The Role of Short-Range Disorder in BaWO4 Crystals in the Intense Green Photoluminescence

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

DFT Study with Inclusion of the Grimme Potential on Anatase TiO2: Structure, Electronic, and Vibrational Analyses

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

Effects of Synthesis Conditions on the Nanostructure of Hybrid Sols Produced by the Hydrolytic Condensation of (3-Methacryloxypropyl)trimethoxysilane

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Structural and Luminescence Properties of Silica-Based Hybrids Containing New Silylated-Diketonato Europium(III) Complex

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

Self-Structuring of Lamellar Bridged Silsesquioxanes with Long Side Spacers

Diurea cross-linked bridged silsesquioxanes (BSs) C(10)C(11)C(10) derived from organosilane precursors, including decylene chains as side spacers and alkylene chains with variable length as central spacers (EtO)(3)Si- (CH(2))(10)-Y(CH(2))(n)-Y-(CH(2))(10)-Si(OEt)(3) (n = 7, 9-12; Y = urea group and Et = ethyl), have been synthesized through the combination of self-directed assembly and an acid-catalyzed sol gel route involving the addition of dimethylsulfoxide (DMSO) and a large excess of water. This new family of hybrids has enabled us to conclude that the length of the side spacers plays a unique role in the structuring of alkylene-based BSs, although their morphology remains unaffected. All the samples adopt a lamellar structure. While the alkylene chains are totally disordered in the case of the C(10)C(7)C(10) sample, a variable proportion of all-trans and gauche conformers exists in the materials with longer central spacers. The highest degree of structuring occurs for n = 9. The inclusion of decylene instead of propylene chains as side spacers leads to the formation of a stronger hydrogen-bonded urea-urea array as evidenced by two dimensional correlation Fourier transform infrared spectroscopic analysis. The emission spectra and emission quantum yields of the C(10)C(n)C(10) Cm materials are similar to those reported for diurea cross-linked alkylene-based BSs incorporating propylene chains as side spacers and prepared under different experimental conditions. The emission of the C(10)C(n)C(10) hybrids is ascribed to the overlap of two distinct components that occur within the urea cross-linkages and within the siliceous nanodomains. Time-resolved photoluminescence spectroscopy has provided evidence that the average distance between the siliceous domains and the urea cross-links is similar in the C(10)C(n)C(10) BSs and in oxyethylene-based hybrid analogues incorporating propylene chains as side spacers (diureasils), an indication that the longer side chains in the former materials adopt gauche conformations. It has also allowed us to demonstrate for the first time that the emission features of the urea-related component of the emission of alkylene-based BSs depend critically on the length of the side spacers.

Structural and Electronic Properties of Lithiated SnO2. A Periodic DFT Study

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Ligand Exchange Inducing Efficient Incorporation of CisPt Derivatives into Ureasil-PPO Hybrid and Their Interactions with the Multifunctional Hybrid Network

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Controlled Cisplatin Delivery from Ureasil-PEO1900 Hybrid Matrix

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Counterion effects on the structure and solubilization properties of anionic detergents. Role of hydrophobic cations in stabilizing micelles and attenuating their solvent properties

A series of alkyl sulfate detergents has been investigated in the presence of the cations Na +, methylviologen(2+) (MV 2+), 4-(cyanomethyl)pyridinium(1+) (CMP +), and tetramethylammonium (TMA +). The binding of these ions to the aqueous micellar assemblies has been measured through studies of luminescence quenching with the extramicellar probe, RuL 34-, where L = 4,4′-dicarboxy-2,2′-bipyridine. A general comparison of the alkyl sulfate aggregates with the nonquenching cations Na + and TMA + shows that the latter ion reduces the critical micelle concentration but at the same time depresses the ability of the detergent assemblies to bind or solubilize the hydrophobic quencher cations MV 2+ or CMP +. The reduced binding ability of the TMA + aggregates compared to that of the corresponding Na + soaps shows up largely in the form of a reduced favorable ΔS° for the solubilization in the case of the former. The results are in accord with a picture of the TMA + micelle as being more stable and more disordered than the corresponding assembly with Na + as the counterion. © 1989 American Chemical Society.

Size, electrophoretic mobility, and ion dissociation of vesicles prepared with synthetic amphiphiles

Vesicles prepared with synthetic amphiphiles (dioctadecyldimethylammonium bromide and chloride, dihexadecyl phosphate and its sodium salt) were obtained by sonication, ethanol injections, and chloroform injections. The hydrodynamic diameter of vesicles (Dh), estimated from the diffusivity measured by quasielastic light scattering, ranged from 230 to 3000 Å. The electrophoretic mobility (Um) was measured by free-flow electrophoresis. The zeta potential (ζ) and the degree of counterion dissociation (α) of the vesicles were calculated from Um and conductivity data, α decreased with increasing Dh of the vesicles, probably due to the decreasing headgroup area and the increasing counterion association needed to relax the surface electrostatic potential. The electrophoretic mobility was also calculated (Uc) according to an impenetrable, nonconducting sphere model with a spherically symmetric charge distribution approximation. Within the limits of the experimental error(s) of the (different) methods employed and the assumptions made in the calculations, the fact that the Um/Uc ratio ranged from 1.3 to 7.5 was considered to be a good agreement between the calculated and the experimental values. © 1990 American Chemical Society.

Extended states in disordered doped polyacetylene chains

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Electronic structure of polyacetylene with bonded oxygen

In this work we have studied the electronic structure of finite polyacetylene chains with structural oxygen-bonding models following data from 13C-NMR experiments. We have used a combination of Austin Method One and Hydrogenic Atoms in Molecules version 3 methods to perform geometric and spectroscopic calculations. Our results show that the electronically-active states are generally unaffected by the incorporation of oxygen. © 1992.

Adsorption of various ions from acetone and ethanol on silica gel modified with 2-, 3-, and 4-aminobenzoate

Chemically bonded phases were obtained by reaction of 2-, 3-, and 4-aminobenzoate with 3-chloropropyl-silica gel. These phases were employed for metal cation adsorption in a batch method and applied to the separation of transition metal cations by chromatographic analysis.

Polyacids self-dissociation model

This work deals with a model to interpret pH measurements of solutions of weak rodlike polyacids, in the absence of added salts or titrating base. The polyacid is modeled as a series of point charges discretely distributod in a straight line with a distance of closest approach for the protons and an average distance between dissociable monomers, projected in the polymer chain axis. Aside from these two geometrical parameters, the dissociation constant for the isolated monomer that describes the proton dissociated monomer interaction forms the basis of the model. The assumption of cylindrical symmetry and the adoption of the cell model lead to a form written in terms of elementary functions for the mean electrostatic potential. Values of pH (related to the proton concentration in a region beyond the influence of the polyacid) as a function of polymer concentration are displayed graphically for some values of the geometrical parameters and of the dissociation, constant. Theoretical predictions of pH values as a function of polymeric concentration are compared with measured values for poly-L-glutamic and polygalacturonic acids, and a good agreement is found. Theoretical values for the dissociation degree in terms of polymeric concentration are shown for the two experimentally investigated systems. These values are in a range appreciably smaller than what is usually studied as a result of titration.

Avaliacao preliminar da utilizacao do residuo industrial de man dioca (manihot esculenta granz) como excipiente em comprimidos: Caracteristicas fisicas e de compressao

The applicability of a residue of manioc (Manihot esculenta Granz) from industrial processing as a direct compression excipient was investigated in comparison with microcrystalline cellulose (Avicel® PH 101). Physical characteristics of the powders like bulk and tap densities, particle size, flow properties (flow rate, index of compressibility and angle of repose) and agglutination were evaluated. The residue had poor performance as excipient for direct compression. However, it showed better disintegration properties than Avicel. The possibility of its use as disintegrant agent will be confirmed on future studies.