C - H ⋯ 0 and N - H ⋯ 0 hydrogen bonds in liquid amides investigated by monte carlo simulation

Monte Carlo simulations of liquid formamide, N-methylformamide (MF), and N, N-dimethytformamide (DMF) have been performed in the isothermal and isobaric ensemble at 298 K and 1 atm, aiming to investigate the C-H ⋯ O and N-H ⋯ O hydrogen bonds. The interaction energy was calculated using the classical 6-12 Lennard-Jones pairwise potential plus a Coulomb term on a rigid six-site molecular model with the potential parameters being optimized in this work. Theoretical values obtained for heat of vaporization and liquid densities are in good agreement with the experimental data. The radial distribution function [RDF, g(r)] obtained compare well with R-X diffraction data available. The RDF and molecular mechanics (MM2) minimization show that the C-H ⋯ O interaction has a significant role in the structure of the three liquids. These results are supported by ab initio calculations. This interaction is particularly important in the structure of MF. The intensity of the N - H ⋯ O hydrogen bond is greater in the MF than formamide. This could explain some anomalous properties verified in MF. © 1997 John Wiley & Sons, Inc.

Structure and weak hydrogen bonds in liquid acetaldehyde

Monte Carlo simulations have been performed to investigate the structure and hydrogen bonds formation in liquid acetaldehyde. An all atom model for the acetaldehyde have been optimized in the present work. Theoretical values obtained for heat of vaporisation and density of the liquid are in good agreement with experimental data. Graphics of radial distribution function indicate a well structured liquid compared to other similar dipolar organic liquids. Molecular mechanics minimization in gas phase leads to a trimer of very stable structure. The geometry of this complex is in very good agreement with the rdf. The shortest site-site correlation is between oxygen and the carbonyl hydrogen, suggesting that this correlation play a important role in the liquid structure and properties. The O⋯H average distance and the C-H⋯O angle obtained are characteristic of weak hydrogen bonds.

La contribución de los gobiernos corporativos responsables a la sostenibilidad ambiental

Incluye Bibliografía

Buenos gobiernos corporativos para los negocios: el caso de Chile

Incluye Bibliografía

Portais corporativos: tecnologia da informação e do conhecimento em empresas de tecnologia da informação

Pós-graduação em Ciência da Informação - FFC

Exposed Collagen In Resin Bonds to Caries-affected Dentin After Dentin Treatment with Aqueous and Alcoholic Chlorhexidine Solutions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Increased durability of resin-dentin bonds following cross-linking treatment

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

Durable bonds at the adhesive/dentin interface: an impossible mission or simply a moving target?

Composite restorations have higher failure rates, more recurrent caries and increased frequency of replacement as compared to dental amalgam. Penetration of bacterial enzymes, oral fluids, and bacteria into the crevices between the tooth and composite undermines the restoration and leads to recurrent decay and failure. The gingival margin of composite restora tions is particularly vulnerable to decay and at this margin, the adhesive and its seal to dentin provides the primary barrier between the prepared tooth and the environment. The intent of this article is to examine physico-chemical factors that affect the integrity and durability of the adhesive/dentin interfacial bond; and to explore how these factors act synergistically with mechanical forces to undermine the composite restoration. The article will examine the various avenues that have been pursued to address these problems and it will explore how alterations in material chemistry could address the detrimental impact of physico-chemical stresses on the bond formed at the adhesive/dentin interface.

Exponential depletion of neutral dangling bonds density (D-0) by rare-earth doping in amorphous Si films

In this work we study the effect reduction in the density of dangling bond species D-0 states in rare-earth (RE) doped a-Si films as a function concentration for different RE-specimens. The films a-Si-1_(x) REx, RE=Y3+, Gd3+, Er3+, Lu3+) were prepared by co-sputtering and investigated by electron spin resonance (ESR) and Raman scattering experiments. According to our data the RE-doping reduces the ESR signal intensity of the D-0 states with an exponential dependence on the rare-concentration. Furthermore, the reduction produced by the magnetic rare-earths Gd3+ and Er3+ is remarkably greater than that caused by Y3+ and Lu3+, which led us to suggest an exchange-like coupling between the spin of the magnetic REs3+ and the spin of silicon neutral dangling bonds. (C) 2011 Elsevier B.V. All rights reserved.

Degradation of resin-dentin bonds of etch-and-rinse adhesive system to primary and permanent teeth

The aim of this in vitro study was to compare the degradation of resin-dentin bonds of an etch-and-rinse adhesive system to primary and permanent teeth. Flat superficial coronal dentin surfaces from 5 primary second molars and 5 permanent third molars were etched with phosphoric acid and bonded with an adhesive system (Adper Single Bond 2, 3M ESPE). Blocks of resin composite (Z250, 3M ESPE) were built up and the teeth sectioned to produce bonded sticks with a 0.8 mm(2) cross-sectional area. The sticks of each tooth were randomly divided and assigned to be subjected to microtensile testing immediately (24 h) or after aging by water storage (6 months). Data were analyzed by two-way repeated measures ANOVA and Tukey post hoc test (alpha = 0.05). Failure mode was evaluated using a stereomicroscope (400x). Microtensile values significantly decreased after the 6 months aging, independent of the dentin substrate. In 24 h, the values obtained to primary dentin were lower compared with permanent dentin. This difference was not maintained after aging. Adhesive/mixed failure was predominant in all experimental groups. In conclusion, degradation of resin-dentin bonds of the etch-and-rinse adhesive system occurred after 6 months of water storage; however, the reduction in bond strength values was higher for permanent teeth.

The nature of Ru-NO bonds in ruthenium tetraazamacrocycle nitrosyl complexes-a computational study

Ruthenium complexes including nitrosyl or nitrite complexes are particularly interesting because they can not only scavenge but also release nitric oxide in a controlled manner, regulating the NO-level in vivo. The judicious choice of ligands attached to the [RuNO] core has been shown to be a suitable strategy to modulate NO reactivity in these complexes. In order to understand the influence of different equatorial ligands on the electronic structure of the Ru-NO chemical bonding, and thus on the reactivity of the coordinated NO, we propose an investigation of the nature of the Ru-NO chemical bond by means of energy decomposition analysis (EDA), considering tetraamine and tetraazamacrocycles as equatorial ligands, prior to and after the reduction of the {RuNO}(6) moiety by one electron. This investigation provides a deep insight into the Ru-NO bonding situation, which is fundamental in designing new ruthenium nitrosyl complexes with potential biological applications.

Degradation of the resin-dentin bonds after simulated and inhibited cariogenic challenge in an in situ model

The aim of this study was to evaluate the resindentin bonds of two simplified etch-and-rinse adhesive after simulated cariogenic and inhibited cariogenic challenge in situ. Dental cavities (4 mm wide, 4 mm long, and 1.5 mm deep) were prepared in 60 bovine teeth with enamel margins. Restorations were bonded with either adhesive Adper Single Bond 2 (3MESPE) or Optibond Solo Plus (Kerr). Forty restorations were included in an intra-oral palatal appliance that was used for 10 adult volunteers while the remaining 20 dental blocks were not submitted to any cariogenic challenge [NC group] and tested immediately. For the simulated cariogenic challenge [C+DA], each volunteer dropped 20% sucrose solution onto all blocks four times a day during 14 days and distilled water twice a day. In the inhibited cariogenic challenge group [C + FA], the same procedure was done, but slurry of fluoride dentifrice (1.100 ppm) was applied instead of water. The restored bovine blocks were sectioned to obtain a slice for cross-sectional Vickers microhardness evaluation and resindentin bonded sticks (0.8 mm2) for resindentin microtensile evaluation. Data were evaluated by two-way ANOVA and Tukey's tests (a = 0.05). Statistically lower microhardness values and degradation of the resindentin bonds were only found in the C + DW group for both adhesives. The in situ model seems to be a suitable short-term methodology to investigate the degradation of the resindentin bonds under a more realistic condition. (c) 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 100B: 14661471, 2012.

Uma análise econômico-atuarial dos death bonds

Um death bond é um título emitido por uma instituição financeira para comprar uma apólice de seguro de vida de um segurado que deseja receber recursos ainda em vida. Este trabalho faz a precificação dos death bonds para ambos os gêneros e diferentes idades de contratação do seguro, empregando técnicas de modelagem atuarial. Os resultados iniciais mostram pouca atratividade para os investidores no título. Uma extensão do modelo mostra que se os investidores conseguirem identificar os segurados com as piores condições de saúde, os retornos são substancialmente mais elevados e os desvios-padrão são bastante reduzidos.

Gestão ambiental e interesses corporativos: imagem ambiental ou novas relações com o ambiente?

Este artigo trata da emergência de um novo sistema de comunicação ambiental a serviço das grandes corporações. Este sistema agrega novos agentes entre os quais podemos destacar: ONGs supostamente ambientalistas, empresas de certificação ambiental, instituições que promovem premiações ambientais. Argumenta-se que esta situação transformou as condições em que ocorre o embate sobre as questões ambientais e sobre as potenciais soluções para estas questões. A pesquisa funda-se em uma revisão da literatura sobre o assunto e em uma análise qualitativa de um conjunto de publicidades brasileiras que se utiliza de temas ambientais. Neste conjunto de publicidades, aparecem elementos para construirmos hipóteses sobre as articulações realizadas pelo setor corporativo para responder ao desafio ambientalista.

Studies on Transformations of H-Phosphonates into DNA Analogues Containing P-S or P-C Bonds

In this thesis, mechanistic and synthetic studies on transformations of H-phosphonates into DNA analogues containing P-S or P-C bonds are described. Configurational stability of dinucleoside H-phosphonates and the stereochemical course of their sulfurisation in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) were investigated. In light of these studies, the reported stereoselective sulfurisation of dinucleoside H-phosphonates and benzoylphosphonates in the presence of DBU was proved to be incorrect. Efficient protocols for the synthesis of new nucleotide analogues with non-ionic C-phosphonate internucleotide linkages were developed. The synthesis of dinucleoside 2-pyridylphosphonates was successfully performed by a DBU-promoted reaction of H-phosphonate diesters with N-methoxypyridinium salts. The thio analogues, 2-pyridyl- and 4-pyridyl phosphonothioate diesters, could be obtained by modifying the reactions developed for their oxo counterparts. Dinucleoside 3-pyridylphosphonates were prepared via a palladium(0)-catalysed cross coupling strategy that could be extended also to the synthesis of nucleotide analogues with metal-complexing properties, i.e. terpyridyl- and bipyridylphosphonate derivatives. Oligonucleotides modified with pyridylphosphonate internucleotide linkages have been prepared and preliminary studies on their hybridisation properties and resistance towards enzymatic degradation were performed. Finally, nucleotidic units for the incorporation of pyridylphosphonate groups at the 5’-terminus of oligonucleotides were designed. Condensations of such units with a suitably protected nucleoside afforded after oxidation the expected dinucleoside (3’-5’)-phosphates with pyridylphosphonate monoester functions at the 5’-ends.