A master equation model for bimolecular reaction via multi-well isomerization intermediates

A reversible linear master equation model is presented for pressure- and temperature-dependent bimolecular reactions proceeding via multiple long-lived intermediates. This kinetic treatment, which applies when the reactions are measured under pseudo-first-order conditions, facilitates accurate and efficient simulation of the time dependence of the populations of reactants, intermediate species and products. Detailed exploratory calculations have been carried out to demonstrate the capabilities of the approach, with applications to the bimolecular association reaction C3H6 + H reversible arrow C3H7 and the bimolecular chemical activation reaction C2H2 +(CH2)-C-1--> C3H3+H. The efficiency of the method can be dramatically enhanced through use of a diffusion approximation to the master equation, and a methodology for exploiting the sparse structure of the resulting rate matrix is established.

Prediction of the chemical composition of lamb carcasses from multi-frequency impedance data

Multi-frequency bioimpedance analysis (MFBIA) was used to determine the impedance, reactance and resistance of 103 lamb carcasses (17.1-34.2 kg) immediately after slaughter and evisceration. Carcasses were halved, frozen and one half subsequently homogenized and analysed for water, crude protein and fat content. Three measures of carcass length were obtained. Diagonal length between the electrodes (right side biceps femoris to left side of neck) explained a greater proportion of the variance in water mass than did estimates of spinal length and was selected for use in the index L-2/Z to predict the mass of chemical components in the carcass. Use of impedance (Z) measured at the characteristic frequency (Z(c)) instead of 50 kHz (Z(50)) did not improve the power of the model to predict the mass of water, protein or fat in the carcass. While L-2/Z(50) explained a significant proportion of variation in the masses of body water (r(2) 0.64), protein (r(2) 0.34) and fat (r(2) 0.35), its inclusion in multi-variate indices offered small or no increases in predictive capacity when hot carcass weight (HCW) and a measure of rib fat-depth (GR) were present in the model. Optimized equations were able to account for 65-90 % of the variance observed in the weight of chemical components in the carcass. It is concluded that single frequency impedance data do not provide better prediction of carcass composition than can be obtained from measures of HCW and GR. Indices of intracellular water mass derived from impedance at zero frequency and the characteristic frequency explained a similar proportion of the variance in carcass protein mass as did the index L-2/Z(50).

Numerical modelling of single-layer folding: clarification of an issue regarding the possible effect of computer codes and the influence of initial irregularities

The influence of initial perturbation geometry and material propel-ties on final fold geometry has been investigated using finite-difference (FLAC) and finite-element (MARC) numerical models. Previous studies using these two different codes reported very different folding behaviour although the material properties, boundary conditions and initial perturbation geometries were similar. The current results establish that the discrepancy was not due to the different computer codes but due to the different strain rates employed in the two previous studies (i.e. 10(-6) s(-1) in the FLAC models and 10(-14) s(-1) in the MARC models). As a result, different parts of the elasto-viscous rheological field were bring investigated. For the same material properties, strain rate and boundary conditions, the present results using the two different codes are consistent. A transition in Folding behaviour, from a situation where the geometry of initial perturbation determines final fold shape to a situation where material properties control the final geometry, is produced using both models. This transition takes place with increasing strain rate, decreasing elastic moduli or increasing viscosity (reflecting in each case the increasing influence of the elastic component in the Maxwell elastoviscous rheology). The transition described here is mechanically feasible but is associated with very high stresses in the competent layer (on the order of GPa), which is improbable under natural conditions. (C) 2000 Elsevier Science Ltd. All rights reserved.

A multi-sectorial committee in directing HIV/AIDS-specific interventions in the occupational setting: An example from South Africa

We present a descriptive analysis of a mechanism to coordinate and implement human immunodeficiency virus (HIV) prevention and care in the occupational setting. The mechanism we describe is a multidisciplinary committee composed of stakeholders in the occupational health environment including unions, management, medical researchers, and medical personnel. The site chosen for the analysis was a South African sugar mill in rural KwaZulu-Natal. The factory is situated in an area of high HIV seroprevalence and has a workforce of 400 employees. The committee was initiated to coordinate a combined prevention-care initiative. The issues that were important in the formation of the committee included confidentiality, trust, and the traditional roles of the stakeholder relationships. When these points were addressed through the focus on a common goal, the committee was able to function in its role as a coordinating body. Central to this success was the inclusion of all stakeholders in the process, including those with traditionally opposing, interests and legitimacy conferred by the stakeholders. This committee was functionally effective and demonstrated the benefit of a freestanding committee dedicated to addressing HIV/acquired immune deficiency syndrome (AIDS) issues. We describe the implementation and feasibility of a multisectoral committee in directing HIV/AIDS initiatives in the occupational setting in rural South Africa.

The polar ionosphere at Zhongshan Station on May 11, 1999, the day the solar wind almost disappeared

The solar wind almost disappeared on May 11,1999: the solar wind plasma density and' dynamic pressure were less than 1 cm(-3) and 0.1 nPa respectively, while the interplanetary magnetic field was northward. The polar ionospheric data observed by the multi-instruments at Zhongshan Station in Antarctica on such special event day was compared with those of the control day (May 14). It was shown that geomagnetic activity was very quiet on May 11 at Zhongshan. The magnetic pulsation, which usually occurred at about magnetic noon, did not appear. The ionosphere was steady and stratified, and the F-2 layer spread very little. The critical frequency of dayside F-2 layer, f(0)F(2), was larger than that of control day, and the peak of f(0)F(2) appeared 2 hours earlier. The ionospheric drift velocity was less than usual. There were intensive auroral E-s appearing at magnetic noon. All this indicates that the polar ionosphere was extremely quiet and geomagnetic field was much more dipolar on May 11. There were some signatures of auroral substorm before midnight, such as the negative deviation of the geomagnetic H component, accompanied with auroral E-s and weak Pc3 pulsation.

Platinum nanoparticles embledded in layer-by-layer films from SnO2/polyallylamine for ethanol electrooxidation

Self-assembled films from SnO2 and polyallylamine (PAH) were deposited on gold via ionic attraction by the layer-by-layer(LbL) method. The modified electrodes were immersed into a H2PtCl6 solution, a current of 100 mu A was applied, and different electrodeposition times were used. The SnO2/PAH layers served as templates to yield metallic platinum with different particle sizes. The scanning tunnel microscopy images show that the particle size increases as a function of electrodeposition time. The potentiodynamic profile of the electrodes changes as a function of the electrodeposition time in 0.5 mol L-1 H2SO4, at a sweeping rate of 50mVs(-1). Oxygen-like species are formed at less positive potentials for the Pt-SnO2/PAH film in the case of the smallest platinum particles. Electrochemical impedance spectroscopy measurements in acid medium at 0.7 V show that the charge transfer resistance normalized by the exposed platinum area is 750 times greater for platinum electrode (300 k Omega cm(2)) compared with the Pt-SnO2/PAH film with 1 min of electrodeposition (0.4 k Omega cm(2)). According to the Langmuir-Hinshelwood bifunctional mechanism, the high degree of coverage with oxygen-like species on the platinum nanoparticles is responsible for the electrocatalytic activity of the Pt-SnO2/PAH concerning ethanol electrooxidation. With these features, this Pt-SnO2/PAH film may be grown on a proton exchange membrane (PEM) in direct ethanol fuel cells (DEFC). (c) 2008 Elsevier B.V. All rights reserved.

Impedance characteristics of the diamond/carbon fiber electrodes for electrical double-layer capacitor

The electrochemical performance of carbon fibers (CF) and boron-doped diamond electrodes grown on carbon fiber substrate (BDD/CF) was studied. CF substrates were obtained from polyacrylonitrile precursor heat treated at two different temperatures of 1000 and 2000 degrees C to produce the desirable CF carbon graphitization index. This graphitization process influenced the CF conductivity and its chemical surface, also analyzed from X-ray photoelectron spectroscopy measurements. These three-dimensional CF structures allowed a high incorporation of diamond films compared to other carbon substrates such as glass carbon or HOPG. The electrochemical responses, from these four classes of electrodes, were evaluated focusing their application as electrical double-layer capacitors using cyclic voltammetry and impedance measurements. Cyclic voltammetry results revealed that the electrode formed from BDD grown on CF-2000 presented a typical capacitor behavior with the best rectangular shape, compared to those electrodes of CF or BDD/CF-1000. Furthermore, the BDD/CF-2000 electrode presented the lowest impedance, associated to its significant capacitance value of 1940 mu F/cm(2) taking into account the BDD films. This behavior was attributed to the strong dependence between diamond coating texture and the CF graphitization temperature. The largest surface area of BDD/CF-2000 was promoted by its singular film growth mechanism associated to the substrate chemical surface. (c) 2008 Elsevier B.V. All rights reserved.

Surface modification of metals by calcium carbonate thin films on a layer-by-layer polyelectrolyte matrix

A multilayer organic film containing poly(acrylic acid) and chitosan was fabricated on a metallic support by means of the layer-by-layer technique. This film was used as a template for calcium carbonate crystallization and presents two possible binding sites where the nucleation may be initiated, either calcium ions acting as counterions of the polyelectrolyte or those trapped in the template gel network formed by the polyelectrolyte chains. Calcium carbonate formation was carried out by carbon dioxide diffusion, where CO, was generated from ammonium carbonate decomposition. The CaCO3 nanocrystals obtained, formed a dense, homogeneous, and continuous film. Vaterite and calcite CaCO3 crystalline forms were detected. (c) 2007 Elsevier B.V All rights reserved.

Interpretation of negative values of the interaction parameter in the adsorption equation through the effects of surface layer heterogeneity

The problem of the negative values of the interaction parameter in the equation of Frumkin has been analyzed with respect to the adsorption of nonionic molecules on energetically homogeneous surface. For this purpose, the adsorption states of a homologue series of ethoxylated nonionic surfactants on air/water interface have been determined using four different models and literature data (surface tension isotherms). The results obtained with the Frumkin adsorption isotherm imply repulsion between the adsorbed species (corresponding to negative values of the interaction parameter), while the classical lattice theory for energetically homogeneous surface (e.g., water/air) admits attraction alone. It appears that this serious contradiction can be overcome by assuming heterogeneity in the adsorption layer, that is, effects of partial condensation (formation of aggregates) on the surface. Such a phenomenon is suggested in the Fainerman-Lucassen-Reynders-Miller (FLM) 'Aggregation model'. Despite the limitations of the latter model (e.g., monodispersity of the aggregates), we have been able to estimate the sign and the order of magnitude of Frumkin's interaction parameter and the range of the aggregation numbers of the surface species. (C) 2004 Elsevier B.V All rights reserved.