A pore-size-dependent equation of state for multilayer adsorption in cylindrical mesopores

The chemical potential of adsorbed film inside cylindrical mesopores is dependent on the attractive interactions between the adsorbed molecules and adsorbent, the curvature of gas/adsorbed phase interface, and surface tension. A state equation of the adsorbed film is proposed to take into account the above factors. Nitrogen adsorption on model adsorbents, MCM-41, which exhibit uniform cylindrical channels, are used to verify the theoretical analysis. The proposed theory is capable of describing the important features of adsorption processes in cylindrical mesopores. According to this theory, at a given relative pressure, the smaller the pore radius is, the thicker the adsorbed film will be. The thickening of adsorbed films in the pores as the vapor pressure increases inevitably causes an increase in the interface curvature, which consequently leads to capillary condensation. Besides, this study confirmed that the interface tension depends substantially on the interface curvature in small mesopores. A quantitative relationship between the condensation pressure and the pore radius can be derived from the state equation and used to predict the pore radius from a condensation pressure, or vice versa.

Carbon structure and porosity of carbonaceous adsorbents in relation to their adsorption properties

A number of carbonaceous adsorbents were prepared by carbonisation at 600 degrees C following acidic oxidation under various conditions. Effects of the chemical nature of the precursor, such as the ratio of aromatic to aliphatic carbons and oxygen content, on the chemical and structural characteristics of the resultant chars were investigated using C-13 NMR and Raman spectroscopy, respectively. The C-13 NMR spectral parameters of the coal samples show that as the severity of oxidation conditions increased, the ratio of aromatic to aliphatic carbons increased. Furthermore, it was also found that the amount of disorganised carbon affects both the pore structure and the adsorption properties of carbonaceous adsorbents. It is demonstrated that higher amount of the disorganised carbon indicates smaller micropore size. (C) 1999 Elsevier Science Ltd. All rights reserved.

Modeling of hepatic elimination and organ distribution kinetics with the extended convection-dispersion model

The conventional convection-dispersion (also called axial dispersion) model is widely used to interrelate hepatic availability (F) and clearance (Cl) with the morphology and physiology of the liver and to predict effects such as changes in liver blood flow on F and Cl. An extended form of the convection-dispersion model has been developed to adequately describe the outflow concentration-time profiles for vascular markers at both short and long times after bolus injections into perfused livers. The model, based on flux concentration and a convolution of catheters and large vessels, assumes that solute elimination in hepatocytes follows either fast distribution into or radial diffusion in hepatocytes. The model includes a secondary vascular compartment, postulated to be interconnecting sinusoids. Analysis of the mean hepatic transit time (MTT) and normalized variance (CV2) of solutes with extraction showed that the discrepancy between the predictions of MTT and CV2 for the extended and conventional models are essentially identical irrespective of the magnitude of rate constants representing permeability, volume, and clearance parameters, providing that there is significant hepatic extraction. In conclusion, the application of a newly developed extended convection-dispersion model has shown that the unweighted conventional convection-dispersion model can be used to describe the disposition of extracted solutes and, in particular, to estimate hepatic availability and clearance in booth experimental and clinical situations.

Intraspecific co-variation between egg and body size affects fertilisation kinetics of free-spawning marine invertebrates

Fertilisation of eggs of free-spawning marine invertebrates depends on factors affecting sperm concentration in the field and also on gamete characteristics such as egg size. In the free-spawning intertidal ascidian Pyura stolonifera mean egg size increased with maternal size in 2 separate populations. The largest ascidian produced eggs that were, on average, 50% greater in volume than the eggs produced by the smallest individual studied. There was no evidence to suggest that egg density varied with adult size and egg dry organic weight increased with maternal size. The fertilisation kinetics of this species were strongly affected by the variation in egg size, with the eggs of large individuals requiring much less concentrated sperm to achieve maximal levels of fertilisation success than the eggs of small individuals. We suggest that variation in egg size between individuals of different sizes and ages may be an important factor in determining fertilisation success for ascidians of this species.

A model for adsorption of condensable vapors on nonporous materials

A new isotherm is proposed here for adsorption of condensable vapors and gases on nonporous materials having type II isotherms according to the Brunauer-Deming-Deming-Teller (BDDH) classification. The isotherm combines the recent molecular-continuum model in the multilayer region, with other widely used models for sub-monolayer coverage, some of which satisfy the requirement of a Henry's law asymptote. The model is successfully tested using isotherm data for nitrogen adsorption on nonporous silica, carbon and alumina, as well as benzene and hexane adsorption on nonporous carbon. Based on the data fits, out of several different alternative choices of model for the monolayer region, the Freundlich and the Unilan models are found to be the most successful when combined with the multilayer model to predict the whole isotherm. The hybrid model is consequently applicable over a wide pressure range. (C) 2000 Elsevier Science B.V. All rights reserved.

Kinetics of propranolol uptake in muscle, skin, and fat of the isolated perfused rat hindlimb

The tissue distribution kinetics of a highly bound solute, propranolol, was investigated in a heterogeneous organ, the isolated perfused limb, using the impulse-response technique and destructive sampling. The propranolol concentration in muscle, skin, and fat as well as in outflow perfusate was measured up to 30 min after injection. The resulting data were analysed assuming (1) vascular, muscle, skin and fat compartments as well mixed (compartmental model) and (2) using a distributed-in-space model which accounts for the noninstantaneous intravascular mixing and tissue distribution processes but consists only of a vascular and extravascular phase (two-phase model). The compartmental model adequately described propranolol concentration-time data in the three tissue compartments and the outflow concentration-time curve (except of the early mixing phase). In contrast, the two-phase model better described the outflow concentration-time curve but is limited in accounting only for the distribution kinetics in the dominant tissue, the muscle. The two-phase model well described the time course of propranolol concentration in muscle tissue, with parameter estimates similar to those obtained with the compartmental model. The results suggest, first that the uptake kinetics of propranolol into skin and fat cannot be analysed on the basis of outflow data alone and, second that the assumption of well-mixed compartments is a valid approximation from a practical point of view las, e.g., in physiological based pharmacokinetic modelling). The steady-state distribution volumes of skin and fat were only 16 and 4%, respectively, of that of muscle tissue (16.7 ml), with higher partition coefficient in fat (6.36) than in skin (2.64) and muscle (2.79. (C) 2000 Elsevier Science B.V. All rights reserved.

Characterization of pore size distributions of mesoporous materials from adsorption isotherms

In this article, a new hybrid model for estimating the pore size distribution of micro- and mesoporous materials is developed, and tested with the adsorption data of nitrogen, oxygen, and argon on ordered mesoporous materials reported in the literature. For the micropore region, the model uses the Dubinin-Rudushkevich (DR) isotherm with the Chen-Yang modification. A recent isotherm model of the authors for nonporous materials, which uses a continuum-mechanical model for the multilayer region and the Unilan model for the submonolayer region, has been extended for adsorption in mesopores. The experimental data is inverted using regularization to obtain the pore size distribution. The present model was found to be successful in predicting the pore size distribution of pure as well as binary physical mixtures of MCM-41 synthesized with different templates, with results in agreement with those from the XRD method and nonlocal density functional theory. It was found that various other recent methods, as well as the classical Broekhoff and de Beer method, underpredict the pore diameter of MCM-41. The present model has been successfully applied to MCM-48, SBA's, CMK, KIT, HMS, FSM, MTS, mesoporous fly ash, and a large number of other regular mesoporous materials.

Adsorption of flavour esters on granular activated carbon

This article reports on the liquid phase adsorption of flavour esters onto granular activated carbon. Ethyl propionate, ethyl butyrate, and ethyl isovalerate were used as adsorbates, and Filtrasorb 400 activated carbon was chosen as the adsorbent. Sips, Toth, Unilan, and Dubinin-Radushkevich isotherm equations which are generally used for heterogeneous adsorbents were used to fit the data. Although satisfactory in fitting the data, inconsistency in parameter values indicated these models to be inadequate. On the other hand the Dubinin-Radushkevich model gave more consistent and meaningful parameter values and adsorption capacities. By employing the Dubinin-Radushkevich equation, the limiting volume of the adsorbed space, which equals the accessible micropore volume, was determined, and found to correlate with the value from carbon dioxide adsorption.

Commentary: Using the convection-dispersion model and transit time density functions in the analysis of organ distribution kinetics

The convection-dispersion model and its extended form have been used to describe solute disposition in organs and to predict hepatic availabilities. A range of empirical transit-time density functions has also been used for a similar purpose. The use of the dispersion model with mixed boundary conditions and transit-time density functions has been queried recently by Hisaka and Sugiyanaa in this journal. We suggest that, consistent with soil science and chemical engineering literature, the mixed boundary conditions are appropriate providing concentrations are defined in terms of flux to ensure continuity at the boundaries and mass balance. It is suggested that the use of the inverse Gaussian or other functions as empirical transit-time densities is independent of any boundary condition consideration. The mixed boundary condition solutions of the convection-dispersion model are the easiest to use when linear kinetics applies. In contrast, the closed conditions are easier to apply in a numerical analysis of nonlinear disposition of solutes in organs. We therefore argue that the use of hepatic elimination models should be based on pragmatic considerations, giving emphasis to using the simplest or easiest solution that will give a sufficiently accurate prediction of hepatic pharmacokinetics for a particular application. (C) 2000 Wiley-Liss Inc. and the American Pharmaceutical Association J Pharm Sci 89:1579-1586, 2000.

Adsorption hysteresis and criticality in regular mesoporous materials

In the present work, various theories predicting the critical diameter for the absence of capillary condensation and hysteresis are applied to experimental adsorption isotherms of vapors on regular mesoporous materials. Among the various theories studied, the tensile strength approximation proposed by the authors was found to be the most successful. Reversibility of nitrogen adsorption at 77.4 K was studied on pure MCM-41 of various pore sizes, as well as mixtures of pure MCM-41 samples in a 1:1 ratio. The results of PSD and hysteresis on MCM-41 mixtures are close to that expected from studies of the pure materials. The estimates of hysteresis critical temperature and diameter of MCM-41, HMS, FSM and KIT materials are also provided.

Altered kinetics and benzodiazepine sensitivity of a GABA(A) receptor subunit mutation [gamma(2)(R43Q)] found in human epilepsy

The gamma-aminobutyric acid type A (GABA(A)) receptor mediates fast inhibitory synaptic transmission in the CNS. Dysfunction of the GABA(A) receptor would be expected to cause neuronal hyperexcitability, a phenomenon linked with epileptogenesis. We have investigated the functional consequences of an arginine-to-glutamine mutation at position 43 within the GABA(A) gamma(2)-subunit found in a family with childhood absence epilepsy and febrile seizures. Rapid-application experiments performed on receptors expressed in HEK-293 cells demonstrated that the mutation slows GABA(A) receptor deactivation and increases the rate of desensitization, resulting in an accumulation of desensitized receptors during repeated, short applications. In Xenopus laevis oocytes, two-electrode voltage-clamp analysis of steady-state currents obtained from alpha(1)beta(2)gamma(2) or alpha(1)beta(2)gamma(2)(R43Q) receptors did not reveal any differences in GABA sensitivity. However, differences in the benzodiazepine pharmacology of mutant receptors were apparent. Mutant receptors expressed in oocytes displayed reduced sensitivity to diazepam and flunitrazepam but not the imiclazopyricline zolpidem. These results provide evidence of impaired GABA(A) receptor function that could decrease the efficacy of transmission at inhibitory synapses, possibly generating a hyperexcitable neuronal state in thalamocortical networks of epileptic patients possessing the mutant subunit.

Kinetics of photoacclimation in corals

Traditional models describing the relationship between photosynthesis (P) and irradiance (I) do not account for photoacclimation to short-term variation in irradiance. Here we develop and test a model that predicts the rate of photosynthesis under fluctuating irradiances at the scale of days to weeks. Using oxygen respirometry, we measured the rates of change in the P-I model parameters P-max (maximum rate of gross photosynthesis) and I-k (sub-saturation irradiance) of the photo-symbiotic coral Turbinaria mesenterina (Lamarck) following large and small increases and decreases in growth irradiance. We analyse the behaviour of the dynamic P-I model in turbid-water conditions using a dataset of 3-month continuous irradiance as the input variable. In response to upward or downward changes in experimental growth irradiance, I-k values decreased or increased exponentially, reaching new and stable levels within 5-10 days. I-k responded 4 times stronger than P-max to changes in growth irradiance. The kinetics of I-k did not show hysteresis, and changed in similar ways when irradiance was increased or decreased in small or large amounts. This suggests that mechanisms associated with photo-protection during increases in irradiance, and the maximisation of photosynthetic efficiency during decreases in irradiance, are equally potent. On the scale of months, the dynamic P-I model did not predict higher rates of photosynthesis than the static P-I model, but buffered the variation in photosynthesis during periods of reduced irradiance. Fourier analysis indicated that the kinetics of I-k closely matches the main periodicities in daily irradiance (1-2 weeks). The recorded kinetics of photoacclimation in the Turbinaria-zooxanthella symbiosis is comparable to that of free-living phytoplankton and faster than that of higher plants.

Characterization of pore wall heterogeneity in nanoporous carbons using adsorption: the slit pore model revisited

In this paper, we propose a new nonlocal density functional theory characterization procedure, the finite wall thickness model, for nanoporous carbons, whereby heterogeneity of pore size and pore walls in the carbon is probed simultaneously. We determine the pore size distributions and pore wall thickness distributions of several commercial activated carbons and coal chars, with good correspondence with X-ray diffraction. It is shown that the conventional infinite wall thickness approach overestimates the pore size slightly. Pore-pore correlation has been shown to have a negligible effect on prediction of pore size and pore wall thickness distributions for small molecules such as argon used in characterization. By utilizing the structural parameters (pore size and pore wall thickness distribution) in the generalized adsorption isotherm (GAI) we are able to predict adsorption uptake of supercritical gases in BPL and Norit RI Extra carbons, in excellent agreement with experimental adsorption uptake data up to 60 MPa. The method offers a useful technique for probing features of the solid skeleton, hitherto studied by crystallographic methods.

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.

Adsorption of cholate anions on layered double hydroxides: effects of temperature, ionic strength and pH

Layered Double Hydroxides are a class of materials that can be described as positively charged planar layers consisting of divalent and trivalent cations in the center of edge-sharing octahedra. The positive charge in the LDH layers must be compensated by anion intercalation. These materials have applications that include adsorption and/or sorption of anionic species. Cholic acid is one of the main acids produced by the liver. It promotes transport of lipids through aqueous systems. This work reports on the adsorption of Cholic acid anions in MgAl-CO3-LDH taking ionic strength, pH, and temperature effects into account. The adsorbent was characterized by different techniques. Cholate anion adsorption was performed at two different temperatures (298 and 323 K), two different ionic strength conditions (0.0 and 0.1 M of NaCl), and two different pH values (7.0 and 10.0). The results show that the sorption of Cholate anions in calcined LDH can remove a considerable amount of these anions from the medium. Cholate anion adsorption in the LDH with no calcining also occurs, but at a lower amount.