A PVC Plasticized Sensor for Ni(II) Ion Based on a Simple Ethylenediamine Derivative

new PVC membrane ion selective electrode which is highly selective towards Ni(II) ions was constructed using a Schiff base containing a binaphthyl moiety as the ionophore. The sensor exhibited a good Nernstian response for nickel ions over the concentration range 1.0 × 10–1 – 5.0 × 10–6 M with a lower limit of detection of 1.3 × 10–6 M. It has a fast response time and can be used for a period of 4 months with a good reproducibility. The sensor is suitable for use in aqueous solutions in a wide pH range of 3.6 – 7.4 and works satisfactorily in the presence of 25% (v/v) methanol or ethanol. The sensor shows high selectivity to nickel ions over a wide variety of cations. It has been successfully used as an indicator electrode in the potentiometric titration of nickel ions against EDTA and also for the direct determination of nickel content in real samples: effluent samples, chocolates and hydrogenated oils.

Desenvolupament computacional de la semblança molecular quàntica

La present Tesi Doctoral, titulada desenvolupament computacional de la semblança molecular quàntica, tracta, fonamentalment, els aspectes de càlcul de mesures de semblança basades en la comparació de funcions de densitat electrònica.El primer capítol, Semblança quàntica, és introductori. S'hi descriuen les funcions de densitat de probabilitat electrònica i llur significança en el marc de la mecànica quàntica. Se n'expliciten els aspectes essencials i les condicions matemàtiques a satisfer, cara a una millor comprensió dels models de densitat electrònica que es proposen. Hom presenta les densitats electròniques, mencionant els teoremes de Hohenberg i Kohn i esquematitzant la teoria de Bader, com magnituds fonamentals en la descripció de les molècules i en la comprensió de llurs propietats.En el capítol Models de densitats electròniques moleculars es presenten procediments computacionals originals per l'ajust de funcions densitat a models expandits en termes de gaussianes 1s centrades en els nuclis. Les restriccions físico-matemàtiques associades a les distribucions de probabilitat s'introdueixen de manera rigorosa, en el procediment anomenat Atomic Shell Approximation (ASA). Aquest procediment, implementat en el programa ASAC, parteix d'un espai funcional quasi complert, d'on se seleccionen variacionalment les funcions o capes de l'expansió, d'acord als requisits de no negativitat. La qualitat d'aquestes densitats i de les mesures de semblança derivades es verifica abastament. Aquest model ASA s'estén a representacions dinàmiques, físicament més acurades, en quant que afectades per les vibracions nuclears, cara a una exploració de l'efecte de l'esmorteïment dels pics nuclears en les mesures de semblança molecular. La comparació de les densitats dinàmiques respecte les estàtiques evidencia un reordenament en les densitats dinàmiques, d'acord al que constituiria una manifestació del Principi quàntic de Le Chatelier. El procediment ASA, explícitament consistent amb les condicions de N-representabilitat, s'aplica també a la determinació directe de densitats electròniques hidrogenoides, en un context de teoria del funcional de la densitat.El capítol Maximització global de la funció de semblança presenta algorismes originals per la determinació de la màxima sobreposició de les densitats electròniques moleculars. Les mesures de semblança molecular quàntica s'identifiquen amb el màxim solapament, de manera es mesuri la distància entre les molècules, independentment dels sistemes de referència on es defineixen les densitats electròniques. Partint de la solució global en el límit de densitats infinitament compactades en els nuclis, es proposen tres nivells de aproximació per l'exploració sistemàtica, no estocàstica, de la funció de semblança, possibilitant la identificació eficient del màxim global, així com també dels diferents màxims locals. Es proposa també una parametrització original de les integrals de recobriment a través d'ajustos a funcions lorentzianes, en quant que tècnica d'acceleració computacional. En la pràctica de les relacions estructura-activitat, aquests avenços possibiliten la implementació eficient de mesures de semblança quantitatives, i, paral·lelament, proporcionen una metodologia totalment automàtica d'alineació molecular. El capítol Semblances d'àtoms en molècules descriu un algorisme de comparació dels àtoms de Bader, o regions tridimensionals delimitades per superfícies de flux zero de la funció de densitat electrònica. El caràcter quantitatiu d'aquestes semblances possibilita la mesura rigorosa de la noció química de transferibilitat d'àtoms i grups funcionals. Les superfícies de flux zero i els algorismes d'integració usats han estat publicats recentment i constitueixen l'aproximació més acurada pel càlcul de les propietats atòmiques. Finalment, en el capítol Semblances en estructures cristal·lines hom proposa una definició original de semblança, específica per la comparació dels conceptes de suavitat o softness en la distribució de fonons associats a l'estructura cristal·lina. Aquests conceptes apareixen en estudis de superconductivitat a causa de la influència de les interaccions electró-fonó en les temperatures de transició a l'estat superconductor. En aplicar-se aquesta metodologia a l'anàlisi de sals de BEDT-TTF, s'evidencien correlacions estructurals entre sals superconductores i no superconductores, en consonància amb les hipòtesis apuntades a la literatura sobre la rellevància de determinades interaccions.Conclouen aquesta tesi un apèndix que conté el programa ASAC, implementació de l'algorisme ASA, i un capítol final amb referències bibliogràfiques.

Photoproduction of heavy quarks in next-to-leading order QCD with longitudinally polarized initial states

We present all relevant details of our calculation of the complete next-to-leading order O(αS2α) QCD corrections to heavy flavor photoproduction with longitudinally polarized point-like photons and hadrons. In particular we provide analytical results for the virtual plus soft gluon cross section. We carefully address the relevance of remaining theoretical uncertainties by varying, for instance, the factorization and renormalization scales independently. Such studies are of importance for a meaningful first direct determination of the polarized gluon density Δg from the total charm production spin asymmetry by the upcoming COMPASS experiment. It is shown that the scale uncertainty is considerably reduced in next-to-leading order, but the dependence on the charm quark mass is sizable at fixed target energies. Finally, we study several differential single-inclusive heavy quark distributions and, for the polarized HERA option, the total bottom spin asymmetry.

Constraining the orbital orientation of eta Carinae from H Paschen lines

During the past decade, several observational and theoretical works have provided evidence of the binary nature of eta Carinae. Nevertheless, there is still no direct determination of the orbital parameters, and the different current models give contradictory results. The orbit is, in general, assumed to coincide with the Homunculus equator although the observations are not conclusive. Among all systems, eta Car has the advantage that it is possible to observe both the direct emission of line transitions in the central source and its reflection by the Homunculus, which is dependent on the orbital inclination. In this work, we studied the orbital phase-dependent hydrogen Paschen spectra reflected by the south-east lobe of the Homunculus to constrain the orbital parameters of eta Car and determine its inclination with respect to the Homunculus axis. Assuming that the emission excess originates in the wind-wind shock region, we were able to model the latitude dependence of the spectral line profiles. For the first time, we were able to estimate the orbital inclination of eta Car with respect to the observer and to the Homunculus axis. The best fit occurs for an orbital inclination to the line of sight of i similar to 60 degrees +/- 10 degrees, and i* similar to 35 degrees +/- 10 degrees with respect to the Homunculus axis, indicating that the angular momenta of the central object and the orbit are not aligned. We were also able to fix the phase angle of conjunction as similar to -40 degrees, showing that periastron passage occurs shortly after conjunction.

Tungsten permanent chemical modifier for fast estimation of Se contents in soil by graphite furnace atomic absorption spectrometry

A tungsten carbide coating on the integrated platform of a transversely heated graphite atomizer was used as a modifier for the direct determination of Se in soil extracts by graphite furnace atomic absorption spectrometry. Diethylenetriaminepentaacetic acid (0.0050 mol L-1) plus ammonium hydrogencarbonate (1.0 mol L-1) extracted predominantly available inorganic selenate from soil. The formation of a large amount of carbonaceous residue inside the atomizer was avoided with a first pyrolysis step at 600 degreesC assisted by air during 30 s. For 20 muL of soil extracts delivered to the atomizer and calibration by matrix matching, an analytical curve (10.0-100 mug of L-1) with good linear correlation (r = 0.999) between integrated absorbance and analyte concentration was established. The characteristic mass was similar to63 pg of Se, and the lifetime of the tube was similar to750 firings. The limit of detection was 1.6 mug L-1, and the relative standard deviations (n = 12) were typically <4% for a soil extract containing 50 mug of L-1. The accuracy of the determination of Se was checked for soil samples by means of addition/recovery tests. Recovery data of Se added to four enriched soil samples varied from 80 to 90% and indicated an accurate method.

On the denominator values and barycentric weights of rational interpolants

We improve upon the method of Zhu and Zhu [A method for directly finding the denominator values of rational interpolants, J. Comput. Appl. Math. 148 (2002) 341-348] for finding the denominator values of rational interpolants, reducing considerably the number of arithmetical operations required for their computation. In a second stage, we determine the points (if existent) which can be discarded from the rational interpolation problem. Furthermore, when the interpolant has a linear denominator, we obtain a formula for the barycentric weights which is simpler than the one found by Berrut and Mittelmann [Matrices for the direct determination of the barycentric weights of rational interpolation, J. Comput. Appl. Math. 78 (1997) 355-370]. Subsequently, we give a necessary and sufficient condition for the rational interpolant to have a pole. (c) 2006 Elsevier B.V. All rights reserved.

Efeitos do pentobarbital sódico e do enfluorano sobre a circulação sanguínea hepática: fluxometria eletromagnética e manometria (estudo experimental no cão)

In 18 dogs, previously anesthetized with sodium pentobarbital for the surgical preparation, catheterism and monitoring, the action of sodium pentobarbital (7.5 mg/kg) and enflurane (1.5 - 2%) in the liver circulation was studied. Measurements of the following parameters were made in four different times, before and 15, 30 and 60 min after the drug administration. By direct determination: hepatic artery flow, portal vein flow, mean pressure of the abdominal aorta, peripheral arterial pressure (mean), pressure in the caudal cava vein, portal pressure; and by indirect determination: total flow, arterial-cava gradient, portal-cava gradient, resistance in the hepatic artery territory, resistance in the territory of the portal vein, and total resistance. Based on the results, it is concluded that in the experiment's conditions: sodium pentobarbital doesn't change significantly the hepatic circulation, and enflurance produces a fall in the total hepatic flow, by reducing the portal flow, without alterations of the hepatic arterial flow. It diminishes the total hepatic resistance by diminishing the arterial resistance without alterations of the portal resistance; it diminishes the arterial-cava gradient in consequence of the reduction of the abdominal aorta pressure and of the portal pressure, but it seems that the caudal cava pressure is not altered. It also occurs a fall in the peripheral mean pressure.

Avaliação da padronização interna na determinação de chumbo em vinagre por espectrometria de absorção atômica em forno de grafite

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Determinação direta de Ca, Mg, Mn e Zn em amostras de leite de búfala da Ilha de Marajó por espectrometria de absorção atômica com chama (FAAS)

ABSTRACT: This work proposes an analytical procedure for direct determination of calcium, magnesium, manganese and zinc in buffalo milk by flame atomic absorption spectrometry (FAAS). Samples were diluted with a solution containing 10% (v/v) of water-soluble tertiary amines (CFA-C) at pH 8. For comparison, buffalo milk samples were digested with HNO₃ and H₂O₂. According to a paired t-test, the results obtained in the determination of Ca, Mg, Mn and Zn in digested samples and in 10% (v/v) CFA-C medium were in agreement at a 95% confidence level. The developed procedure is simple, rapid, decrease the possibility of contamination and can be applied for the routine determination of Ca, Mg, Mn and Zn in buffalo milk samples without any difficulty caused by matrix constituents, such as fat content, and particle size distribution in the milk emulsion

Mecanismos termorreguladores de cabras da raça Saanen -

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Determinação direta de selênio em água de coco e em leite de coco utilizando espectrometria de absorção atômica com atomização eletrotérmica em forno de grafite

Selenium is both essential and toxic to man and animals, depending on the concentration and the ingested form. Most fruits and vegetables are poor sources of selenium, but coconut can be a good selenium source. Samples were suspended (1 + 4 v/v) in a mixture of tertiary amines soluble in water (10% v/v CFA-C). This simple sample treatment avoided contamination and decreased the analysis time. The standard additions method was adopted for quantification. The action of the autosampler was improved by the presence of the amines mixture in the suspension. A Varian model AA-800 atomic absorption spectrometer equipped with a graphite furnace and a GTA 100 autosampler was used for selenium determination in coconut water and coconut milk. Background correction was performed by means of the Zeeman effect. Pyrolytically coated graphite tubes were employed. Using Pd as chemical modifier, the pyrolysis and the atomization temperatures were set at 1400 and 2200oC, respectively. For six samples, the selenium concentration in coconut water varied from 6.5 to 21.0 mg L^-1 and in coconut milk from 24.2 to 25.1 mg L^-1. The accuracy of the proposed method was evaluated by an addition-recovery experiment and all recovered values are in the 99.5^-102.3% range. The main advantage of the proposed method is that it can be directly applied without sample decomposition.

Herbicidas mais empregados no cultivo de cana-de-açúcar no município de Araraquara (SP): desenvolvimento e validação de método de quantificação e avaliação do potencial de lixiviação em solos argiloso e arenoso (área de recarga do Sistema Aquífero Guarani)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Utilização de imagens omnidirecionais georreferenciadas como controle de campo para orientação de imagens orbitais

Pós-graduação em Ciências Cartográficas - FCT

Sílica mesoporosa como suporte sólido para o ancoramento da molécula 4-amino-3-hidrazino-5-mercapto-1,2,4-triazole e aplicação na adsorção de Cu(II), Cd(II), Ni(II), Pb(II) e Co(II) em amostras aquosas

Pós-graduação em Química - IQ

Quantificação de metais potencialmente tóxicos em mexilhão dourado (Limnoperna fortunei) por espectrometria de absorção atômica com fonte contínua e alta resolução empregando amostragem direta de sólidos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)