); conventional tillage/maize rotation with soybean-bare fallow (CT2)-, no-till/maize-bare fallow (NT1); no-till/maize rotation with soybean-bare fallow (NT2); no-till/maize-cajanus (NT3) and no cultivated soil under natural vegetation (NC). Soil HA samples were analyzed by electron paramagnetic resonance (EPR), solid-state C-13 nuclear magnetic resonance (C-13 NMR), Fourier transform intra-red (FTIR) and UV-Vis fluorescence spectroscopies and elemental analysis (CHNS). The FTIR spectra of the HAs were similar for all treatments. The level of semiquinone-type free radical determined from the EPR spectra was lower for treatments no-till/maize-cajanus (NT3) and noncultivated soil (1.74 X 10(17) and 1.02 x 10(17) spins g(-1) HA, respectively), compared with 2.3 X 10(17) spins g(-1) HA for other soils under cultivation. The percentage of aromatic carbons determined by C-13 NMR also decreases for noncultivated soil to 24%, being around 30% for samples of the other treatments. The solid-state C-13 NMR and EPR spectroscopies showed small differences in chemical composition of the HA from soils where incorporation of vegetal residues was higher, showing that organic matter (OM) formed in this cases is less aromatic. The fluorescence intensities were in agreement with the percentage of aromatic carbons, determined by NMR (r = 0.97 P < 0.01) and with semiquinone content, determined by EPR (r = 0.97 P < 0.01). No important effect due to tillage system was observed in these areas after 5 years of cultivation. Probably, the studied Oxisol has a high clay content that offers protection to the clay-Fe-OM complex against strong structural alterations. (C) 2003 Elsevier B.V. All rights reserved.

Correlation between the mobility of spin-labeled peptide chains and resin solvation: An approach to optimize the synthesis of aggregating sequences

Resin solvation properties affect the efficiency of the coupling reactions in solid-phase peptide synthesis. Here we report a novel approach to evaluate resin solvation properties, making use of spin label electron paramagnetic resonance (EPR) spectroscopy. The aggregating VVLGAAIV and ING sequences were assembled in benzhydrylamine-resin with different amino group contents (up to 2.6 mmol/g) to examine the extent of chain association within the beads. These model peptidyl-resins were first labeled at their N-terminus with the amino acid spin label 2,2,6,6-tetramethylpiperidine-N-oxyl-4-amino-4-carboxylic acid (Toac). Their solvation properties in different solvents were estimated, either by bead swelling measurement or by assessing the dynamics of their polymeric matrixes through the analysis of Toac EPR spectra, and were correlated with the yield of the acylation reaction. In most cases the coupling rate was found to depend on bead swelling. Comparatively, the EPR approach was more effective. Line shape analysis allowed the detection of more than one peptide chain population, which influenced the reaction. The results demonstrated the unique potential of EPR spectroscopy not only for improving the yield of peptide synthesis, even in challenging conditions, but also for other relevant polymer-supported methodologies in chemistry and biology.

Synthesis and pharmacological properties of TOAC-labeled angiotensin and bradykinin analogs

Angiotensin II (AngII) and bradykinin (BK) derivatives containing the TOAC (2,2,6,6-tetramethylpiperidine-N-oxyl-4-amino-4-carboxylic acid) spin label were synthesized by solid phase methodology. Ammonium hydroxide (pH 10, 50degreesC, 1 h) was the best means for reverting nitroxide protonation occurring during peptide cleavage. EPR spectra yielded rotational correlation times for internally labeled analogs that were nearly twice as large as those of N-terminally labeled analogs. Except for TOAC(1)-AngII and TOAC(0)-BK, which showed high intrinsic activities, other derivatives were inactive in smooth muscle preparations. These active paramagnetic analogs may be useful for conformational studies in solution and in the presence of model and biological membranes. (C) 2002 Elsevier B.V. All rights reserved.

The role of oxygen vacancies on the microstructure development and on the electrical properties of SnO2-based varistors

Variations on the microstructure development and on the electrical properties of SnO2-based varistors are discussed on the basis of the oxygen vacancies created or annihilated by the presence of different additives. Electron paramagnetic resonance (EPR) analysis of sintered samples evidenced a substantial increase in the paramagnetic oxygen vacancies concentration when Nb2O5 is added to the SnO2 center dot Co3O4 system. on the other hand, the observed diminution in the concentration of such species after the addition of Fe2O3 indicates solid solution formation. The quantification of paramagnetic oxygen vacancies allowed to confirm the proposed substitutions taking place in the lattice during sintering. These findings are supported by scanning electron microscopy, by density measurements and by current density versus electric field curves. The characterization of secondary phases through EDS assisted SEM and TEM is also reported in this work.

A laser-induced fluorescence spectroscopic study of organic matter in a Brazilian Oxisol under different tillage systems

Laser-induced fluorescence (LIF) spectroscopy has been proposed as new method for determining the degree of humification of organic matter (OM) in whole soils. It can be also used to analyze the OM in whole soils containing large amounts of paramagnetic materials, and which are neither feasible to Electron Paramagnetic Resonance (EPR) nor to C-13 Nuclear Magnetic Resonance (NMR) spectroscopy. In the present study, 3 LIF spectroscopy was used to investigate the OM in a Brazilian Oxisol containing high concentration of Fe+3. Soil samples were collected from two areas under conventional tillage (CT), two areas under no-till management (NT) and from a non-cultivated (NC) area under natural vegetation. The results of LIF spectroscopic analysis of the top layer (0-5 cm) of whole soils showed a less aromatic OM in the non-cultivated than in the cultivated soils. This is consistent with data corresponding to HA samples extracted from the same soils and analyzed by EPR, NMR and conventional fluorescence spectroscopy. The OM of whole soils at 5-10 and 10-20 cm depth was also characterized by LIF spectroscopy.Analysis of samples of NT and NC soils showed a higher OM aromatic content at depth. This is a consequence of the accumulation of plant residues at the soil surface in quantities that are too large for microorganisms to metabolize fully, thus, resulting in less aromatic or less hurnified humic substances. In deeper soil layers, the input of residues was lower and further decomposition of humic substances by microorganisms continued, and the aromaticity and degree of humification increased with soil depth. This data indicates that the gradient of humification of OM in the NT soil was similar to those observed in natural soils. Nevertheless, the degree of humification of the OM in the soils under no-till management varied less than that corresponding to non-cultivated soils. This may be because the former have been managed under these practices for only 5 years, in contrast to the continuous humification process occurring in the natural soils. on the other band, LIF spectroscopic analysis of the CT soils showed less pronounced changes or no change in the degree of humification with depth. This indicates that the ploughing and harrowing involved in CT lead to homogenization of the soil and thereby also of the degree of humification of OM throughout the profile. (c) 2006 Elsevier B.V. All rights reserved.

Polymeric organic-inorganic hybrid material containing iron(III) porphyrin using sol-gel process

Here we describe the preparation of iron(II) porphyrinosilica in a simple one-pot reaction, where the -SO2Cl groups present in the phenyl rings of FeTDCSPP+ react with 3-aminopropyltriethoxysilane and tetraethoxysilane in the presence of a nitrogenous base, leading to iron(III) porphyrinosilica. In this same procedure, molecular cavities containing regularly spaced functional groups are created through the molecular imprinting technique, in which the nitrogenous base coordinated to the iron(III) porphyrin serves as a template. The removal of such template in a Soxhlet extractor leads to a cavity with the same shape and size as the nitrogenous base, enabling the construction of shape-selective catalysts mimicking cytochrome P-450. Five different imprinting molecules have been used: imidazole, 1-methylimidazole, 2-methylbenzimidazole, 4-phenylimidazole and miconazole and ultra-violet/visible absorption spectroscopy, thermogravimetric analysis and electron paramagnetic resonance carried out. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Fmoc-POAC: [(9-fluorenylmethyloxycarbonyl)-2,2,5,5-tetramethylpyrrolidine-N-oxyl-3-amino-4-carboxylic acid]: A novel protected spin labeled beta-amino acid for peptide and protein chemistry

The stable free radical 2,2,6,6-tetramethylpiperidine-N-oxyl-4-amino-4-carboxylic acid (TOAC) is the only spin labeled amino acid that has been used to date to successfully label peptide sequences for structural studies. However, severe difficulty in coupling the subsequent amino acid has been the most serious shortcoming of this paramagnetic marker. This problem stems from the low nucleophilicity of TOAC's amine group towards the acylation reaction during peptide chain elongation. The present report introduces the alternative beta -amino acid 2,2,5,5-tetramethylpyrrolidine-N-oxyl-3-amino-4-carboxylic acid (POAC), potentially useful in peptide and protein chemistry. Investigations aimed at addressing the stereochemistry of this cyclic molecule through X-ray diffraction measurements of crystalline and bulk samples revealed that it consists only of the trans conformer. The 9-fluorenylmethyloxyearbonyl group (Fmoc) was chosen for temporary protection of the POAC amine function, allowing insertion of the probe at any position in a peptide sequence. The vasoactive octapeptide angiotensin II (AII, DRVYIHPF) was synthesized by replacing Pro(7) with POAC. The reaction of Fmoc-POAC with the peptidyl-resin occurred smoothly, and the coupling of the subsequent amino acid showed a much faster reaction when compared with TOAC. POAC(7)-AII was obtained in good yield, demonstrating that, in addition to TOAC, POAC is a convenient amino acid for the synthesis of spin labeled peptide analogues. The present findings open the possibility of a wide range of chemical and biological applications for this novel beta -amino acid derivative, including structural investigations involving its differentiated bend-inducing characteristics.

Organic complexation and translocation of ferric iron in podzols of the Negro River watershed. Separation of secondary Fe species from Al species

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

CeO2 nanoparticles synthesized by a microwave-assisted hydrothermal method: evolution from nanospheres to nanorods

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

Er(3+) doped phosphoniobate glasses and planar waveguides: structural and optical properties

Phosphoniobate glasses with composition (mol%) (100-x) NaPO(3)-xNb(2)O(5) ( x varying from 11 to 33) were prepared and characterized by means of thermal analysis, Fourier transform infrared spectroscopy, Raman scattering and (31)P nuclear magnetic resonance. The addition of Nb(2)O(5) to the polyphosphate base glass leads to depolymerization of the metaphosphate structure. Different colors were observed and assigned as indicating the presence of Nb(4+) ions, as confirmed by electron paramagnetic resonance measurements. The color was observed to depend on the glass composition and melting temperature as well. Er(3+) containing samples were also prepared. Strong emission in the 1550 nm region was observed. The Er(3+4)I(15/2) emission quantum efficiency was observed to be 90% and the quenching concentration was observed to be 1.1 mol%( 1.45 x 10(20) ions cm(-3)). Planar waveguides were prepared by Na(+)-K(+)-Ag(+) ion exchange with Er(3+) containing samples. Optical parameters of the waveguides were measured at 632.8, 543.5 and 1550 nm by the prism coupling technique as a function of the ion exchange time and Ag(+) concentration. The optimized planar waveguides show a diffusion depth of 5.9 mu m and one propagating mode at 1550 nm.

Chemical process to separate iron oxides particles in pottery sample for EPR dating

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

Photoluminescence in quasi-amorphous Pb0.8X0.2Zr0.53Ti0.47O3 (X = Ca, Sr and Ba) powders: An optical and structural study

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

Synthesis, characterization, crystal structure, and biological studies of vanadium complexes with glycolic acid

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Structural conditions that leads to photoluminescence emission in SrTiO3: An experimental and theoretical approach

Complex cluster [TiO5 center dot V-O(z)] and [SrO11 center dot V-O(z)] (where V-O(z)=V-O(X), V-O(center dot), V-O(center dot center dot)) vacancies were identified in disordered SrTiO3 powders prepared by the polymeric precursor method, based on experimental measurements by x-ray absorption near edge structure spectroscopy. The paramagnetic complex states of [TiO5 center dot V-O(center dot)] and [SrO11 center dot V-O(center dot)] with unpaired electrons were confirmed by electron paramagnetic resonance spectroscopy. The disordered powders showed strong photoluminescence at room temperature. Structural defects of disordered powders, in terms of band diagram, density of states, and electronic charges, were interpreted using high-level quantum mechanical calculations in the density functional framework. The four periodic models used here were consistent with the experimental data and explained the presence of photoluminescence. (C) 2008 American Institute of Physics.