Application of the Williams-Landel-Ferry model to the viscosity-temperature relationship of Australian honeys

The rheological behaviour of nine unprocessed Australian honeys was investigated for the applicability of the Williams-Landel-Ferry (WLF) model. The viscosity of the honeys was obtained over a range of shear rates (0.01-40 s(-1)) from 2degrees to 40 degreesC, and all the honeys exhibited Newtonian behaviour with viscosity reducing as the temperature was increased. The honeys with high moisture were of lower viscosity, The glass transition temperatures of the honeys, as measured with a differential scanning calorimeter (DSC), ranged from -40degrees to -46 degreesC, and four models (WLF. Arrhenius, Vogel-Tammann-Fulcher (VTF), and power-law) were investigated to describe the temperature dependence of the viscosity. The WLF was the most suitable and the correlation coefficient averaged 0.999 +/- 0.0013 as against 0.996 +/- 0.0042 for the Arrhenius model while the mean relative deviation modulus was 0-12% for the WLF model and 10-40% for the Arrhenius one. With the universal values for the WLF constants, the temperature dependence of the viscosity was badly predicted. From non-linear regression analysis, the constants of the WLF models for the honeys were obtained (C-1 = 13.7-21.1: C-2 = 55.9-118.7) and are different from the universal values. These WLF constants will be valuable for adequate modeling of the rheology of the honeys, and they can be used to assess the temperature sensitivity of the honeys. (C) 2002 Elsevier Science Ltd. All rights reserved.

Novel composites of TiO2 (anatase) and silicate nanoparticles

Thermally stable composite nanostructures of titanium dioxide (anatase) and silicate nanoparticles were prepared from Laponite clay and a sol of titanium hydrate in the presence of poly(ethylene oxide) (PEO) surfactants. Laponite is a synthetic clay that readily disperses in water and exists as exfoliated silicate layers of about 1-nm thick in transparent dispersions of high pH. The acidic sol solution reacts with the clay platelets and leaches out most of the magnesium in the clay, while the sol particles hydrolyze further due to the high pH of the clay dispersion. As a result, larger precursors of TiO2 nanoparticles form and condense on the fragmentized pieces of the leached silicate. Introducing PEO surfactants into the synthesis can significantly increase the porosity and surface area of the composite solids. The TiO2 exists as anatase nanoparticles that are separated by silicate fragments and voids such that they are accessible to organic molecules. The size of the anatase particle can be tailored by manipulating the experimental parameters at various synthesis stages. Therefore, we can design and engineer composite nanostructures to achieve better performance. The composite solids exhibit superior properties as photocatalysts for the degradation of Rhodamine 6G in aqueous solution.

Secondary structure of the third extracellular loop responsible for ligand selectivity of a mammalian gonadotropin-releasing hormone receptor

The extracellular loop 3 (ECL3) of the mammalian gonadotropin-releasing hormone receptor (GnRH-R) contains an acidic amino acid (Glu(301) in the mouse GnRH-R,) that confers agonist selectivity for Are in mammalian GnRH. It is proposed that a specific conformation of ECL3 is necessary to orientate the carboxyl side chain of the acidic residue for interaction with Arg(8) of GnRH, which is supported by decreased affinity for Arg(8) GnRH but not Gln(8) GnRH when an adjacent Pro is mutated to Ala. To probe the structural contribution of the loop domain to the proposed presentation of the carboxyl side chain, we synthesized a model peptide (CGPEMLNRVSEPGC) representing residues 293-302 of mouse ECL3, where Cys and Gly residues are added symmetrically at the N and C termini, respectively, allowing the introduction of a disulfide bridge to simulate the distances at which the ECL3 is tethered to the transmembrane domains 6 and 7 of the receptor. The ability of the ECL3 peptide to bind GnRH with low affinity was demonstrated by its inhibition of GnRH stimulation of inositol phosphate production in cells expressing the GnRH-R. The CD bands of the ECL3 peptides exhibited a superposition of predominantly unordered structure and partial contributions from beta-sheet structure. Likewise, the analysis of the amide I and amide III bands from micro-Raman and FT Raman experiments revealed mainly unordered conformations of the cyclic and of the linear peptide. NMR data demonstrated the presence of a beta-hairpin among an ensemble of largely disordered structures in the cyclic peptide. The location of the turn linking the two strands of the hairpin was assigned to the three central residues L-296, N-297, and R-298. A small population of structured species among an ensemble of predominantly random coil conformation suggests that the unliganded receptor represents a variety of structural conformers, some of which have the potential to make contacts with the ligand. We propose a mechanism of receptor activation whereby binding of the agonist to the inactive receptor state induces and stabilizes a particular structural state of the loop domain, leading to further conformational rearrangements across the transmembrane domain and signal propagating interaction with G proteins. Interaction of the Glu(301) of the receptor with Arg(8) of GnRH induces a folded configuration of the ligand. Our proposal thus suggests that conformational changes of both ligand and receptor result from this interaction.

New Zealand climate in the Neogene and implications for global atmospheric circulation

New Zealand has a good Neogene plant fossil record. During the Miocene it was without high topography and it was highly maritime, meaning that its climate, and the resulting vegetation, would be controlled dominantly by zonal climate conditions. Its vegetation record during this time suggests the climate passed from an ever-wet and cool but frostless phase in the Early Miocene in which Nothofagus subgenus Brassospora was prominent. Then it became seasonally dry, with vegetation in which palms and Eucalyptus were prominent and fires were frequent, and in the mid-Miocene, it developed a dry-climate vegetation dominated by Casuarinaceae. These changes are reflected in a sedimentological change from acidic to alkaline chemistry and the appearance of regular charcoal in the record. The vegetation then changed again to include a prominent herb component including Chenopodiaceae and Asteraceae. Sphagnum became prominent, and Nothofagus returned, but mainly as the subgenus Fuscospora (presently restricted to temperate climates). This is interpreted as a return to a generally wet, but now cold climate, in which outbreaks of cold polar air and frost were frequent. The transient drying out of a small maritime island and the accompanying vegetation/climate sequence could be explained by a higher frequency of the Sub-Tropical High Pressure (STHP) cells (the descending limbs of the Hadley cells) over New Zealand during the Miocene. This may have resulted from an increased frequency of 'blocking', a synoptic situation which occurs in the region today. An alternative hypothesis, that the global STHP belt lay at a significantly higher latitude in the early Neogene (perhaps 55degreesS) than today (about 30degreesS), is considered less likely because of physical constraints on STHP belt latitude. In either case, the difference between the early Neogene and present situation may have been a response to an increased polar-equatorial temperature gradient. This contrasts with current climate models for the geological past in which the latitude of the High Pressure belt impact is held invariant though geological time. (C) 2003 Elsevier Science B.V. All rights reserved.

In situ characterization of stickiness of sugar-rich foods using a linear actuator driven stickiness testing device

A stickiness testing device based on the probe tack test has been designed and tested. It was used to perform in situ characterization of drying hemispherical drops with an initial radius 3.5 mm. Tests were carried out in two drying temperatures, 63 and 95 degreesC. Moisture and temperature histories of the drying drops of fructose, honey, sucrose, maltodextrin and sucrose-maltodextrin mixtures were determined. The rates of moisture evaporation of the fructose solution was the fastest while those of the maltodextrin solution was the lowest. A profile reversal was observed when the temperature profiles of these materials were compared. Different modes of failure were observed during the stickiness tests. Pure fructose and honey solutions remained completely sticky and failed cohesively until the end of drying. Pure sucrose solution remained sticky and failed cohesively until complete crystallization occurred. The surface of the maltodextrin drops formed a skin shortly after the start of drying. It exhibited adhesive failure and reached a state of non-adhesion. Addition of maltodextrin significantly altered the stickiness of sucrose solution. (C) 2002 Elsevier Science Ltd. All rights reserved.

Subsoil nitrogen mineralisation and its potential to contribute to NH4 accumulation in a Vertosol

High concentrations of NH4+ (up to 270 kg N/ha) have been observed in a Vertosol below 1 m depth in south-east Queensland. This study examined the possibility that mineralisation associated with the removal of native vegetation (Acacia harpophylla) for cropping was responsible for the production of NH4+. Particularly, the potential contribution of decomposing root material and/or dissolved organic nitrogen (DON) leached into the subsoil after clearing was investigated. The amount of N that was contained within native vegetation root material was determined from an area of native vegetation adjacent to the cleared site containing elevated NH4+ concentrations. In addition, the amount of NH4+ that could be mineralised in the native vegetation soil was determined by monitoring NH4+ concentrations over 360 days in intact cores, and by conducting waterlogged incubations. To determine the rate at which a source of DON leached into the subsoil would mineralise, soil was amended with glutamic acid at a rate of 250 mg N/kg and placed under waterlogged incubation. The possibility that the acidic pH of the subsoil, or the lack of a significant subsoil microbial population, was inhibiting mineralisation was also examined by increasing soil pH from 4.4 to 7.0, and inoculating the subsoil with surface soil microorganisms during waterlogged incubations. Low concentrations of N, approximately 90 kg N/ha between 1.2 and 3 m, were found in the native vegetation root material. In addition, no net N mineralisation was observed in either the extended incubation of intact cores or in the control samples of the waterlogged incubations. Net N mineralisation was also not detected when the subsoil was amended with a source of organic N. Results indicate that this lack of mineralisation is largely due to pH inhibition of the microbial population. It is concluded that the mineralisation of either in situ organic material, or DON transported to the subsoil during leaching events, is unlikely to have significantly contributed to the subsoil NH4 accumulation at the study site.

Characterization of the surface stickiness of fructose-maltodextrin solutions during drying

A probe tack test has been used for the in situ characterization of the surface stickiness of hemispherical drops with an initial radius of 3.5 mm while drying. Surface stickiness of drops of fructose and maltodextrin solutions dried at 63degreesC and 95degreesC was determined. The effect of addition of maltodextrin on fructose solution-was studied with fructose/maltodextrin solid mass ratios of 4: 1, 1: 1, and 1:4. Pure fructose solutions remained completely sticky and failed cohesively even when their moisture approached zero. Shortly after the start of drying, the surface of the maltodextrin drops formed a skin, which rapidly grew in thickness. Subsequently the drop surface became completely nonsticky probably due to transformation of outer layers into a glassy material. Addition of malto,dextrin significantly altered the surface stickiness of drops of fructose solutions, demonstrating its use as an effective drying aid.

Effect of lifter design on drying performance in rotary dryers

Lifter use in dryers improves mass transfer by increasing the amount of surface area available for transfer and also by increasing the velocity of gas over the particle surface. An even cross-sectional distribution of particles in a dryer improves the efficiency of operation by ensuring that evaporation from falling particles is taking place for the maximum fraction of the rotation period of the drier. Studies on lifter design to improve the cross-sectional particle distribution were performed on angled lifters. A single lifter was used and the mass-transfer rate examined as a function of angular lifter displacement. Analysis of the mass transfer characteristics of single lifters allowed performance comparisons and recommendations for lifter design.

Surface stickiness of drops of carbohydrate and organic acid solutions during convective drying: Experiments and modeling

Drying kinetics of low molecular weight sugars such as fructose, glucose, sucrose and organic acid such as citric acid and high molecular weight carbohydrate such as maltodextrin (DE 6) were determined experimentally using single drop drying experiments as well as predicted numerically by solving the mass and heat transfer equations. The predicted moisture and temperature histories agreed with the experimental ones within 6% average relative (absolute) error and average difference of +/- 1degreesC, respectively. The stickiness histories of these drops were determined experimentally and predicted numerically based on the glass transition temperature (T-g) of surface layer. The model predicted the experimental observations with good accuracy. A nonsticky regime for these materials during spray drying is proposed by simulating a drop, initially 120 mum in diameter, in a spray drying environment.

Dissolution of sucrose crystals in the anhydrous sorbitol melt

The dissolution of a sugar (sucrose as a model) with higher melting point was studied in a molten food polyol (sorbitol as a model) with lower melting point, both in anhydrous state. A DSC and optical examination revealed the dissolution of anhydrous sucrose crystals (mp 192 degreesC) in anhydrous sorbitol (mp 99 degreesC) liquid melt. The sucrose-sorbitol crystal mixtures at the proportions of 10, 30, 60, 100 and 150 g of sucrose per 100 g of sorbitol were heat scanned in a DSC to above melting endotherm of sorbitol but well below the onset temperature of melting of sucrose at three different temperatures 110, 130 and 150 degreesC. The heat scanning modes used were with or without isothermal holding. The dissolution of sucrose in the sorbitol liquid melt was manifested by an increase in the glass transition temperature of the melt and corresponding decrease in endothermic melting enthalpy of sucrose. At given experimental conditions, as high as 25 and 85% of sucrose dissolved in the sorbitol melt during 1 h of isothermal holding at 110 and 150 degreesC, respectively. Optical microscopic observation also clearly showed the reduction in the size of sucrose crystals in sorbitol melt during the isothermal holding at those temperatures. (C) 2003 Elsevier Science Ltd. All rights reserved.

Solubility of selected esters in supercritical carbon dioxide

The solubility of ethyl propionate, ethyl butyrate, and ethyl isovalerate in supercritical carbon dioxide was measured at temperature ranging from 308.15 to 333.15 K and pressure ranging from 85 to 195 bar. At the same temperature, the solubility of these compounds increases with pressure. The crossover pressure region was also observed in this study. The experimental data were correlated by the semi-empirical Chrastil equation and Peng-Robinson equation of state (EOS) using several mixing rules. The Peng-Robinson EOS gives better solubility prediction than the empirical Chrastil equation. (C) 2002 Elsevier Science B.V. All rights reserved.

Vendas de bebidas alcóolicas : questões (im)pertinentes

O objetivo deste estudo é analisar a disponibilidade e o acesso à bebida alcoólica num bairro da cidade de Vitória/ES. Os dados foram obtidos através de pesquisa de campo na região selecionada utilizando a observação simples e a entrevista através da aplicação de questionários numa amostra de 10% dos estabelecimentos encontrados. Os pontos de venda funcionam 7 dias por semana; 68,8% vendem a credito e a um preço médio de R$ 0,41 (a dose de cachaça). 93,8% dos entrevistados não solicitam documento de identidade ao cliente antes de lhe vender bebidas. A relação entre número de moradias e número de pontos de venda foi de 3:1. A alta concentração de estabelecimentos que vendem bebidas alcoólicas no bairro aponta para a necessidade de pensar o entorno (regiões vizinhas) da mesma. Estas regiões envolvem áreas marginalizadas onde ocorre tráfico de drogas, fazendo da região estudada uma área importante para o comércio, pela facilidade de acesso aos outros bairros adjacentes da cidade.

Análise de Parafinas por APCI-FT-ICR MS : Uma Análise Rápida e Simples na Identificação de Hidrocarbonetos Saturados, Cíclicos e Poliaromáticos

A análise de hidrocarbonetos por técnicas de ionização a pressão atmosférica ou ambiente continua a ser um desafio na espectrometria de massas. Normalmente, a ionização ocorre através de mecanismos de protonação e desprotonação. Para isso, as moléculas de interesse devem apresentar um grupo básico ou ácido que proporcionem a geração de íons [M+H]+ ou [M-H]-. Para superar essa limitação, um método analítico simples, fácil, rápido e poderoso foi desenvolvido com sucesso, adaptado a partir da literatura, para ionizar saturado e insaturado, linear, ramificado, e hidrocarbonetos cíclicos, bem como hidrocarbonetos poliaromáticos e heteroaromáticos presentes em frações de hidrocarbonetos e de misturas de parafina/petróleo bruto utilizando ionização química à pressão atmosférica (APCI), favorecido pela utilização de solventes alifáticos de cadeia curta em um espectrômetro de massas FT-ICR. Entre os reagentes alifáticos estudados, isoctano proporcionou os melhores resultados quando comparado com outros solventes. Além disso, foram estudados outros interferentes do processo de ionização, como concentração da solução injetada e misturas parafina/óleo, que influenciavam desde o perfil dos espectros até as principais classes de compostos identificados. O método torna possível a ionização de hidrocarbonetos pela produção de íons [M -H]+ sem ocorrência de fragmentação.

Eu bebo sim e estou vivendo : qualidade de vida, masculinidade, padrões de consumo de álcool e representações sociais de bebida alcoólica para homens usuários de unidade de saúde da família

A Política Nacional de Atenção Integral à Saúde do Homem propõe formas diferenciadas de atuação da equipe de saúde no atendimento da população masculina, uma vez que este público demanda estratégias diferenciadas de serviço. Ao se deparar com a realidade vivenciada pelos homens, surgem várias questões acerca do estereótipo social construído acerca das características masculinas e suas vivências. O objetivo da pesquisa foi compreender alguns aspectos relevantes para as práticas de saúde de homens usuários de Unidade de Saúde da Família, como qualidade de vida, consumo de álcool, representações sociais da bebida alcoólica e características de masculinidade. Foi utilizada uma amostra de 300 homens, frequentadores de Unidade de Saúde da Família, e aplicado um questionário contendo os dados sociodemográficos, o World Health Organization Quality of Life (Whoqol-bref), o Bem Sex-Role Inventory (BSRI), um exercício de evocação sobre bebida alcoólica, o Alcohol Use Disorders Identification Test (Audit) e um bloco para verificar os problemas ocasionados pelo consumo de álcool e a procura por tratamento. Os dados dos instrumentos quantitativos foram analisados com testes estatísticos de comparação de médias e de correlação. Os dados das evocações foram analisados com o software EVOC (Ensemble de Programmes Permettant l’Analyse des Évocations). Na primeira análise, constatou-se adesão mais alta a características femininas, alta percepção de qualidade de vida e padrões de consumo de álcool semelhantes às médias nacionais. Homens que declararam praticar sua religião apresentaram média significativamente menor de consumo de álcool. Apresentaram correlação inversamente proporcional ao consumo de álcool as características femininas de gênero, os domínios físico, social, psicológico e percepção global de qualidade de vida. Na análise das evocações, constatou-se que os elementos com tendência à centralidade são, em sua maioria, de cunho negativo. Os dados da população geral apresentaram o termo gosto como um aspecto positivo e central da bebida alcoólica. O grupo de abstinentes não apresentou avaliação positiva do termo e o grupo de bebedores apresentou o termo diversão na primeira periferia, referindo-se aos aspectos positivos e de socialização da bebida alcoólica. Os resultados indicaram uma qualidade de vida satisfatória, a religião e as características femininas destacaram-se como um fator de proteção ao uso de bebida alcoólica. Apresentaram, ainda, percepção dos problemas associados ao próprio consumo. Apesar de a maioria dos termos relacionados à bebida alcoólica ser negativo, este consumo ainda se dá em um nível considerável. Por isso, se faz necessária a construção de vínculo entre o profissional e o usuário do serviço de saúde a fim de dar oportunidade para que as reais práticas sobre a bebida alcoólica sejam evidenciadas. Esses dados podem ajudar profissionais de Saúde da Família a refletirem sobre as representações sociais que constroem acerca dos homens de classe popular usuários do serviço