New insights into the interactions of serum proteins with bis(maltolato)oxovanadium(IV): Transport and biotransformation of insulin-enhancing vanadium pharmaceuticals

Significant new insights into the interactions of the potent insulin-enhancing compound bis(maltolato)oxovanadium(IV) (BMOV) with the serum proteins, apo-transferrin and albumin, are presented. Identical reaction products are observed by electron paramagnetic resonance (EPR) with either BMOV or vanadyl sulfate (VOSO4) in solutions of human serum apo-transferrin. Further detailed study rules out the presence of a ternary ligand-vanadyl-transferrin complex proposed previously. By contrast, differences in reaction products are observed for the interactions of BMOV and VOSO4 with human serum albumin (HSA), wherein adduct formation between albumin and BMOV is detected. In BMOV-albumin solutions, vanadyl ions are bound in a unique manner not observed in comparable solutions Of VOSO4 and albumin. Presentation of chelated vanadyl ions precludes binding at the numerous nonspecific sites and produces a unique EPR spectrum which is assigned to a BMOV-HSA adduct. The adduct species cannot be produced, however, from a solution Of VOSO4 and HSA titrated with maltol. Addition of maltol to a VOSO4-HSA solution instead results in formation of a different end product which has been assigned as a ternary complex, VO(ma)(HSA). Furthermore, analysis of solution equilibria using a model system of BMOV with 1-methylimidazole (formation constant log K = 4.5(1), by difference electronic absorption spectroscopy) lends support to an adduct binding mode (VO(ma)(2)-HSA) proposed herein for BMOV and HSA. This detailed report of an in vitro reactivity difference between VOSO4 and BMOV may have bearing on the form of active vanadium metabolites delivered to target tissues. Albumin binding of vanadium chelates is seen to have a potentially dramatic effect on pharmacokinetics, transport, and efficacy of these antidiabetic chelates.

Solid transport in a pyrolysis pilot-scale rotary kiln: Preliminary results?stationary and dynamic results

Experiments for the investigation of the flow of granular solids in a pyrolysis pilot-scale rotary kiln are presented. These experiments consisted first in measuring the volumetric filling ratio (steady-state experiences) for several operating conditions and second in recording the exit flow rates after a positive or negative step in one of the operating parameters (dynamic experiences). A dynamical model computing the evolution of the flow rate of granular solids through the kiln has been developed based on Saeman model [Chem. Eng. Prog. 47 (1951) 508]. The simulations are compared with experimental results; the model gives good results for the rolling mode, but for the slipping mode too. (C) 2004 Elsevier B.V. All rights reserved.

Momentum transfer effects in the transport of adsorbate at a nano-patterned surface

Adsorbate molecules scattered in the repulsive field of a surface feature in the form of a semi-cylindrical stripe may be considered as a simple model for a nano-patterned surface. The extent of scattering was conveniently expressed as the tangential momentum accommodation coefficient. An analytical result was obtained using a simple local specular reflection hypothesis in contrast to the more complicated situation of an array of atoms discussed elsewhere, in which screening and secondary reflection may occur (Nicholson and Bhatia 2005). It was also demonstrated that a simple 2D representation leads to the same result for the tangential momentum accommodation coefficient.

Sheet flow sediment transport under waves with acceleration skewness and boundary layer streaming

The effect of acceleration skewness on sheet flow sediment transport rates (q) over bar (s) is analysed using new data which have acceleration skewness and superimposed currents but no boundary layer streaming. Sediment mobilizing forces due to drag and to acceleration (similar to pressure gradients) are weighted by cosine and sine, respectively, of the angle phi(.)(tau)phi(tau) = 0 thus corresponds to drag dominated sediment transport, (q) over bar (s)similar to vertical bar u(infinity)vertical bar u(infinity), while phi(tau) = 90 degrees corresponds to total domination by the pressure gradients, (q) over bar similar to du(infinity)/dt. Using the optimal angle, phi = 51 degrees based on that data, good agreement is subsequently found with data that have strong influence from boundary layer streaming. Good agreement is also maintained with the large body of U-tube data simulating sine waves with superimposed currents and second-order Stokes waves, all of which have zero acceleration skewness. The recommended model can be applied to irregular waves with arbitrary shape as long as the assumption negligible time lag between forcing and sediment transport rate is valid. With respect to irregular waves, the model is much easier to apply than the competing wave-by-wave models. Issues for further model developments are identified through a comprehensive data review.

Estimation of water retention curve from mercury intrusion porosimetry and van Genuchten model

The water retention curve (WRC) is a hydraulic characteristic of concrete required for advanced modeling of water (and thus solute) transport in variably saturated, heterogeneous concrete. Unfortunately, determination by a direct experimental method (for example, measuring equilibrium moisture levels of large samples stored in constant humidity cells) is a lengthy process, taking over 2 years for large samples. A surrogate approach is presented in which the WRC is conveniently estimated from mercury intrusion porosimetry (MIP) and validated by water sorption isotherms: The well-known Barrett, Joyner and Halenda (BJH) method of estimating the pore size distribution (PSD) from the water sorption isotherm is shown to complement the PSD derived from conventional MIP. This provides a basis for predicting the complete WRC from MIP data alone. The van Genuchten equation is used to model the combined water sorption and MIP results. It is a convenient tool for describing water retention characteristics over the full moisture content range. The van Genuchten parameter estimation based solely on MIP is shown to give a satisfactory approximation to the WRC, with a simple restriction on one. of the parameters.

Selective transport of attached particles across the pulp-froth interface

A technique for determining the recovery of attached particles across the froth phase in flotation that relies on measuring the rate at which bubble-particle aggregates enter the froth is used to investigate the selectivity of attached particles across the froth phase. Combining these measurements with those of other techniques for determining the froth recovery of attached particles provides an insight into the different sub-processes of particle rejection in the froth phase. The results of experiments conducted in a 3 m(3) Outokumpu tank cell show that the detachment of particles from aggregates in the froth phase occurs largely at the pulp-froth interface. In particular it is shown that the pulp-froth interface selectively detaches particles from aggregates according to their physical attributes. (C) 2005 Elsevier Ltd. All rights reserved.

Prediction of slurry transport in SAG mills using SPH fluid flow in a dynamic DEM based porous media

DEM modelling of the motion of coarse fractions of the charge inside SAG mills has now been well established for more than a decade. In these models the effect of slurry has broadly been ignored due to its complexity. Smoothed particle hydrodynamics (SPH) provides a particle based method for modelling complex free surface fluid flows and is well suited to modelling fluid flow in mills. Previous modelling has demonstrated the powerful ability of SPH to capture dynamic fluid flow effects such as lifters crashing into slurry pools, fluid draining from lifters, flow through grates and pulp lifter discharge. However, all these examples were limited by the ability to model only the slurry in the mill without the charge. In this paper, we represent the charge as a dynamic porous media through which the SPH fluid is then able to flow. The porous media properties (specifically the spatial distribution of porosity and velocity) are predicted by time averaging the mill charge predicted using a large scale DEM model. This allows prediction of transient and steady state slurry distributions in the mill and allows its variation with operating parameters, slurry viscosity and slurry volume, to be explored. (C) 2006 Published by Elsevier Ltd.

Artificial pumping errors in the Kool-Parker scaling model of soil moisture hysteresis

Hysteresis models that eliminate the artificial pumping errors associated with the Kool-Parker (KP) soil moisture hysteresis model, such as the Parker-Lenhard (PL) method, can be computationally demanding in unsaturated transport models since they need to retain the wetting-drying history of the system. The pumping errors in these models need to be eliminated for correct simulation of cyclical systems (e.g. transport above a tidally forced watertable, infiltration and redistribution under periodic irrigation) if the soils exhibit significant hysteresis. A modification is made here to the PL method that allows it to be more readily applied to numerical models by eliminating the need to store a large number of soil moisture reversal points. The modified-PL method largely eliminates any artificial pumping error and so essentially retains the accuracy of the original PL approach. The modified-PL method is implemented in HYDRUS-1D (version 2.0), which is then used to simulate cyclic capillary fringe dynamics to show the influence of removing artificial pumping errors and to demonstrate the ease of implementation. Artificial pumping errors are shown to be significant for the soils and system characteristics used here in numerical experiments of transport above a fluctuating watertable. (c) 2005 Elsevier B.V. All rights reserved.

Mechanisms influencing levitation and the scaling laws in nanopores: Oscillator model theory

We provide here a detailed theoretical explanation of the floating molecule or levitation effect, for molecules diffusing through nanopores, using the oscillator model theory (Phys. Rev. Lett. 2003, 91, 126102) recently developed in this laboratory. It is shown that on reduction of pore size the effect occurs due to decrease in frequency of wall collision of diffusing particles at a critical pore size. This effect is, however, absent at high temperatures where the ratio of kinetic energy to the solid-fluid interaction strength is sufficiently large. It is shown that the transport diffusivities scale with this ratio. Scaling of transport diffusivities with respect to mass is also observed, even in the presence of interactions.

Structure of saccharose-based carbon and transport of confined fluids: hybrid reverse Monte Carlo reconstruction and simulation studies

We present results of the reconstruction of a saccharose-based activated carbon (CS1000a) using hybrid reverse Monte Carlo (HRMC) simulation, recently proposed by Opletal et al. [1]. Interaction between carbon atoms in the simulation is modeled by an environment dependent interaction potential (EDIP) [2,3]. The reconstructed structure shows predominance of sp(2) over sp bonding, while a significant proportion of sp(3) hybrid bonding is also observed. We also calculated a ring distribution and geometrical pore size distribution of the model developed. The latter is compared with that obtained from argon adsorption at 87 K using our recently proposed characterization procedure [4], the finite wall thickness (FWT) model. Further, we determine self-diffusivities of argon and nitrogen in the constructed carbon as functions of loading. It is found that while there is a maximum in the diffusivity with respect to loading, as previously observed by Pikunic et al. [5], diffusivities in the present work are 10 times larger than those obtained in the prior work, consistent with the larger pore size as well as higher porosity of the activated saccharose carbon studied here.

AUSLEM (AUStralian Land Erodibility Model): A tool for identifying wind erosion hazard in Australia

We present AUSLEM (AUStralian Land Erodibility Model), a land erodibility modelling system that utilizes a rule-set of surficial and climatic thresholds applied through a Geographic Information System (GIs) modelling framework to predict landscape susceptibility to wind erosion. AUSLEM is distinctive in that it quantitatively assesses landscape susceptibility to wind erosion at a 5 x 5 km. spatial resolution on a monthly time-step across Australia. The system was implemented for representative wet (1984), dry (1994), and average rainfall (1997) years with corresponding low, high and moderate dust storm day frequencies. Results demonstrate that AUSLEM can identify landscape erodibility, and provide an interpretation of the physical nature and distribution of erodible landscapes in Australia. Further, results offer an assessment of the dynamic tendencies of erodibility in space and time in response to the El Nino Southern Oscillation (ENSO) and seasonal synoptic scale climate variability. A comparative analysis of AUSLEM output with independent national and international wind erosion, atmospheric aerosol and dust event records indicates a high level of model competency. (c) 2006 Elsevier B.V. All rights reserved.

Stochastic modelling and simulations for solute transport in porous media

A stochastic model for solute transport in aquifers is studied based on the concepts of stochastic velocity and stochastic diffusivity. By applying finite difference techniques to the spatial variables of the stochastic governing equation, a system of stiff stochastic ordinary differential equations is obtained. Both the semi-implicit Euler method and the balanced implicit method are used for solving this stochastic system. Based on the Karhunen-Loeve expansion, stochastic processes in time and space are calculated by means of a spatial correlation matrix. Four types of spatial correlation matrices are presented based on the hydraulic properties of physical parameters. Simulations with two types of correlation matrices are presented.

Simulation of air traffic controllers' behaviour using the operator choice model

The Operator Choice Model (OCM) was developed to model the behaviour of operators attending to complex tasks involving interdependent concurrent activities, such as in Air Traffic Control (ATC). The purpose of the OCM is to provide a flexible framework for modelling and simulation that can be used for quantitative analyses in human reliability assessment, comparison between human computer interaction (HCI) designs, and analysis of operator workload. The OCM virtual operator is essentially a cycle of four processes: Scan Classify Decide Action Perform Action. Once a cycle is complete, the operator will return to the Scan process. It is also possible to truncate a cycle and return to Scan after each of the processes. These processes are described using Continuous Time Probabilistic Automata (CTPA). The details of the probability and timing models are specific to the domain of application, and need to be specified using domain experts. We are building an application of the OCM for use in ATC. In order to develop a realistic model we are calibrating the probability and timing models that comprise each process using experimental data from a series of experiments conducted with student subjects. These experiments have identified the factors that influence perception and decision making in simplified conflict detection and resolution tasks. This paper presents an application of the OCM approach to a simple ATC conflict detection experiment. The aim is to calibrate the OCM so that its behaviour resembles that of the experimental subjects when it is challenged with the same task. Its behaviour should also interpolate when challenged with scenarios similar to those used to calibrate it. The approach illustrated here uses logistic regression to model the classifications made by the subjects. This model is fitted to the calibration data, and provides an extrapolation to classifications in scenarios outside of the calibration data. A simple strategy is used to calibrate the timing component of the model, and the results for reaction times are compared between the OCM and the student subjects. While this approach to timing does not capture the full complexity of the reaction time distribution seen in the data from the student subjects, the mean and the tail of the distributions are similar.