Enantioselective synthesis of aziridines using asymmetric transfer hydrogenation as a precursor for chiral derivatives used as bonding agent for rocket solid propellants

A rapid, expedient and enantioselective method for the synthesis of beta-hydroxy amines and monosubstituted aziridines in up to 99% e.e., via asymmetric transfer hydrogenation of a-amino ketones and cyclisation through treatment with tosyl chloride and base, is described. (1R,2R)-N-(para-toluenesulfonyl)-1,2-ethylenediamine with formic acid has been utilised as a ligand for the Ruthenium (II) catalysed enantioselective transfer hydrogenation of the ketones.The chiral 2-methyl aziridine, which is a potentially more efficient bonding agent for Rocket Solid Propellant has been successfully achieved.

Construção e avaliação de célula de fluxo para estudo da tensão interfacial dinâmica da interface fluxo líquido - sólido por despolarização da fluorescência

A simple low-cost flow cell was developed, built and optimized in order to observe dynamic interfacial tension of continuous flow systems. Distinct materials can be used in one of the cell walls in order to observe the intermolecular forces between the flowing liquid and the chemical constitution of the walls. The fluorescence depolarization was evaluated using Rhodamine B as fluorescent probe seeded in ethylene glycol. The effects of the positioning angles on the data acquired across the cell are reported. The reproducibility of the data was evaluated with a spectrometer assembled in-house and the relative standard deviation was below 3%.

Self-assembly of supermolecular species directed by hydrogen bonding and aromatic π-π stacking interactions

A new Cu(II) trimers, [Cu3(dcp)2(H2O)8]. 4DMF, with the ligand 3,5-pyrazoledicarboxylic acid monohydrate (H3dcp) has been prepared by solvent method. Its solid-state structure has been characterized by elemental analysis, thermal analysis (TGA and DSC), and single crystal X-ray diffraction. X-ray crystallographic studies reveal that this complex has extended 1-D,2-D and 3-D supramolecular architectures directed by weak interactions (hydrogen bond and aromatic π-π stacking interaction) leading to a sandwich solid-state structure.

Advances and challenges in oral health after a decade of the “Smiling Brazil” Program

ABSTRACT OBJECTIVE To analyze oral health work changes in primary health care after Brazil’s National Oral Health Policy Guidelines were released. METHODS A literature review was conducted on Medline, LILACS, Embase, SciELO, Biblioteca Virtual em Saúde, and The Cochrane Library databases, from 2000 to 2013, on elements to analyze work changes. The descriptors used included: primary health care, family health care, work, health care policy, oral health care services, dentistry, oral health, and Brazil. Thirty-two studies were selected and analyzed, with a predominance of qualitative studies from the Northeast region with workers, especially dentists, focusing on completeness and quality of care. RESULTS Observed advances focused on educational and permanent education actions; on welcoming, bonding, and accountability. The main challenges were related to completeness; extension and improvement of care; integrated teamwork; working conditions; planning, monitoring, and evaluation of actions; stimulating people’s participation and social control; and intersectorial actions. CONCLUSIONS Despite the new regulatory environment, there are very few changes in oral health work. Professionals tend to reproduce the dominant biomedical model. Continuing efforts will be required in work management, training, and permanent education fields. Among the possibilities are the increased engagement of managers and professionals in a process to understand work dynamics and training in the perspective of building significant changes for local realities.

Estudio estructural del MoO3 y sus planos cristalinos

In the present work we present geometric models of the most studied MoO3 surfaces, which were obtained using the DTMM 2.0 Molecular Modeller software. MoO3 has an orthorhombic layered structure, with each layer comprised of two interleaved planes of MoO6 octahedral. These layers are parallel to the (010) crystal plane and only oxygen ions are exposed on their surfaces. This situation results in weak van der Waals bonding between layers and in a relatively inert surface. In our approach to surface geometric structure we consider "ideal" crystal surface, in which the bulk atomic arrangement is maintained. These surfaces were generated by imaginary cleavage along appropriate planes in the bulk crystal structure.

Aplicação de modelo matemático às propriedades reológicas de géis mistos de agarose e de goma guar

Certain biopolymers are capable of forming physically cross-linked gels in aqueous medium, stabilized by forces such as Coulombic, charge transfer, hydrogen bonding, dipole-dipole, van der Waals, and hydrophobic interactions. The mathematical description of these physical networks are difficult, but should contribute to a better understanding of the gelling process. The Clark and Ross-Murphy model was applied to experimental data for agarose-guar gum mixed systems, in which only agarose is the gelling polysaccharide. A computational routine based on the statistical maximum likehood principle was employed to estimate the f, K and a characteristic parameters. Statistical t-test and F-test were used to analyse the set of parameters.

Alcatrão ou creosoto de eucalipto na produção de adesivos fenólicos para colagem de madeira

This study has shown that Eucalyptus tar and creosote can be used in phenolic adhesive formulations (resols) for wood products bonding. Some adhesives were prepared substituting 0; 17.7; 35.0 and 67.0% of the phenol by anhydrous tar and 0; 15.0 e 28.5% by creosote. In gluing Brazilian pine veneers, eucalypt tar and creosote based adhesives required longer pressing times for curing than conventional phenol-formaldehyde adhesives. By using 13C NMR, the number of carbons in side chains and hydroxyl, carbonyl, carboxyl and methoxyl groups related to 100 aromatic rings could be estimated in tar and creosote. In creosote, after reaction with excess formaldehyde in alkaline medium, only 0,28 hydroxymethyl groups was detected per phenolic ring. This low amount of hydroxymethylation explains the lack of reactivity in curing observed when creosote was introduced in a standard adhesive formulation.

Optical characterization of sol-gel glasses derived from Eu3+ complex-forming precursors

Fabrication of new optical devices based upon the incorporation of rare earth ions via sol-gel methods depends on elimination of dopant ion clusters and residual hydroxyl groups from the final material. The optical absorption and/or luminescence properties of luminescent rare earth ions are influenced by the local bonding environment and the distribution of the rare-earth dopants in the matrix. Typically, dopants are incorporated into gel via dissolution of soluble species into the initial precursor sol. In this work, Eu3+ is used as optical probe, to assess changes in the local environment. Results of emission, excitation, fluorescence line narrowing and lifetimes studies of Eu3+-doped gels derived from Si(OCH3)4 and fluorinated/chelate Eu3+ precursors are presented. The precursors used in the sol-gel synthesis were: tris (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate) Eu(III), Eu (III) trifluoromethanesulfonate, Eu(III) acetylacetonate hydrate, Eu (III) trifluoroacetate trihidrate, tris (2,2,6,6-tetramethyl-3,5- heptanedionate) Eu(III) and Eu(NO3)3.6H2O. The results were interpreted in terms of the evolution of the Eu3+ fluorescence in systems varying from solution to the gels densified to 800ºC. The lifetimes studies indicate that the fluorinated precursors are effective at reducing the water content in densified gels.

Síntese e caracterização de cloro[ácido 2-(difenilfosfino)benzóico]-ouro(I) e alguns de seus derivados

In this contribution a few new gold(I)phosphine complexes, [2-(PPh2)C6H4CO 2H]AuX (where X = Cl, SCN, Br3) and a similar gold(III) derivative [{2-(PPh2)C6H4CO 2H}AuIII Cl (C6H4CH2NMe2 )]Cl have been synthesised and characterised. The phosphine, 2-(diphenylphosphino)benzoic acid, has been employed for the first time in gold chemistry. This ligand is potentially bidentate through bonding of the phosphine and carboxylate groups. The X-ray structure of the complex chloro[2-(diphenylphosphino) benzoic acid]gold(I) has been elucidated and the bond lengths encountered show great similarity to those of chloro(triphenylphosphine)gold(I). [2-(PPh2)C6H4CO 2H]AuCl crystallises in the space group P2(1)/c with a = 9.113(2) Å, b = 10.925(2) Å, c = 23.069(4) Å, beta = 99.95º(3), V = 2299 ų, Z = 4 and R = 0.091. Biological tests for anti-fungal and anti-bacterial activity demostrate that [2-(PPh2)C6H4CO 2H]AuCl exhibits broad spectrum activity against a range of organisms.

Íon Be H+ em campo elétrico uniforme intenso

The influence of a strong external electric field in chemical bonding is not extensively studied. In this work, the behavior of the potential energy curves of the BeH+ ion in an external electric field is investigated by means of variational calculations using molecular orbitals. For simplicity we consider the case where the external field is parallel to the molecular axis, in the direction of the dipole moment, which raises the polarization of the ion. The effects on dissociation are investigated.

Adsorção de íons Cu2+ em latossolo vermelho-amarelo húmico

In environmental studies it is necessary to know the adsorption behavior of metals by soils, since the unfavorable effects of heavy metals and even the micronutrients at high concentrations in the environment are related to these adsorbents' ability to immobilize them. A sample of a humic yellow red oxisol from Araponga region in the State of Minas Gerais, Brazil, was used to verify the adsorption behavior of Cu2+ ions in this substrate. The mathematical model described by Langmuir's adsorption equation in its linearized form was applied and the values of the maximum capacity b and those of the constant related to the bonding energy a were obtained. Aliquots of copper nitrate solutions containing several concentrations of this metal were added to soil samples, the pH being predetermined for developing the adsorption experiments. The chemical and physical characterization of soil sample were performed by determining the organic carbon, nitrogen and phosphorus concentrations, cation exchange capacity (CEC), pH, concentration of metals (Al, Fe, K, Mg, Ca, Zn, Cu, Ni, Cr, Co, Pb, and Cd), granulometric analysis and X-ray diffraction. Langmuir isotherms presented two distinct adsorption regions at both pH 4 and pH 5, showing that the adsorptive phenomenon occurs in two distinct stages. The adsorption sites for the lower part presented greater bonding energy and low adsorption capacity compared with the adsorption sites of the part of the curve corresponding to higher Cu concentrations in the equilibrating solution.

Caracterização de catalisadores Cu/CeO2/Al2O3 por redução a temperatura programada e atividade para oxidação de CO

The kinetic parameters for the CO oxidation reaction using copper/alumina-modified ceria as catalysts were determined. The catalysts with different concentrations of the metals were prepared using impregnation methods. In addition, the reduction-oxidation behaviour of the catalysts were investigated by temperature-programmed reduction. The activity results show that the mechanism for CO oxidation is bifunctional : oxygen is activated on the anionic vacancies of ceria surface, while carbon monoxide is adsorbed preferentially on the higher oxidation copper site. Therefore, the reaction occurs on the interfacial active centers. Temperatures-programmed Reduction patterns show a higher disperdion when cerium oxide is present.

Propelente sólido compósito polibutadiênico: I- influência do agente de ligação

In the Brazilian Complete Spacial Mission, the research of Vehicle Satellite Launcher is important. The solid propellant composite used in this vehicle is made with ammonium perchlorate, aluminiun powder and hydroxy terminated polibutadiene resin. In the propellant the bonding agent has a function to promote the interaction between solids and polimeric matrix, improving mechanical properties as stress, strain, aging characteristics and moisture embrittlement. Due its importance in propellant, bonding agent is consider as industrial secret and the literature about it is generic, without greater informations.

Fases estacionárias para cromatografia líquida de alta eficiência em fase reversa (CLAE-FR) baseadas em superfícies de óxidos inorgânicos funcionalizados

Particles of porous silica or other solvent resistent inorganic oxides can be functionalized by aliphatic (e.g., C-8 or C-18) or other groups to give stationary phases for use in reversed phase HPLC. The functionalization can be done by bonding of individual groups to the surface of the support particles, by producing an organic polymeric film from pre-polymers, or by adsorbing/immobilizing pre-formed polymers on the surfaces. These three types of functionalization are reviewed.

Anestésicos locais: interação com membranas de eritrócitos de sangue humano, estudada por ressonância magnética nuclear de ¹H e 31P

The literature carries many theories about the mechanism of action of local anesthetics (LA). We can highlight those focusing the direct effect of LA on the sodium channel protein and the ones that consider the interaction of anesthetic molecules with the lipid membrane phase. The interaction between local anesthetics and human erythrocyte membranes has been studied by ¹H and 31P nuclear magnetic resonance spectroscopy. It was found that lidocaine (LDC) and benzocaine (BZC) bind to the membranes, increase the mobility of the protons of the phospholipid's acyl chains, and decrease the mobility and/or change the structure of the polar head groups. The results indicate that lidocaine molecules are inserted across the polar and liquid interface of the membrane, establishing both electrostatic (charged form) and hydrophobic (neutral form) interactions. Benzocaine locates itself a little deeper in the bilayer, between the interfacial glycerol region and the hydrophobic core. These changes in mobility or conformation of membrane lipids could affect the Na+-channel protein insertion in the bilayer, stabilizing it in the inactivated state, thus causing anesthesia.