Kinetics and mechanism of the induced redox reaction of [Ni(cyclam)](2+) promoted by SO5 center dot-

Oxidation of [Ni(cyclam)](2+), cyclam = 1,4,8,11-tetraazacyclotetradecane, accelerated by sulfur dioxide, was studied spectrophotometrically by following the formation of [Ni(cyclam)](3+) under the conditions: [Ni(cyclam)](2+) = 6.0 x 10(-3) M; initial [Ni(cyclam)](3+) = 8.0 x 10(-6) M; [cyclam] = 6.0 x 10(-3) M; [SO2] = (1.0-5.0) x 10(-4) M and 1.0 M perchloric acid in oxygen saturated solutions at 25.0 degrees C and ionic strength = 1.0 M. The oxidation reaction exhibits autocatalytic behavior in which the induction period depends on the initial Ni(III) concentration. A kinetic study of the reduction of Ni(III) by SO2 under anaerobic conditions, and the oxidation of Ni(II), showed that the rate-determining step involves reduction of Ni(III) by SO2 to produce the SO3.- radical, which rapidly reacts with dissolved oxygen to produce SO5.- and rapidly oxidizes Ni(II). The results clearly show a redox cycling process which depends on the balance of SO2 and oxygen concentrations in solution.

Synthesis and X-ray structure of the dinuclear platinum(II) complex with saccharin {K[Pt(sac)(3)(H2O)] center dot H2O}(2): Studies on its antiproliferative activity in aqueous solution

Synthesis and X-ray structure of a dinuclear platinum(II) complex with the ligand saccharin(sac) are described. The structure shows two approximately square-planar platinum centers. Each platinum atom is coordinated to one water molecule and three N-bonded saccharinate ligands. The two centers are linked through two potassium atoms. Each potassium atom interacts with six oxygen atoms from hydration and coordinated water molecules and from carbonyl and sulfonate groups of the ligands. It is suggested that, in aqueous solution, the dimeric structure of the complex is dissociated and the monomeric species K[Pt(sac)(3)(H2O)] is formed. The complex was dissolved in water and submitted to in vitro cytotoxic analyses using HeLa cells (human cervix cancer). It was shown that the monomeric complex elicited a potent cytotoxic activity when compared to the vehicle-treated cells. The IC50 value for the monomeric complex is 6.8 mu M, a little bit higher than that obtained for cisplatin. (c) 2007 Elsevier B.V. All rights reserved.

Multidisciplinary approach to chronic pain from myofascial pain dysfunction syndrome: A four-year experience at a Brazilian center

Chronic pain is the major complaint of myofascial pain dysfunction syndrome (MPDS) and is a complex problem which involves physical, psychological and social aspects, the etiology of MPDS is multifactorial and the multidisciplinary approach is essential for differential diagnosis and for comprehensive treatment planning, In 1993, the Dental School of Piracicaba-UNICAMP, Brazil, opened a Center for Pain Studies (CPS), staffed by health care providers including, dentists, psychologists, physicians, physiotherapists and phonoaudiologists. The major aims of the CPS are to provide clinical care and to develop basic and applied research, Sixty-two MPDS patients had been admitted to the CPS by 1997, There were 60 females and 2 males, mean age -32.5 years, the mean duration of chronic pain was 48 months. Pain intensity and unpleasantness were measured employing the Visual Analogue Scale, the tendency to develop stress-related diseases was assessed by the Social Readjustment de Scale, There was a mean reduction of chronic pain of 69.89% and 71.78% relative to intensity and unpleasantness, respectively, the experience of clinical attendance at a multidisciplinary center showed the relevance of a team consisting of health care providers from different specialties with well-established aims, completely integrated and sensitive enough to understand the painful complaints of MPDS patients.

Kinetic aspects of ion exchange in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds: A combined electrical and mass transfer functions approach

The present paper quantifies and develops the kinetic aspects involved in the mechanism of interplay between electron and ions presented elsewhere(1) for KhFek[Fe(CN)(6)](l)center dot mH(2)O (Prussian Blue) host materials. Accordingly, there are three different electrochemical processes involved in the PB host materials: H3O+, K+, and H+ insertion/extraction mechanisms which here were fully kinetically studied by means of the use of combined electronic and mass transfer functions as a tool to separate all the processes. The use of combined electronic and mass transfer functions was very important to validate and confirm the proposed mechanism. This mechanism allows the electrochemical and chemical processes involved in the KhFek[Fe(CN)(6)](l)center dot mH(2)O host and Prussian Blue derivatives to be understood. In addition, a formalism was also developed to consider superficial oxygen reduction. From the analysis of the kinetic processes involved in the model, it was possible to demonstrate that the processes associated with K+ and H+ exchanges are reversible whereas the H3O+ insertion process was shown not to present a reversible pattern. This irreversible pattern is very peculiar and was shown to be related to the catalytic proton reduction reaction. Furthermore, from the model, it was possible to calculate the number density of available sites for each intercalation/deintercalation processes and infer that they are very similar for K+ and H+. Hence, the high prominence of the K+ exchange observed in the voltammetric responses has a kinetic origin and is not related to the amount of sites available for intercalation/deintercalation of the ions.

MAGNETOOPTICAL PROPERTIES OF F-2(+) CENTER IN KCL-SH-

The magnetic circular dichroism (MCD) of F2+ centers in KCl:SH- has been measured in absorption in the 1ssigma(g) --> 2p(y)pi(u) transitions at 493 and 509 nm, with fields up to 5 T and in the temperature range 1.5 K < T < 77 K. Within the limit of detection, no MCD is observed in the near infrared transition 1ssigma(g) --> 2psigma(u) as well as in both emissions 2ppi(u) --> 1ssigma(g) and 2psigma(u) --> 1ssigma(g). The optical detection of EPR in the F2+ ground state presents an isotropic single band with g = 1.965 +/- 0.007. The spin-lattice relaxation measured at H = 0.32 T is typical of a direct process T-1 = 4.3 x 10(-2_ coth (gmu(B)H/2k(B)T). The spectral variation of the MCD is calculated using perturbation theory to first order. The Hamiltonian includes the spin-orbit interaction in the 2ppi(u) excited state and the orbital molecular wave functions are obtained by a linear combination of 1s and 2p atomic orbitals. The calculated MCD is in good agreement with the observed one, for the spin-orbit interaction strength Pound(z) = 3.6 meV.

Nonlinear behavior of TiO2 center dot Ta2O5 center dot MnO2 material doped with BaO and Bi2O3

A study was made on the effect of the addition of BaO (0.025-0.05 mol%) and Bi2O3 (0.025-0.05 mol%) to the TiO2.Ta2O5.MnO2 material. The samples were characterized by X-ray diffraction, and current-voltage measurements were accomplished for determination of the nonlinear coefficient. An analysis was made to evaluate the microstructural characteristics of the materials. The most appropriate sintering conditions for the materials were analyzed with the purpose of obtaining the best nonlinear coefficient associated with the smallest breakdown electric field. After sintering at 1400 degreesC for 2 h, a low-voltage (30 V cm(-1)) varistor was obtained, which, however, presented a low nonlinear coefficient (6). It was found that the sintering conditions must be controlled in order to improve the electrical properties of these materials. (C) 2004 Elsevier B.V. All rights reserved.

Thermodynamic aspects of ion intercalation in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds: Application to the Everit's salt/Prussian Blue transition

The K+ reversible processes for ion exchange in KhFek[Fe(CN)(6)](l)center dot mH(2)O host compounds (Prussian Blue) were thermodynamically analyzed. A thermodynamic approach was established and developed based on the consideration of a lattice-gas model where the electronic contribution to the chemical potential is neglected and the ion-host interaction is not considered. The occupation fraction of the intercalation process was calculated from the kinetic parameters obtained through ac-electrogravimetry in a previous paper. In this way, the mass potential transfer function introduces a new way to evaluate the thermodynamic aspect of intercalation. Finally, based on the thermodynamic approach, the energy used to put each K+ ion into the host material was calculated. The values were shown to be in good agreement with the values obtained through transient techniques, for example, cyclic voltammetry. As a result, this agreement between theory and experimental data validates the thermodynamic approach considered here, and for the first time, the thermodynamic aspects of insertion were considered for mixed valence materials.

New Ni(II)-sulfonamide complexes: Synthesis, structural characterization and antibacterial properties. X-ray diffraction of [Ni(sulfisoxazole)(2)(H2O)(4)] center dot 2H(2)O and [Ni(sulfapyridine)(2)]

The synthesis, structural characterization, voltammetric experiments and antibacterial activity of [Ni(sulfisoxazole)(2)(H2O)(4)] center dot 2H(2)O and [Ni(sulfapyridine)(2)] were studied and compared with similar previously reported copper complexes. [Ni(sulfisoxazole)(2)(H2O)(4)] center dot 2H(2)O crystallized in a monoclinic system, space group C2/c where the nickel ion was in a slightly distorted octahedral environment, coordinated with two sulfisoxazole molecules through the heterocyclic nitrogen and four water molecules. [Ni(sulfapyridine)(2)] crystallized in a orthorhombic crystal system, space group Pnab. The nickel ion was in a distorted octahedral environment, coordinated by two aryl amine N from two sulfonamides acting as monodentate ligands and four N atoms (two sulfonamidic N and two heterocyclic N) from two different sulfonamide molecules acting as bidentate ligands. Differential pulse voltammograms were recorded showing irreversible peaks at 1040 and 1070 mV, respectively, attributed to Ni(II)/Ni(III) process. [Ni(sulfisoxazole)(2)(H2O)(4)] center dot 2H(2)O and [Ni(sulfapyridine)(2)] presented different antibacterial behavior against Staphylococcus aureus and Escherichia coli from the similar copper complexes and they were inactive against Mycobacterium tuberculosis. (c) 2007 Elsevier B.V. All rights reserved.

A new processing method of CaZn2(OH)(6)center dot 2H(2)O powders: Photoluminescence and growth mechanism

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Centers on center manifolds in the Lu system

We confirm a conjecture of Mello and Coelho [Phys. Lett. A 373 (2009) 1116] concerning the existence of centers on local center manifolds at equilibria of the Lu system of differential equations on R(3). Our proof shows that the local center manifolds are algebraic ruled surfaces, and are unique. (C) 2011 Elsevier B.V. All rights reserved.

Neonatal meningitis according to the microbiological diagnosis: a decade of experience in a tertiary center

The aim of this study was to evaluate the incidence of and mortality due to meningitis and compare data according to microbiological diagnosis. This was a ten-year retrospective study conducted at a neonatal intensive care unit (NICU). Newborns with meningitis confirmed by positive CSF culture were included; those with congenital infection or malformations that made lumbar puncture impossible were excluded. The variables investigated were birth weight, gestational and postnatal age, procedures, hematological and CSF parameters, and complications. Parametric and non-parametric tests were used (statistical value p<0.05). The incidence of meningitis was 0.6% and mortality was 27%. of the 22 cases, 59% involved Gram-negative bacteria; 36% Gram-positive and 5% fungi. The groups did not differ in relation to birth weight, gestational and postnatal age, procedures or hematological and CSF parameters. Sepsis, convulsions and deaths were frequent in both groups, without statistical difference. Gram-negative cases showed abscesses and higher frequency of ventriculitis and hydrocephaly. Meningitis was infrequent, but presented high mortality and frequent complications.

Epidemiology of the Cnidarian Physalia physalis stings attended at a health care center in beaches of Adicora, Venezuela

Stings caused by jellyfish and jellyfish-like colonies are common all around the world, with serious manifestations and occasional deaths reported in some countries. Between December 2006 and 2007, epidemiological, clinical and treatment aspects of stings caused by the Portuguese man-of-war (Physalia physalis) in 59 patients consulting the ambulatory emergency in Adicora, Falcon State, Venezuela, were studied. Most of the stings occurred in males (59%) preschool and school-aged children (49%), visitors from other areas of the country (92%) during holidays when bathing or diving at the beach (97%). Injuries presented linear erythematous plaques at the point of contact with the animal, located in several anatomical sites. Most clinical manifestations observed were: intense burning pain, urticaria, erythema and inflammation (100%), as well dyspnea with laryngeal edema and fever (19%). Patients were treated with topical drugs, including antihistamine and antipyretic drugs, but also with systemic hydrocortisone. P. physalis stings in Adicora appeared to have a seasonal pattern, with systemic complications potentially life-threatening. Thus, epidemiological surveillance program is recommended, particularly in travelers. (C) 2012 Elsevier Ltd. All rights reserved.

Performance of constructed wetland system for public water supply

The project is being conducted in the town of Analândia, São Paulo, Brazil. The constructed wetlands system for water supply consists of a channel with floating aquatic macrophytes, HDS system (Water Decontamination with Soil - Patent PI 850.3030), chlorinating system, filtering system and distribution. The project objectives include investigating the process variables to further optimize design and operation factors, evaluating the relation of nutrients and plants development, biomass production, shoot development, nutrient cycling and total and fecal coliforms removal, comparing the treatment efficiency among the seasons of the year; and moreover to compare the average values obtained between February and June 1998 (Salati et al., 1998) with the average obtained for the same parameters between March and June 2000. Studies have been developed in order to verify during one year the drinking quality of the water for the following parameters: turbidity, color, pH, dissolved oxygen, total of dissolved solids, COD, chloride, among others, according to the Ministry of Health's Regulation 36. This system of water supply projected to treat 15 L s-1 has been in continuous operation for 2 years, it was implemented with support of the National Environment Fund (FNMA), administered by the Center of Environmental Studies (CEA-UNESP), while the technical supervision and design were performed by the Institute of Applied Ecology. The actual research project is being supported by FAPESP.

Optimization of neutral hydrolysis reaction of post-consumer PET for chemical recycling

The neutral hydrolysis reaction of post-consumer poly(ethylene terephthalate) in solid state was studied through the reaction of the polymer with water at the molar ratio 1:91 with autogenous pressure. Two sizes of post-consumer PET flakes and temperatures of 135 °C, 170°C and 205°C with pressures of 4.0 atm, 7.5 atm and 13.5 atm, respectively, were considered. With reaction time equal to 6h, the method reached 99% depolymerization at 205°C, 8.2% at 170 °C and 1.7% at 135°C. The reaction extension was measured by separating the terephthalic acid formed in the process and calculating by gravimetry how much material could still be reacted. Through the viscosimetry of diluted, solutions and the counting of carboxylic end groups in the remaining material from the gravimetric assay, it was possible to suggest that the reaction occurs randomly and in the whole volume of the polymeric particle and not solely on the surface. The terephthalic acid obtained and then purified was characterized by elemental analysis, magnetic nuclear resonance, size and panicle size distribution and spectrophotometry in the visible spectrum, and it was similar to the petrochemical equivalent, with purity recorded in carbon base equal to 99.9%.

Reversible Hamiltonian Liapunov center theorem

We study the existence of periodic solutions in the neighbourhood of symmetric (partially) elliptic equilibria in purely reversible Hamiltonian vector fields. These are Hamiltonian vector fields with an involutory reversing symmetry R. We contrast the cases where R acts symplectically and anti-symplectically. In case R acts anti-symplectically, generically purely imaginary eigenvalues are isolated, and the equilibrium is contained in a local two-dimensional invariant manifold containing symmetric periodic solutions encircling the equilibrium point. In case R acts symplectically, generically purely imaginary eigenvalues are doubly degenerate, and the equilibrium is contained in two two-dimensional invariant manifolds containing nonsymmetric periodic solutions encircling the equilibrium point. In addition, there exists a three-dimensional invariant surface containing a two-parameter family of symmetric periodic solutions.