The effect of non-uniform radiative damping on the zonal-mean dynamics of the extratropical middle atmosphere

The effect of spatial and temporal variations in the radiative damping rate on the response to an imposed forcing or diabatic heating is examined in a zonal-mean model of the middle atmosphere. Attention is restricted to the extratropics, where a linear approach is viable. It is found that regions with weak radiative damping rates are more sensitive in terms of temperature to the remote influence of the diabatic circulation. The delay in the response in such regions can mean that ‘downward’ control is not achieved on seasonal time-scales. A seasonal variation in the radiative damping rate modulates the evolution of the response and leaves a transient-like signature in the annual mean temperature field. Several idealized examples are considered, motivated by topical questions. It is found that wave drag outside the polar vortex can significantly affect the temperatures in its interior, so that high-latitude, high-altitude gravity-wave drag is not the only mechanism for warming the southern hemisphere polar vortex. Diabatic mass transport through the 100 hPa surface is found to lag the seasonal evolution of the wave drag that drives the transport, and thus cannot be considered to be in the downward control regime. On the other hand, the seasonal variation of the radiative damping rate is found to make only a weak contribution to the annual mean temperature increase that has been observed above the ozone hole. Copyright © 2002 Royal Meteorological Society.

The ocean’s role in setting the mean position of the Inter-Tropical Convergence Zone

Through study of observations and coupled climate simulations, it is argued that the mean position of the Inter-Tropical Convergence Zone (ITCZ) north of the equator is a consequence of a northwards heat transport across the equator by ocean circulation. Observations suggest that the hemispheric net radiative forcing of climate at the top of the atmosphere is almost perfectly symmetric about the equator, and so the total (atmosphere plus ocean) heat transport across the equator is small (order 0.2 PW northwards). Due to the Atlantic ocean’s meridional overturning circulation, however, the ocean carries significantly more heat northwards across the equator (order 0.4 PW) than does the coupled system. There are two primary consequences. First, atmospheric heat transport is southwards across the equator to compensate (0.2 PW southwards), resulting in the ITCZ being displaced north of the equator. Second, the atmosphere, and indeed the ocean, is slightly warmer (by perhaps 2 °C) in the northern hemisphere than in the southern hemisphere. This leads to the northern hemisphere emitting slightly more outgoing longwave radiation than the southern hemisphere by virtue of its relative warmth, supporting the small northward heat transport by the coupled system across the equator. To conclude, the coupled nature of the problem is illustrated through study of atmosphere–ocean–ice simulations in the idealized setting of an aquaplanet, resolving the key processes at work.

Supercritical fluid extracts from the Brazilian cherry (Eugenia uniflora L.): Relationship between the extracted compounds and the characteristic flavour intensity of the fruit

Supercritical carbon dioxide (SC-CO(2)) extractions of Brazilian cherry (Eugenia uniflora L.) were carried out under varied conditions of pressure and temperature, according to a central composite 2(2) experimental design, in order to produce flavour-rich extracts. The composition of the extracts was evaluated by gas chromatography coupled with mass spectrometry (GC/MS). The abundance of the extracted compounds was then related to sensory analysis results, assisted by principal component and factorial discriminant analysis (PCA and FDA, respectively). The identified sesquiterpenes and ketones were found to strongly contribute to the characteristic flavour of the Brazilian cherry. The extracts also contained a variety of other volatile compounds, and part of the fruit wax contained long-chain hydrocarbons that according to multivariate analysis, contributed to the yield of the extracts, but not the flavour. Volatile phenolic compounds, to which antioxidant properties are attributed, were also present in the extracts in high proportion, regardless of the extraction conditions. (C) 2010 Elsevier Ltd. All rights reserved.

Lipid bilayer pre-transition as the beginning of the melting process

We investigate the bilayer pre-transition exhibited by some lipids at temperatures below their main phase transition, and which is generally associated to the formation of periodic ripples in the membrane. Experimentally we focus on the anionic lipid dipalmytoylphosphatidylglycerol (DPPG) at different ionic strengths, and on the neutral lipid dipalmytoylphosphatidylcholine (DPPC). From the analysis of differential scanning calorimetry traces of the two lipids we find that both pre- and main transitions are part of the same melting process. Electron spin resonance of spin labels and excitation generalized polarization of Laurdan reveal the coexistence of gel and fluid domains at temperatures between the pre- and main transitions of both lipids, reinforcing the first finding. Also, the melting process of DPPG at low ionic strength is found to be less cooperative than that of DPPC. From the theoretical side, we introduce a statistical model in which a next-nearest-neighbor competing interaction is added to the usual two-state model. For the first time, modulated phases (ordered and disordered lipids periodically aligned) emerge between the gel and fluid phases as a natural consequence of the competition between lipid-lipid interactions. (C) 2009 Elsevier B.V. All rights reserved.

An investigation of the activation process of high temperature shift catalyst

The aim of this work is to address the activation process of a high temperature shift (HTS) catalyst, composed of Fe2O3/Cr2O3/CuO, by analyzing it before activation (HTS-V) and after activation (HTS-A) using complementary characterization techniques. The textural and morphological characterizations were done by transmission electron rnicroscopy (TEM) and nitrogen physisorption at 77 K; crystallographic structure was confirmed by X-ray diffraction (XRD); electronic structure was analyzed by X-ray absorption spectroscopy (XAS) and the chemical composition of the catalyst`s surface was obtained by X-ray photoelectron spectroscopy (XPS). The investigation pointed out that the HTS-V catalyst presents good textural and morphological properties, which are not deeply affected by the activation process (sample HTS-A). The iron oxide phase in the HTS-V catalyst is hematite whereas in HTS-A catalyst is magnetite with Fe2+/Fe3+ ratio close to the expected value (0.5). For both samples, the Cr ions seem to be incorporated in the iron oxide lattice with higher concentration at particle surface. In the HTS-V catalyst, the Cu ions have oxidation number II and occupy in average distorted octahedral sites; after the activation, the Cu ions are partially reduced, suggesting that the reduction of the Cu species is complex. (C) 2007 Elsevier B.V. All rights reserved.

Investigation of the drying process of linseed oil using FTIR and ToF-SIMS

The drying process of linseed oil, oxidized at 80 oC, has been investigated with rheology measurements, Fourier transformation infrared spectroscopy (FTIR), and time of flight secondary ion mass spectrometry (ToF-SIMS). The drying process can be divided into three main steps: initiation, propagation and termination. ToF-SIMS spectra show that the oxidation is initiated at the linolenic (three double bonds) and linoleic fatty acids (two double bonds). ToF-SIMS spectra reveal peaks that can be assigned to ketones, alcohols and hydroperoxides. In this article it is shown that FTIR in combination with ToF-SIMS are well suited tools for investigations of various fatty acid components and reaction products of linseed oil.

Effect of the estufagem process on the chemical constituents of Madeira wines

Madeira wine is a product of well-established reputation, whose aroma and flavour is the result of unique combinations. Particularly, its maturation may include estufagem, wherein wine is usually heated at 45 °C for three months. During this period, several chemical changes may occur, so it is essential to assess its impact on the wine. In this sense, the main objective of the thesis was to evaluate the effect estufagem on the chemical constituents of Madeira wine, specifically on those molecules potentially important in the development of its typical features. Firstly, analytical methodologies capable of determining the target compounds, combining precision and reproducibility to execution effectiveness, were developed. Then various monovarietal Madeira wines were analysed during estufagem under standard and overheating conditions in order to assess its effect. The following compounds were evaluated: furans, amino acids, biogenic amines, polyphenols, organic acids and volatile compounds. In addition, the total polyphenolic composition, the antioxidant potential and the colour of these wines were also evaluated. The results show that most constituents change due to the heating process. Particularly, the heating promotes the development of 5-hydroxymethylfurfural (HMF) in sweet wines submitted to estufagem at higher temperatures. Moreover, estufagem provides the decrease of most amino acids, suggesting their involvement in the formation of the bouquet of these wines. Regarding the total polyphenol content and antioxidant potential of these wines they do not seem to be greatly affected by the heating step, however most monomeric polyphenols decrease during this process. The thermal processing of Madeira wines favours the development of the volatile composition, especially of volatiles usually reported as typical aromas of Madeira wines. Finally, it was demonstrated that the thermal degradation of sugars, especially of fructose, promotes the emergence of volatile compounds identified in baked wines.

Magnetic images of the disintegration process of tablets in the human stomach by ac biosusceptometry

Oral administration of solid dosage forms is usually preferred in drug therapy. Conventional imaging methods are essential tools to investigate the in vivo performance of these formulations. The non-invasive technique of ac biosusceptometry has been introduced as an alternative in studies focusing on gastrointestinal motility and, more recently, to evaluate the behaviour of magnetic tablets in vivo. The aim of this work was to employ a multisensor ac biosusceptometer system to obtain magnetic images of disintegration of tablets in vitro and in the human stomach. The results showed that the transition between the magnetic marker and the magnetic tracer characterized the onset of disintegration (t(50)) and occurred in a short time interval (1.1 +/- 0.4 min). The multisensor ac biosusceptometer was reliable to monitor and analyse the in vivo performance of magnetic tablets showing accuracy to quantify disintegration through the magnetic images and to characterize the profile of this process.

Analysis of the healing process in delayed tooth replantation after root canal filling with calcium hydroxide, Sealapex and Endofill: a microscopic study in rats

The major concern in the therapeutics of tooth replantation refers to the occurrence of root resorption and different approaches have been proposed to prevent or treat these complications. The purpose of this study was to evaluate tissue response to delayed replantation of anterior rat teeth treated endodontically using calcium hydroxide, Sealapex, and Endofill without the placement of gutta-percha cones. Thirty rats had their right upper incisor extracted and maintained in dry storage for 60 min. After removal of the dental papilla, enamel organ, pulp tissue, and periodontal ligament remnants, the teeth were immersed in 2% sodium fluoride phosphate acidulated, pH 5.5, for 10 min. The root canals were dried with absorbent paper points and the teeth were assigned to three groups (n = 10) according to the filling material. Group I - calcium hydroxide and propyleneglycol paste, Group II - Sealapex, and Group III - Endofill. The sockets were irrigated with saline and the teeth were replanted. Replacement resorption, inflammatory resorption and ankylosis were observed in all groups. Although the occurrence of inflammatory resorption was less frequent in Group I, there were no statistically significant differences among the groups. It may be concluded that compared to the paste, filling the root canals with Sealapex and Endofill sealers without the placement of gutta-percha cones did not provide better results.

Histomorphometric analysis of the repair process of autogenous bone grafts fixed at rat calvaria with cyanoacrylate

Objective: The purpose of this study was to perform histological and histometric analyses of the repair process of autogenous bone grafts fixed at rat calvaria with ethyl-cyanoacrylate adhesive. Material and Methods: Thirty-two rats were divided into two groups (n=16), Group I - Control and Group II - Adhesive. Osteotomies were made at the right parietal bone for graft obtainment using a 4-mm-diameter trephine drill. Then, the bone segments were fixed with the adhesive in the parietal region of the opposite side to the donor site. After 10 and 30 days, 8 animals of each group were euthanized and the calvarias were laboratorially processed for obtaining hematoxylin and eosin-stained slides for histological and histometric analyses. Results: An intense inflammatory reaction was observed at the 10-day period. At 30 days, this reaction was less intense, despite the presence of adhesive at the recipient-site/graft interface. Graft incorporation to the recipient site was observed only at the control group, which maintained the highest graft size at 10 and 30 days. Conclusions: Although the fragment was stable, the presence of adhesive in Group II did not allow graft incorporation to the recipient site, determining a localized, discrete and persistent inflammatory reaction.

A spectroelectrochemical study of the inhibition of the electrode process on copper by 2-mercaptobenzothiazole in ethanolic solutions

The effect of 2-mercaptobenzothiazole (MBT) on the corrosion of copper in ethanol-water mixture with 0.01 mol dm(-3) HClO4 was investigated by linear sweep voltammetry and surface enhanced Raman scattering spectroscopy. The linear sweep voltammetry for the copper electrode in the presence of MBT shows one anodic process associated with the oxidation of MBT, which leads to the formation of a film on the electrode. This film inhibits the anodic copper dissolution and cathodic hydrogen evolution reaction. SERS studies indicated that MBT oxidizes and forms polymeric complexes involving copper ions and the ionized form of thiol. (C) 1997 Elsevier B.V. Ltd.

Electrochemical capacitance spectroscopy and capacitive relaxation of the changeover process in iron hexacyanoferrate molecular compound

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

Study of the growth process of in situ polyaniline deposited films

Polyaniline (PAni) thin films were deposited onto BK7 glass substrates using the in situ deposition technique. The control of the time and the aniline concentration in the PAni polymerization reaction on the film deposition allowed us to prepare films with different thickness, down to similar to 25 nm. The film growth process was monitored by measuring the UV-vis spectra and the AFM height profiles of the film surface. The curves of adsorption kinetics were analyzed with the Avrami's model, yielding an exponent it n = 3, thus indicating nucleation of spheroids at the initial stages of polymerization that grow through a diffusion process. AFM images of the surface height profiles corroborate this hypothesis, with spheroids growing with no preferred orientation during the in situ deposition. (C) 2007 Elsevier B.V. All rights reserved.

Thermal decomposition of crystalline Ni-II-Cr-III layered double hydroxide: A structural study of the segregation process

A structural study of the thermal evolution of Ni0.69Cr0.31(OH)(2)(CO3)(0.155)(.)nH(2)O into NiO and tetragonal NiCr2O4 is reported. The characteristic structural parameters of the two coexisting crystalline phases, as well as their relative abundance, were determined by Rietveld refinement of powder x-ray diffraction (PXRD) patterns. The results of the simulations allowed us to elucidate the mechanism of the demixing process of the oxides. It is demonstrated that nucleation of a metastable nickel chromite within the common oxygen framework of the parent Cr-III-doped bunsenite is the initial step of the cationic redistribution. The role that trivalent cations play in the segregation of crystalline spinels is also discussed.