Síntese, caracterização e estudo fotofísico de complexos de 4,4- diaminoestilbeno-2,2-dissulfonato com íons lantanídeos

This is a work involving fundamental studies of chemistry where the synthesis and structural characterization, as well as a possible future application of these new compounds as luminescent sensors or sunscreen agents, complexes with 4,4 diaminostilbene-2,2-disulfonic (DSD) and trivalent lanthanide ions La3+, Nd3+, Eu3+, Gd3+ and Yb3+, were synthesized in the ratio of 3 mmol: 1 mmol (DSD: lanthanides). The complexes obtained with these ions were present in powder form and were characterized by complexometric titration with EDTA CHN Elemental analysis, molecular absorption spectroscopy in the ultraviolet region, the absorption spectroscopy in the infrared, thermal analysis (TG / DTG), Nuclear Magnetic Resonance - NMR 1H and Luminescence Spectroscopy. The complexometric titration and CHN analysis, confirmed the TG / DTG which suggest that these complexes have the following general chemical formulas: [La2(C14H12S2O6N2)2(H2O)2Cl2].7H2O,[Nd2(C14H12S2O6N2)2(H2O)2Cl2].6H2O,[Eu2(C14 H12S2O6N2)2(H2O)2Cl2].7H2O,[Gd2(C14H12S2O6N2)2(H2O)2Cl2].4H2O e [Yb2(C14H12S2O6N2)2(H2O)2].6H2O. The disappearance of the bands in the infrared spectrum at 2921 cm-1 and 2623 cm-1 and the displacement of the bands in the spectra of the amine complex indicate that the lanthanide ion is coordinated to the oxygen atoms and the sulfonate groups of the nitrogens amines, suggesting the formation of the dimer. The disappearance of the signal and the displacement signal SO3H amines in the 1H NMR spectrum of this complex are also indicative coordination and dimer formation. The Thermogravimetry indicates that the DSD is thermally stable in the range of 40º to 385°C and their complexes with lanthanide ions exhibit weight loss between 4 and 5 stages. The Uv-visible spectra indicated that the DSD and complexes exhibit cis isomers. The analysis of luminescence indicates that the complexes do not exhibit emission in the region of the lanthanides but an intense emission part of the binder. This is related to the triplet states of the ligand, which are in the lowest energy state emitting lanthanide ions, and also the formation of the dimer that suppress the luminescence of ion Eu3+. The formation of dimer was also confirmed by calculating the europium complex structure using the model Hamiltonian PM6 and Sparkle

Em direção a uma representação para equações algébricas :uma lógica equacional local

The intervalar arithmetic well-known as arithmetic of Moore, doesn't possess the same properties of the real numbers, and for this reason, it is confronted with a problem of operative nature, when we want to solve intervalar equations as extension of real equations by the usual equality and of the intervalar arithmetic, for this not to possess the inverse addictive, as well as, the property of the distributivity of the multiplication for the sum doesn t be valid for any triplet of intervals. The lack of those properties disables the use of equacional logic, so much for the resolution of an intervalar equation using the same, as for a representation of a real equation, and still, for the algebraic verification of properties of a computational system, whose data are real numbers represented by intervals. However, with the notion of order of information and of approach on intervals, introduced by Acióly[6] in 1991, the idea of an intervalar equation appears to represent a real equation satisfactorily, since the terms of the intervalar equation carry the information about the solution of the real equation. In 1999, Santiago proposed the notion of simple equality and, later on, local equality for intervals [8] and [33]. Based on that idea, this dissertation extends Santiago's local groups for local algebras, following the idea of Σ-algebras according to (Hennessy[31], 1988) and (Santiago[7], 1995). One of the contributions of this dissertation, is the theorem 5.1.3.2 that it guarantees that, when deducing a local Σ-equation E t t in the proposed system SDedLoc(E), the interpretations of t and t' will be locally the same in any local Σ-algebra that satisfies the group of fixed equations local E, whenever t and t have meaning in A. This assures to a kind of safety between the local equacional logic and the local algebras

Convergent variational calculation of positronium-hydrogen-atom scattering lengths

We present a convergent variational basis-set calculational scheme for elastic scattering of the positronium atom by the hydrogen atom in S wave. Highly correlated trial functions with appropriate symmetry are needed to achieve convergence. We report convergent results for scattering lengths in atomic units for both singlet (= 3.49 +/-0.20) and triplet (= 2.46 +/-0.10) states.

Spontaneous breaking of the lepton number and invisible majoron in a 3-3-1 model

In this work we implement the spontaneous breaking of lepton number in version II of the 3-3-1 models and study their phenomenological consequences. The main result of this work is that our majoron is invisible even though it belongs to a triplet representation by the 3-3-1 symmetry.

Search for heavy lepton partners of neutrinos in proton-proton collisions in the context of the type III seesaw mechanism

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Decay properties of a class of doubly charged Higgs bosons

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Cubic interactions and quantum criticality in dimerized antiferromagnets

In certain Mott-insulating dimerized antiferromagnets, triplet excitations of the paramagnetic phase display both three-particle and four-particle interactions. When such a magnet undergoes a quantum phase transition into a magnetically ordered state, the three-particle interaction becomes part of the critical theory provided that the lattice ordering wave vector is zero. One microscopic example is the staggered-dimer antiferromagnet on the square lattice, for which deviations from O(3) universality have been reported in numerical studies. Using both symmetry arguments and microscopic calculations, we show that a nontrivial cubic term arises in the relevant order-parameter quantum field theory, and we assess its consequences using a combination of analytical and numerical methods. We also present finite-temperature quantum Monte Carlo data for the staggered-dimer antiferromagnet which complement recently published results. The data can be consistently interpreted in terms of critical exponents identical to that of the standard O(3) universality class, but with anomalously large corrections to scaling. We argue that the cubic interaction of critical triplons, although irrelevant in two spatial dimensions, is responsible for the leading corrections to scaling due to its small scaling dimension.

Natural Peccei-Quinn symmetry in the 3-3-1 model with a minimal scalar sector

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Triangular-lattice anisotropic dimerized Heisenberg antiferromagnet: Stability and excitations of the quantum paramagnetic phase

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

Synthesis and Study of the Photophysical Properties of a New Eu3+ Complex with 3-Hydroxypicolinamide

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Kinetic model of poly(3-hydroxybutyrate) thermal degradation from experimental non-isothermal data

The non-isothermal data given by TG curves for poly(3-hydroxybutyrate) (PHB) were studied in order to obtain a consistent kinetic model that better represents the PHB thermal decomposition. Thus, data obtained from the dynamic TG curves were suitably managed in order to obtain the Arrhenius kinetic parameter E according to the isoconversional F-W-O method. Once the E parameters is found, a suitable logA and kinetic model (f(alpha)) could be calculated. Hence, the kinetic triplet (E +/- SD, logA +/- SD and f(alpha)) obtained for the thermal decomposition of PHB under non-isothermal conditions was E=152 +/- 4 kJ mol(-1), logA=14.1 +/- 0.2 s(-1) for the kinetic model, and the autocatalytic model function was: f(alpha)=alpha(m)(1-alpha)(n)=alpha(0.42)(1-alpha)(0.56).

Electroluminescence of zinc oxide thin-films prepared via polymeric precursor and via sol-gel methods

Zinc oxide (ZnO) is an electroluminescent (EL) material that can emit light in different regions of electromagnetic spectrum when electrically excited. Since ZnO is chemically stable, inexpensive and environmentally friendly material, its EL property can be useful to construct solid-state lamps for illumination or as UV emitter. We present here two wet chemical methods to prepare ZnO thin-films: the Pechini method and the sol-gel method, with both methods resulting in crystalline and transparent films with transmittance > 85% at 550 nm. These films were used to make thin-film electroluminescent devices (TFELD) using two different insulator layers: lithium fluoride (LiF) or silica (SiO2). All the devices exhibit at least two wide emission bands in the visible range centered at 420 nm and at 380 nm attributed to the electronic defects in the ZnO optical band gap. Besides these two bands, the device using SiO2 and ZnO film obtained via sol-gel exhibits an additional band in the UV range centered at 350 nm which can be attributed to excitonic emission. These emission bands of ZnO can transfer their energy when a proper dopant is present. For the devices produced the voltage-current characteristics were measured in a specific range of applied voltage. (C) 2007 Elsevier B.V. All rights reserved.

Mechanistic insights into the reaction between VO2+ and propene based on a DFT study

Calculations based on density functional theory have been carried out to investigate the free energy profiles at singlet and triplet electronic states associated with the gas-phase ion/molecule reactions of VO2++ ((1)A(1)/(3)A) with propene. The complex potential energy Surfaces, including Six reaction pathways (three dehydrogenation and three oxygen transfer processes), have been explored and analyzed. Along dehydrogenation reactive channels, three final products can be obtained: V(OH)(2)(+) ((1)Sigma(+)/(3)Sigma(-)) and allene (path Dehl), being the most kinetically and thermodynamically favorable reaction pathway, V(OH)(2)(+) ((1)Sigma(+)/(3)Sigma(-)) and propyne (path Deh2),and VO2+ ((1)A(1)/(3)A) and H-2 plus allene (path Deh3). The oxyoenation processes can yield its final products Vo(+) ((1)Delta/(3)Sigma) and acetone (path Ox1), VO+ ((1)Delta/(3)Sigma 2) and propanaldehyde (path Ox2), and VO+ ((1)Delta/(3)Sigma) and H-2 and propenaldehyde (path Ox3). Both paths Deh1 and Deh2 are associated with two consecutive hydrogen transfer processes from carbon atoms of the propene fragment to vanadyl oxygen atoms, while in path Deh3 the second hydrogen migration takes place to the vanadiurn atorn followed by the formation ola hydrogen molecule. Both paths Ox1 and Ox2 comprise an intramolecular hydrogen transfer between the ethylenic moiety of the propene fragment, while two consecutive hydrogen transfer processes take place from the propene fragment to oxygen and vanadium atoms of the vanadyl moiety along path Ox3. Three crossing points between both electronic states take place along path Deh1 (CP-Deh1) and path Deh2 (CP-Deh2) and in the entrance channel of oxidation processes (CP-Ox). A comparison with previous works on related reactions VO2+ + C2H4, VO2 + C2H6, and VO2+ + C3H8 allows us to rationalize the different reactivity patterns.

Analysis of the ethidium bromide bound to DNA by photoacoustic and FTIR spectroscopy

Under physiological conditions B-form DNA is an exceedingly stable structure. However, experimental evidences obtained through nuclear magnetic resonance and fluorescence anisotropy suggest that the structure of the double helix fluctuates substantially. We describe photoacoustic phase modulation frequency measurements of ethidium bromide (Eb) with calf thymus, DNA. As in fluorescence phase modulation measurements, we used an intercalating dye as a probe; however, we monitored the triplet excited state lifetime at different ionic strengths. The triplet lifetime of Eb varied from about 0.30 ms, with no DNA present, to 20 ms, (at a DNA:Eb molar ratio of 5). With salt titration, this value falls, to about 2.0 ms. This result suggests, a strong coupling between the phenantridinium ring of the ethidium and the base pairs because of the stacking movement of the DNA molecule under salt effect. This, effect may be understood considering DNA as a polyelectrolyte. The counterions, in the solution shield the phosphate groups, reducing the electrostatic repulsion force between them, hence compacting the DNA molecule. The results from Fourier transform infrared demonstrated two important bands: 3187 cm(-1) corresponding to the symmetric stretching of the NH group of the bases, and 1225 cm(-1) corresponding to the asymmetric stretching of phosphate groups shifted toward higher wavenumbers, suggesting a proximity between the intercalant and base pairs and a modification of the DNA backbone state, both induced by salt accretion.

DFT study of the reaction between VO2+ and C2H6

The molecular mechanisms of the reaction VO2+ ((1)A(1)/(3)A'') + C2H6 ((1)A(g)) to yield V(OH)(2)(+) ((1)Sigma(+)/(3)Sigma(-)) + C2H4 ((1)A(g)) and/or VO+ ((1)Delta/(3)Sigma) + H2O ((1)A(1)) + C2H4 (Ag-1) have been investigated with density functional theory (DFT) at the B3LYP/6-311G(2d,p) level. Calculations including geometry optimization, vibrational analysis, and Gibbs free energy for the stationary points on the reactive potential energy surfaces at both the singlet (s) and first excited triplet (t) electronic states have been carried out. The most thermodynamically and kinetically favorable pathway is the formation of t-V(OH)(2)(+) + C2H4 along a four-step molecular mechanism (insertion, two consecutive hydrogen transfers, and elimination). A crossing point between s and t electronic states has been characterized. A comparison with previous works on VO2+ + C2H4 (Gracia et al. J. Phys. Chem. A 2003, 107, 3107-3120) and VO2+ + C3H8 (Engeser et al. Organometallics 2003, 22, 3933-3943) reactions allows us a rationalization of the different reactivity patterns. The catalytic role of water molecules in the tautomerization process between hydrated oxide cation, VO(H2O)(+,) and dihydroxide cation, V(OH)(2)(+), is achieved by a water-assisted mechanism.