Synthesis and structure of a new heteronuclear (eta(6)-arene) tricarbonylchromium compound incorporating propargyl amine unit

Reaction of equimolar amounts of [Co-2(CO)(6)(dppm)] and [Cr(eta(6)-C6H5)(C=-CCH2NMe2)(CO)(3)] (1) in benzene gives the novel heterotrimetallic complex [Cr(eta(6)-C6H5){(mu(2)-eta(2)-C=CCH2NMe2)Co-2(CO)(4)(dppm)}(CO)(3)] (2) in 40% yield. The X-ray structure analysis of 2 reveals that the Cr(CO)(3) tripod adopts a nearly anti-eclipsed conformation. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Automatic identification by C-13 NMR of substituent groups bonded in natural product skeletons

The aim of this paper is to present a procedure that utilizes C-13 NMR for identification of substituent groups which are bonded to carbon skeletons of natural products. For so much was developed a new version of the program (MACRONO), that presents a database with 161 substituent types found in the most varied terpenoids. This new version was widely tested in the identification of the substituents of 60 compounds that, after removal of the signals that did not belong to the carbon skeleton, served to test the prediction of skeletons by using other programs of the expert system (SISTEMAT). (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Design of Gaussian basis sets to the theoretical interpretation of IR-spectrum of hexaaquachromium (III) ion, tetraoxochromium (IV) ion, and tetraoxochromium (VI) ion

The Generator Coordinate Hartree-Fock (GCHF) method is employed to design 16s, 16s10p, 24s17p13d, 25s17p13d, and 26s17p Gaussian basis sets for the H ((2)S), O ((3)P), O(2-) ((1)S), Cr(3+) ((4)F), Cr(4+) ((3)F), and Cr(6+) ((1)S) atomic species. These basis sets are then contracted to (4s) for H ((2)S), (6s4p) for O ((3)P), and O(2-) ((1)S), (986p3d) for Cr(3+) ((4)F), (10s8p3d) for Cr(4+) ((3)F), and (13s7p) for Cr(6+) (1S) by a standard procedure. For evaluation of the quality of those basis sets in molecular calculations, we have accomplished studies of total and orbital (HOMO and HOMO-1) energies at the HF-Roothaan level for the molecular species of our interest. The results obtained with the contracted basis sets are compared to the values obtained with our extended basis sets and to the standard 6-311G basis set from literature. Finally, the contracted basis sets are enriched with polarization function and then utilized in the theoretical interpretation of IR-spectrum of hexaaquachromium (III) ion, [Cr(H(2)O)(6)](3+), tetraoxochromium (IV) ion, [CrO(4)](4-), and tetraoxochromium (VI) ion, [CrO(4)](2-). The respective theoretical harmonic frequencies and IR-intensities were computed at the density functional theory (DFT) level. In the DFT calculations we employed the Becke's 1988 functional using the LYP correlation functional. The comparison between the results obtained and the corresponding experimental values indicates a very good description of the IR-spectra of the molecular ions studied, and that the GCHF method is still a legitimate alternative for selection of Gaussian basis sets. (C) 2003 Elsevier B.V. All rights reserved.

Evaluation of hygrothermal effects on the shear properties of Carall composites

Fiber metal laminates are the frontline materials for aeronautical and space structures. These composites consists of layers of 2024-T3-aluminum alloy and composite prepreg layers. When the composite layer is a carbon fiber prepreg, the fiber metal laminate, named Carall, offers significant improvements over current available materials for aircraft structures. While weight reduction and improved damage tolerance characteristics were the prime drivers to develop this new family of materials, it turns out that they have additional benefits, which become more and more important for today's designers, such as cost reduction and improved safety. The degradation of composites is due to environmental effects mainly on the chemical and/or physical properties of the polymer matrix leading to loss of adhesion of fiber/resin interface. Also, the reduction of fiber strength and stiffness are expected due to environmental degradation. Changes in interface/interphase properties leads to more pronounced changes in shear properties than any other mechanical properties. In this work, the influence of moisture in shear properties of carbon fiber/epoxy composites and Carall have been investigated by using interlaminar shear (ILSS) and Iosipescu tests. It was observed that hygrothermal conditioning reduces the Iosipescu shear strength of CF/E and Carall composites due to the moisture absorption in these materials. (c) 2006 Elsevier B.V. All rights reserved.

Infrared and far-infrared spectroscopy of (CH3OH)-C-13: TeraHertz laser lines and assignments

We use a (CO2)-C-13 laser as optical pumping source to search for new THz laser lines generated from (CH3OH)-C-13. Nineteen new THz laser lines (also identified as far-infrared, FIR) ranging from 42.3 mu m (7.1 THz) to 717.7 mu m (0.42 THz) are reported. They are characterized in wavelength, offset, relative polarization, relative intensity, and optimum working pressure. We have assigned eight laser lines to specific rotational energy levels in the excited state associated with the C-O stretching mode. (c) 2006 Elsevier B.V. All rights reserved.

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.

A fast microwave-assisted, acid-vapor, steam-cleaning procedure for autosampler cups

A new and fast procedure is proposed for cleaning autosampler cups using acid-vapor steam-cleaning with a miniaturized assembly in a microwave-heated sealed Teflon vessel. A glass cactus-shaped holder was made to support six polyethylene autosampler cups (volume, 2.0 mt) inside a 100 mt microwave vessel. Regent-grade nitric acid was added to the vessels, and the system was heated in a microwave oven for 5 min at 300 W. Chromium was determined by graphite-furnace atomic-absorption spectrophotometry. The blank values were lower with cleaned cups compared to untreated cups (i.e., as received from supplier). The quantification limits, estimated from detection limits established with Milli-Q water, were 0.66 and 0.95 mu g Cr L-1 for cleaned and untreated auto-sampler cups, respectively. (C) 1998 Elsevier B.V. B.V. All rights reserved.

Effect of PbO excess on the formation of lead magnesium niobate perovskite by the columbite method

The effect of lead excess on the pyrochlore-type formation in Pb(Mg1/3Nb2/3)O-3 (PMN) powders has been investigated. The polymeric precursor method was used in the synthesis of the columbite in association to the partial oxalate method to synthesize the PMN powder samples. Structure refinement of the columbite precursor and PMN powders was carried out using the Rietveld method. The quantitative phase analysis showed that the amount of perovskite phase is not affected by PbO excess, but a great excess drives the pyrochlore-type formation so that 3 wt.% of PbO causes the predominance of Mg-containing pyrochlore phase. Using the refined data obtained from the Rietveld refinement, the compositional fluctuation in the perovskite phase was calculated from Nb/Mg ratio values and Pb occupation factor. Mg inclusion occurs concomitant with Ph one into PMN perovskite phase and this effect is directed by PbO excess during powder synthesis. (C) 2003 Elsevier B.V. All rights reserved.

Structural evolution up to 1100 degrees C of xerogels prepared from TEOS sonohydrolysis and liquid phase exchanged by acetone

Silica xerogels were prepared from sonohydrolysis of tetraethoxysilane and exchange of the liquid phase of the wet gel by acetone. Monolithic xerogels were obtained by slow evaporation of acetone. The structural characteristics of the xerogels were studied as a function of temperature up to 1100 degrees C by means of bulk and skeletal density measurements, linear shrinkage measurements and thermal analyses (DTA, TG and DL). The results were correlated with the evolution in the UV-Vis absorption. Particularly, the initial pore structure of the dried acetone-exchanged xerogel was studied by small-angle X-ray scattering and nitrogen adsorption. The acetone-exchanged xerogels exhibit greater porosity in the mesopore region presenting greater mean pore size (similar to 4 nm) when compared to non-exchanged xerogels. The porosity of the xerogels is practically stable in the temperature range between 200 degrees C and 800 degrees C. Evolution in the structure of the solid particles (silica network) is the predominant process upon heating up to about 400 degrees C and pore elimination is the predominant process above 900 degrees C. At 1000 degrees C the xerogels are still monolithic and retain about 5 vol.% pores. The xerogels exhibited foaming phenomenon after hold for 10 h at 1100 degrees C. This temperature is even higher than that found for foaming of non-exchanged xerogels. (c) 2005 Elsevier B.V. All rights reserved.

Endothelial dysfunction in DOCA-salt hypertension - Possible involvement of prostaglandin endoperoxides

The effects of the arachidonic acid metabolism inhibitors on the acetylcholine responses of aortae from control (CR) and deoxycorticosterone acetate (DOCA)-salt hypertensive (HR) rats were investigated. The acetylcholine decreased response observed in HR [relaxation (%): CR 95.5 +/- 2.7, n = 4; HR 52.0 +/- 6.3, n = 5, p < 0.05] was restored by the cyclooxygenase inhibitor piroxicam [relaxation (%): CR 99.8 +/- 0.2, n = 4; HR 86.0 +/- 4.0, n = 5] and by the thromboxane synthetase inhibitor and the thrombox ane A(2)/prostaglandin H-2 receptor antagonist ridogrel [relaxation (%): CR 92.1 +/- 4.4, n = 7; HR 93.1 +/- 2.0, n = 7] but not by the inhibitors of thromboxane synthetase, prostacyclin synthetase, cytochrome P-450 monooxygenase, and lipoxygenase. So, endoperoxide intermediates seem to be involved in the decreased endothelium-dependent relaxation to acetylcholine in DOCA-salt hypertension. (C) 1999 Elsevier B.V. All rights reserved.

Effect of the bath pH on the electrodeposition of nanocrystalline Pd-Co alloys and their magnetic properties

The effect of the bath pH on the electrodeposition of nanocrystalline Pd-Co alloys and on their magnetic properties was studied. The pH practically did not affect the alloy composition. Conversely, the pH showed a significant influence on the shape and size of crystallites. Two different crystallites morphology were observed depending on the bath pH. A crystallite size ranging from 18.2 to 30 nm was obtained from X-ray diffractometry (XRD) patterns using the Scherrer's method. Also from the XRD patterns the lattice strain percentage was calculated and correlated with the residual stress, which probably originated during the film electrodeposition on the substrate. Some alloy magnetic properties showed small variations. In contrast, high and unexpected coercivities were obtained reaching a maximum of 1.69 kOe at pH 5.5. The high coercivity values were attributed to the presence of residual stress at the film-substrate interface, which increased as the bath pH and crystallite size decrease, both of them contributing simultaneously to increase in coercivity. (C) 2006 Elsevier B.V. All rights reserved.

Characterization of iron(III)porphyrin-hydroxo complexes in organic media through UV-Vis and EPR spectroscopies

The interaction of OH- with Fe(TPP)(+), Fe(TDCPP)(+), Fe(TMP)(+) and Fe(TFPP)(+) in 1,2-dichloroethane was studied by titrating FeP solutions with aliquots of a solution of tetrabutylammonium hydroxide in acetonitrile. The number of OH- ions (n) coordinated to the FeP and the stability constants (beta(n)) for the FeP-OH- complexes were calculated from UV-Vis absorbance data and iron spin states were determined through EPR spectroscopy, Fe(TMP) (+) forms a high-spin mono-hydroxo complex, while Fe(TPP)I and Fe(TDCPP)(+) form high-spin bis-hydroxo complexes. To our knowledge, this is the first time that the formation of bis-hydroxo complexes from Fe(TPP) (+) has been reported, and this was possible because the studies were carried out in basic organic media, In this same medium, Fe-III-Fe-II reduction upon OH- addition to Fe(TFPP) (+) was observed, without concomitant formation of the mu-oxo dimeric species [Fe(TFPP)](2)O. (C) 1999 Elsevier B.V., All rights reserved.

Development of a voltammetric sensor for chromium(VI) determination in wastewater sample

Screen-printed carbon electrode (SPCE) modified with poly-L-histidine film can be successfully applied for chromium(VI) determination based on its pre-concentration. Optimum adherence and stability of the POIY-L-histidine film was obtained by direct addition of PH solution 1% (w/v) on the electrode surface, followed by heating at 80 degrees C during 5 min. Linear response range, sensitivity and limit of detection were 0. 1-150 [mu mol L-1, 4. 13 LA mu mol L` and 0.046 mu mol L-1. The repeatability of the proposed sensor, evaluated in terms of relative standard deviation, was measured as 3.2% for 10 experiments in 40 mu mol L-1 using the same electrode and 4.0% using screen-printed electrode as disposable sensor, respectively. The voltammetric sensor was applied to determination of Cr(VI) and indirect determination of Cr(III) in wastewater samples previously treated by a leather dyeing industry and the average recovery for these samples was around 97%. (C) 2006 Elsevier B.V. All rights reserved.

Immobilization and electrochemical properties of anionic complexes on a V2O5/surfactant nanocomposite

in this work, we report a new way of modifying an electrode by combining the intrinsic conductivity property of vanadium pentoxide xerogel with its water insolubility in the presence of the cationic surfactant N-cetyl-N,N,N,trimethyl-ammonium bromide (CTA(+)Br(-)). The obtained hybrid compound enables the immobilization of electroactive anions such as hexacyanoferrate (III) ([Fe(CN)(6)](3-)) and its analogue pentacyanonitrosylferrate (II) ([Fe(CN)(5)NO](2-)), rather than cations. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Synthesis, characterisation and thermal behaviour of solid state compounds of 4-methylbenzylidenepyruvate with some bivalent metal ions

Solid state M-4-Me-BP compounds, where M stands for bivalent Mn, Fe, Co, Ni, Cu, Zn, Pb and 4-Me-BP is 4-methylbenzylidenepyruvate, have been synthesized. Simultaneous thermogravimetry-differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), X-ray powder diffractometry, infrared spectroscopy, elemental analysis, and complexometry were used to characterise and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, thermal stability and thermal decomposition of the isolated complexes. (C) 2002 Elsevier B.V. B.V. All rights reserved.