Characterization and catalytic activity of iron(III) mono(4-N-methyl pyridyl)-tris(halophenyl) porphyrins in homogeneous and heterogeneous systems

The synthesis, characterization and catalytic activity of the cationic iron porphyrins Fe[M(4-N-MePy)TDCPP]Cl-2 and Fe[M(4-N-MePy)TFPP]Cl-2 in the epoxidation of (Z)-cyclooctene by PhIO in homogeneous solution and supported on silica gel (SG), imidazole propyl gel (IPG) or SG modified with 2-(4-sulfonatophenyl)ethyl groups (SiSO3) have been accomplished. When supported on IPG, both cationic FeP bind to the support via Fe-imidazole coordination. Fe[M(4-N-MePy)TDCPP]IPG contains a mixture of low-spin bis-coordinated (FeP)-P-III and high-spin mono-coordinated (FeP)-P-III species, whereas Fe[M(4-N-MePy)TFPP]IPG only contains high-spin mono-coordinated (FeP)-P-III. These FePIPG catalysts also contain (FeP)-P-II species, whose presence was confirmed by EPR spectroscopy using NO as a paramagnetic probe. Both cationic FePs coordinate to SG through Fe-O ligation and they are present as high-spin (FeP)-P-III species. The cationic FePs supported on SiSO3- are also high-spin (FeP)-P-III species and they bind to the support via electrostatic interaction between the 4-N-methylpyridyl groups and the SO3- groups present on the matrix. In homogeneous solution, both Fe[M(4-N-MePy)TDCPP]Cl-2 and Fe[M(4-N-MePy)TFPP]Cl-2 have similar catalytic activity to Fe(TDCPP)Cl and Fe(TFPP)Cl, leading to cis-epoxycyclooctane yields of 92%. When supported on inorganic matrices,both FePs lead to epoxide yields comparable to their homogeneous analogues and their anchoring enables catalyst recovery and re-use. Recycling of Fe[M(4-N-MePy)TDCPP]SiSO3- shows that this FeP maintains its activity in a second reaction. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Electrochemical Determination of Inorganic Contaminants in Automotive Fuels

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

NMR study of ion-conducting organic-inorganic nanocomposites poly(ethylene glycol) - Silica - LiClO4

Hybrid organic-inorganic ionic conductors, also called ormolytes, were obtained by dissolution of LiClO4 into silica/poly(ethylene glycol) matrices. Solid-state nuclear magnetic resonance (NMR) was used to probe the inorganic phase structure (Si-29) and the effects of the temperature and composition on the dynamic behavior of the ionic species (Li-7) and the polymer chains (H-1 and C-13). The NMR results between -100 and +90 degrees C show a strong correlation with ionic conductivity and differential scanning calorimetry experiments. The results also demonstrate that the cation mobility is assisted by segmental motion of the polymer, which is in agreement with the results previously reported for pure poly(ethylene oxide), PEG, electrolytes.

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.

Inorganic pyrophosphate-phosphohydrolytic activity associated with rat osseous plate alkaline phosphatase

Purified membrane-bound alkaline phosphatase from rat osseous plate hydrolyzed pyrophosphate in the presence of magnesium ions, with a specific activity of 92.7 U/mg. Optimal apparent pH for pyrophosphatase activity was 8.0 and it remained unchanged on increasing the pyrophosphate concentration. In the absence of magnesium ions the enzyme had a K-m = 88 mu M and V = 36.7 U/mg for pyrophosphate and no inhibition by excess substrate was observed. Pyrophosphatase activity was rapidly destroyed at temperatures above 40 degrees C, but magnesium ions apparently protected the enzyme against danaturation. Sodium metavanadate (Ki = 1.0 mM) was a competitive inhibitor of pyrophosphatase activity, while levamisole (Ki = 8.2 mM) and theophylline (Ki = 7.4 mM) were uncompetitive inhibitors. Magnesium ions (K-0.5 = 1.7 mu M) stimulated pyrophosphatase activity, while cobalt (Ki = 48.5 mu M) and zinc (Ki = 22.0 mu M) ions were non-competitive inhibitors. Manganese and calcium ions had no effect on pyrophosphatase activity. The M-w of the pyrophosphatase: protein was 130 kDa by gel filtration, but a value of 65 kDa was obtained by dissociative gel electrophoresis, suggesting that it was a dimer of apparently identical subunits. These results suggested that pyrophosphatase activity stems from the membrane-bound osseous plate alkaline phosphatase and not from a different protein.

Ionized-air-treated curaua fibers as reinforcement for phenolic matrices

Curaua fibers were treated with ionized air to improve the fiber/phenolic matrix adhesion.The treatment with ionized air did not change the thermal stability of the fibers. The impact strength increased with increase in the fiber treatment time. SEM micrographs of the fibers showed that the ionized air treatment led to separation of the fiber bundles. Treatment for 12 h also caused a partial degradation of the fibers, which prompted the matrix to transfer the load to a poorer reinforcing agent during impact, thereby decreasing the impact strength of the related composite. The composites reinforced with fibers treated with ionized air absorbed less water than those reinforced with untreated fibers.

Ruthenium(II) phosphine/diimine/picolinate complexes: Inorganic compounds as agents against tuberculosis

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Single real transformation matrices applied to double three-phase transmission lines

Single real transformation matrices are tested as phase-mode transformation matrices of typical symmetrical systems with double three-phase and two parallel double three-phase transmission lines. These single real transformation matrices are achieved from eigenvector matrices of the mentioned systems and they are based on Clarke's matrix. Using linear combinations of the Clarke's matrix elements, the techniques applied to the single three-phase lines are extended to systems with 6 or 12 phase conductors. For transposed double three-phase lines, phase Z and Y matrices are changed into diagonal matrices in mode domain. Considering non-transposed cases of double three-phase lines, the results are not exact and the error analyses are performed using the exact eigenvalues. In case of two parallel double three-phase lines, the exact single real transformation matrix has not been obtained yet. Searching for this exact matrix, the analyses are based on a single homopolar reference. For all analyses in this paper, the homopolar mode is used as the only homopolar reference for all phase conductors of the studied system. (C) 2008 Elsevier B.V. All rights reserved.

Structural damage identification and location using grammian matrices

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

Bacterial cellulose-silica organic-inorganic hybrids

Bacterial cellulose (BC) hydrated membranes present nanometric reticulated structure that can be used as a template in the preparation of new organic-inorganic hybrids. BC-silica hybrids were prepared from BC membranes and tetraethoxysilane, (TEOS) at neutral pH conditions at room temperature. Macroscopically homogeneous membranes were obtained containing up to 66 wt.% of silica spheres, 20-30 nm diameter. Scanning electron micrographs clearly show the silica spheres attached to cellulose microfibrils. By removing the cellulose, the silica spheres can be easily recovered. The new hybrids are stable up to 300 degrees C and display a broad emission band under UV excitation assigned to oxygen-related defects at the silica particles surface. Emission color can be tuned by changing the excitation wavelength.

Tissue response to polyanionic collagen: elastin matrices implanted in rat calvaria

The tissue response to polyanionic collagen matrices, prepared from bovine pericardium and implanted subperiosteally in rat calvaria, was studied. The materials were implanted in 72 male rats (Rattus norvegicus, albinus, Holtzman), randomly divided into four groups: GI-MBP hydrolyzed for 24 h; GII-MBP hydrolyzed for 36 h; GIII-MBP hydrolyzed for 48 h; GIV-native M BP. The materials were explanted after 15, 30 and 60 days and analyzed by routine histological procedures. Except for group IV (native bovine pericardium), polyanionic collagen from groups GI, GII and GIII showed low inflammatory reaction associated with bone formation, partially or completely integrated to the cranial bone; group GIV was characterized by an intense inflammatory reaction with occasional dystrophic mineralization and with occasional bone formation at 60 days when there was a decrease in the inflammatory reaction. Thus, the MBP from groups I, II and III were biologically compatible, enhancing bone formation with a slight delay at 60 days in GII. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

The volumetric fraction of inorganic particles and the flexural strength of composites for posterior teeth

Objective. To evaluate the content of inorganic particles and the flexural strength of new condensable composites for posterior teeth in comparison to hybrid conventional composites.Method. The determination of the content of inorganic particles was performed by mass weighing of a polymerized composite before and after the elimination of the organic phase. The volumetric particle content was determined by a practical method based on Archimedes' principle, which calculates the volume of the composite and their particles by differential mass measured in the air and in water. The flexural. strength of three points was evaluated according to the norm ISO 4049:1988.Results. The results showed the following filter content: Alert, 67.26%; Z-100, 65.27%; Filtek P 60, 62.34%; Ariston pHc, 64.07%; Tetric Ceram, 57.22%; Definite, 54.42%; Solitaire, 47.76%. In the flexural strength test, the materials presented the following decreasing order of resistance: Filtek P 60 (170.02 MPa) > Z-100 (151.34 MPa) > Tetric Ceram (126.14 MPa) = Alert (124.89 MPa) > Ariston pHc (102.00 MPa) = Definite (93.63 MPa) > Solitaire (56.71 MPa).Conclusion. New condensable composites for posterior teeth present a concentration of inorganic particles similar to those of hybrid composites but do not necessarily present higher flexural strength. (C) 2003 Elsevier B.V. Ltd. Alt rights reserved.

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

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

MATHEMATICA notebook for computing tetrahedral finite element shape functions and matrices for the Helmholtz equation

A MATHEMATICA notebook to compute the elements of the matrices which arise in the solution of the Helmholtz equation by the finite element method (nodal approximation) for tetrahedral elements of any approximation order is presented. The results of the notebook enable a fast computational implementation of finite element codes for high order simplex 3D elements reducing the overheads due to implementation and test of the complex mathematical expressions obtained from the analytical integrations. These matrices can be used in a large number of applications related to physical phenomena described by the Poisson, Laplace and Schrodinger equations with anisotropic physical properties.

Hierarchy and anarchy in quark mass matrices, or can hierarchy tolerate anarchy?

The consequences of adding random perturbations (anarchy) to a baseline hierarchical model of quark masses and mixings are explored. Even small perturbations of the order of 5% of the smallest non-zero element can already give deviations significantly affecting parameters of the Cabibbo-Kobayashi-Maskawa (CKM) matrix, so any process generating the anarchy should in general be limited to this order of magnitude. The regularities of quark masses and mixings thus appear to be far from a generic feature of randomness in the mass matrices, and more likely indicate an underlying order. (C) 2001 Published by Elsevier B.V. B.V.