NMR imaging of the diffusion of water at 310 K into semi-IPNs of PEM and Poly(HEMA-co-THFMA)

Magnetic resonance imaging has been used to monitor the diffusion of water at 310 K into a series of semi-IPNs of poly(ethyl methacrylate), PEM, and copolymers of 2-hydroxyethyl methacrylate, HEMA, and tetrahydrofurfuryl methacrylate, THFMA. The diffusion was found to be well described by a Fickian kinetic model in the early stages of the water sorption process, and the diffusion coefficients were found to be slightly smaller than those for the copolymers of HEMA and THFMA, P(HEMA-co-THFMA), containing the same mole fraction of HEMA in the matrix. A second stage sorption process was identified in the later stage of water sorption by the PEM/PTHFMA semi-IPN and for the systems containing a P(HEMA-co-THFMA) component with a mole fraction HEMA of 0.6 or less. This was characterized by the presence of Water near the surface of the cylinders with a longer NMR T-2 relaxation time, which would be characteristic of mobile water, such as water present in large pores or surface fissures. The presence of the drug chlorhexidine in the polymer matrixes at a concentration of 5.625 wt % was found not to modify the properties significantly, but the diffusion coefficients for the water sorption were systematically smaller when the drug was present.

Mass uptake study of the diffusion of water and SBF into poly(2-hydroxyethyl methacrylate-co-tetrahydrofurfuryI methacrylate) containing aspirin or vitamin B-12

The ingress of water and Kokubo simulated body fluid (SBF) into poly (2-hydroxyethyl methacrylate) (PHEMA), and its co-polymers with tetrahydrofurduryl methacrylate (THFMA), loaded with either one of two model drugs, vitamin 1312 or aspirin, was studied by mass uptake over the temperature range 298-318 K. The polymers were studied as cylinders and were loaded with either 5 wt% or 10 wt% of the drugs. From DSC studies it was observed that vitamin B-12 behaved as a physical cross-linker restricting chain segmental mobility, and so had a small anti-plasticisation effect on PHEMA and the co-polymers rich in HEMA, but almost no effect on the T-g of co-polymers rich in THFMA. On the other hand, aspirin exhibited a plasticising effect on PHEMA and the copolymers. All of the polymers were found to absorb water and SBF according to a Fickian diffusion mechanism. The polymers were all found to swell to a greater extent in SBF than in water, which was attributed to the presence of Tris buffer in the SBF. The sorptions of the two penetrants were found to follow Fickian kinetics in all cases and the diffusion coefficients at 310 K for SBF were found to be smaller than those for water, except for the polymers containing aspirin where the diffusion coefficients were higher than for the other systems. For example, for sorption into PHEMA the diffusion coefficient for water was 1.41 X 10(-11) m(2)/s and for SBF was 0.79 x 10-11 m(2)/s, but in the presence of 5 wt% aspirin the corresponding values were 1.27 x 10(-1)1 m(2)/s and 1.25 x 10(-11) m(2)/s, respectively. The corresponding values for PHEMA loaded with 5 wt% B-12 were 1.25 x 10(-11) m(2)/s and 0.74 x 10(-11) m(2)/s, respectively.

Vitamin B-12 release from P(HEMA-co-THFMA) in water and SBF: A model drug release study

A model drug release study on the ingress of water and Kokubo simulated body fluid (SBF) into poly(2-hydroxyethyl methacrylate) (THFMA) and its copolymers with tetrahydrofurfuryl methacrylate (THFMA) loaded with vitamin B-12 was undertaken over the temperature range 298-318 K. The polymers were studied as cylinders and were loaded with either 5 or 10 wt-% of the drug. The drug release from the polymers was found to follow a Fickian diffusion mechanism in the early stages of the drug release, with higher normalized release rates at higher temperatures and higher drug loadings. The normalized release rates were also found to be higher for the SBF solution than for water. The copolymer composition was found to have a significant effect on the rate of release of the drug, with the rate falling rapidly between HEMA mole fractions of 1.0 and 0.8, but for lower mole fractions of HEMA the normalized release rate decreased more slowly. This behaviour followed the trend found for the changes in the equilibrium penetrant contents for the copolymers.

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.

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.

Field observations of instantaneous water slopes and horizontal pressure gradients in the swash-zone

Field observations of instantaneous water surface slopes in the swash zone are presented. For free-surface flows with a hydrostatic pressure distribution the surface slope is equivalent to the horizontal pressure gradient. Observations were made using a novel technique which in its simplest form consists of a horizontal stringline extending seaward from the beach face. Visual observation, still photography or video photography is then sufficient to determine the surface slope where the free-surface cuts the line or between reference points in the image. The method resolves the mean surface gradient over a cross-shore distance of 5 m or more to within +/- 0.001, or 1/20th -1/100th of typical beach gradients. In addition, at selected points and at any instant in time during the swash cycle, the water surface slope can be determined exactly to be dipping either seaward or landward. Close to the location of bore collapse landward dipping water surface slopes of order 0.05-0.1 occur over a very small region (order 0.5 m) at the blunt or convex leading edge of the swash. In the middle and upper swash the water surface slope at this leading edge is usually very close to horizontal or slightly seaward. Behind the leading edge, the water surface slope was observed to be very close to horizontal or dipping seaward at all times throughout the swash uprush. During the backwash the water surface slope was observed to be always dipping seaward, approaching the beach slope, and remained seaward until a new uprush edge or incident bore passed any particular cross-shore location of interest. The observations strongly Suggest that the swash boundary layer is subject to an adverse pressure gradient during uprush and a favourable pressure gradient during the backwash. Furthermore, assuming Euler's equations are a good approximation in the swash, the observations also show that the total fluid acceleration is negative (offshore) for almost the whole of the uprush and for the entire backwash. The observations are contrary to recent work suggesting significant shoreward directed accelerations and pressure gradients occur in the swash (i.e., delta u/delta t > 0 similar to delta p/delta x < 0), but consistent with analytical and numerical solutions for swash uprush and backwash. The results have important implications for sediment transport modelling in the swash zone.

Characterisation of sea-water intrusion in the Pioneer Valley, Australia using hydrochemistry and three-dimensional numerical modelling

Sea-water intrusion is actively contaminating fresh groundwater reserves in the coastal aquifers of the Pioneer Valley,north-eastern Australia. A three-dimensional sea-water intrusion model has been developed using the MODHMS code to explore regional-scale processes and to aid assessment of management strategies for the system. A sea-water intrusion potential map, produced through analyses of the hydrochemistry, hydrology and hydrogeology, offsets model limitations by providing an alternative appraisal of susceptibility. Sea-water intrusion in the Pioneer Valley is not in equilibrium, and a potential exists for further landward shifts in the extent of saline groundwater. The model required consideration of tidal over-height (the additional hydraulic head at the coast produced by the action of tides), with over-height values in the range 0.5-0.9 m giving improved water-table predictions. The effect of the initial water-table condition dominated the sensitivity of the model to changes in the coastal hydraulic boundary condition. Several salination processes are probably occurring in the Pioneer Valley, rather than just simple landward sea-water advancement from modern sources of marine salts. The method of vertical discretisation (i.e. model-layer subdivision) was shown to introduce some errors in the prediction of watertable behaviour.

Electrolyte transport in the mammalian colon: mechanisms and implications for disease Kunzelmann and Marcus Mall

Electrolyte Transport in the Mammalian Colon: Mechanisms and Implications for Disease. Physiol. Rev. 82: 245-289, 2002.The colonic epithelium has both absorptive and secretory functions. The transport is characterized by a net absorption of NaCl, short-chain fatty acids (SCFA), and water, allowing extrusion of a feces with very little water and salt content. In addition, the epithelium does secret mucus, bicarbonate, and KCl. Polarized distribution of transport proteins in both luminal and basolateral membranes enables efficient salt transport in both directions, probably even within an individual cell. Meanwhile, most of the participating transport proteins have been identified, and their function has been studied in detail. Absorption of NaCl is a rather steady process that is controlled by steroid hormones regulating the expression of epithelial Na+ channels (ENaC), the Na+-K+-ATPase, and additional modulating factors such as the serum- and glucocorticoid-regulated kinase SGK. Acute regulation of absorption may occur by a Na+ feedback mechanism and the cystic fibrosis transmembrane conductance regulator (CFTR). Cl- secretion in the adult colon relies on luminal CFTR, which is a cAMP-regulated Cl- channel and a regulator of other transport proteins. As a consequence, mutations in CFTR result in both impaired Cl- secretion and enhanced Na+ absorption in the colon of cystic fibrosis (CF) patients. Ca2+- and cAMP-activated basolateral K+ channels support both secretion and absorption of electrolytes and work in concert with additional regulatory proteins, which determine their functional and pharmacological profile. Knowledge of the mechanisms of electrolyte transport in the colon enables the development of new strategies for the treatment of CF and secretory diarrhea. It will also lead to a better understanding of the pathophysiological events during inflammatory bowel disease and development of colonic carcinoma.