Preparation, characterization, and catalytic properties of clay-based nickel catalysts for methane reforming

Naturally occurring clays and pillared clays are used as supports of nickel catalysts for the methane reforming reaction with carbon dioxide to synthesis gas. The structural and textural characteristics of the supports and catalysts are systematically examined by N-2 adsorption/desorption and X-ray diffraction (XRD) techniques. It is found that the pore structures and surface properties of supports greatly affect the catalytic activities of the catalysts prepared. The catalysts supported on the mesoporous clays or pillared clays are obviously superior to those on microporous supports because the mesoporous supports are highly thermal stable compared to the microporous ones. It is found that introducing lanthanum to the supports can improve the catalyst basicity and thus enhance the catalytic activities of these catalysts. Deactivation of catalysts prepared and factors influencing their stability are also discussed. (C) 1998 Academic Press.

Relationships between blood pressure and heart rate in the saltwater crocodile Crocodylus porosus

The cardiac limb of the baroreflex loop was studied in the saltwater crocodile Crocodylus porosus, The classical pharmacological methodology using phenylephrine and sodium nitroprusside was used to trigger blood pressure changes, and the resulting alterations in heart rate were analysed quantitatively using a logistic function. Interindividual differences in resting heart rates and blood pressures were observed, but all seven animals displayed clear baroreflex responses. Atropine and sotalol greatly attenuated the response. A maximal baroreflex gain of 7.2 beats min(-1) kPa(-1) was found at a mean aortic pressure of 6.1 kPa, indicating the active role of the baroreflex in a wide pressure range encompassing hypotensive and hypertensive states. At the lowest mean aortic pressures (5.0 kPa), the synergistic role of the pulmonary-to-systemic shunt in buffering the blood pressure drop also contributes to blood pressure regulation, Pulse pressure showed a better correlation,vith heart rate and also a higher gain than mean aortic, systolic or diastolic pressures, and this is taken as an indicator of the existence of a differential control element working simultaneously with a linear proportional element.

Analysis of pore-fluid pressure gradient and effective vertical-stress gradient distribution in layered hydrodynamic systems

A theoretical analysis is carried out to investigate the pore-fluid pressure gradient and effective vertical-stress gradient distribution in fluid saturated porous rock masses in layered hydrodynamic systems. Three important concepts, namely the critical porosity of a porous medium, the intrinsic Fore-fluid pressure and the intrinsic effective vertical stress of the solid matrix, are presented and discussed. Using some basic scientific principles, we derive analytical solutions and explore the conditions under which either the intrinsic pore-fluid pressure gradient or the intrinsic effective vertical-stress gradient can be maintained at the value of the lithostatic pressure gradient. Even though the intrinsic pore-fluid pressure gradient can be maintained at the value of the lithostatic pressure gradient in a single layer, it is impossible to maintain it at this value in all layers in a layered hydrodynamic system, unless all layers have the same permeability and porosity simultaneously. However, the intrinsic effective vertical-stress gradient of the solid matrix can be maintained at a value close to the lithostatic pressure gradient in all layers in any layered hydrodynamic system within the scope of this study.

Thermal diffusion in molecular dynamics simulations of thin film diamond deposition

Molecular dynamics simulations of carbon atom depositions are used to investigate energy diffusion from the impact zone. A modified Stillinger-Weber potential models the carbon interactions for both sp2 and sp3 bonding. Simulations were performed on 50 eV carbon atom depositions onto the (111) surface of a 3.8 x 3.4 x 1.0 nm diamond slab containing 2816 atoms in 11 layers of 256 atoms each. The bottom layer was thermostated to 300 K. At every 100th simulation time step (27 fs), the average local kinetic energy, and hence local temperature, is calculated. To do this the substrate is divided into a set of 15 concentric hemispherical zones, each of thickness one atomic diameter (0.14 nm) and centered on the impact point. A 50-eV incident atom heats the local impact zone above 10 000 K. After the initial large transient (200 fs) the impact zone has cooled below 3000 K, then near 1000 K by 1 ps. Thereafter the temperature profile decays approximately as described by diffusion theory, perturbed by atomic scale fluctuations. A continuum model of classical energy transfer is provided by the traditional thermal diffusion equation. The results show that continuum diffusion theory describes well energy diffusion in low energy atomic deposition processes, at distance and time scales larger than 1.5 nm and 1-2 ps, beyond which the energy decays essentially exponentially. (C) 1998 Published by Elsevier Science S.A. All rights reserved.

Thermal and mechanical properties of radiation crosslinked poly(tetrafluoroethylene-co-perfluoromethyl vinyl ether)

The gamma-radiolysis of poly(tetrafluoroethylene-co-perfluoromethyl vinyl ether) (TFE/PMVE) was investigated using chemical and mechanical analyses. The polymer was found to form an insoluble network with a dose of gelation of 15.8 kGy. Tensile and glass transition temperature measurements indicated the predominance of crosslinking, with optimal elastomeric properties reached in the dose range of 120 to 200 kGy. Photoacoustic FTIR spectroscopy CPAS) showed the formation of new carboxylic acid end groups on irradiation. These new end groups were shown to decrease the thermal oxidative stability of the crosslinked network as determined by thermal gravimetric analysis. Electron spin resonance (ESR) studies of the polymer at 77 K indicated the presence of radical precursors. A G-value of 1.1 was determined for radical production at 77 K. Comparison of radical concentrations for a copolymer with a different mole ratio of PMVE, indicated that the PMVE units contribute to scission reactions. (C) 1998 Elsevier Science Ltd. All rights reserved.

X-ray properties of the Parkes sample of flat-spectrum radio sources: dust in radio-loud quasars?

We investigate the X-ray properties of the Parkes sample of Bat-spectrum radio sources using data from the ROSAT All-Sky Survey and archival pointed PSPC observations. In total, 163 of the 323 sources are detected. For the remaining 160 sources, 2 sigma upper limits to the X-ray flux are derived. We present power-law photon indices in the 0.1-2.4 keV energy band for 115 sources, which were determined either with a hardness ratio technique or from direct fits to pointed PSPC data if a sufficient number of photons were available. The average photon index is <Gamma > = 1.95(-0.12)(+0.13) for flat-spectrum radio-loud quasars, <Gamma > = 1.70(-0.24)(+0.23) for galaxies, and <Gamma > = 2.40(-0.31)(+0.12) for BL Lac objects. The soft X-ray photon index is correlated with redshift and with radio spectral index in the sense that sources at high redshift and/or with flat (or inverted) radio spectra have flatter X-ray spectra on average. The results are in accord with orientation-dependent unification schemes for radio-loud active galactic nuclei. Webster et al. discovered many sources with unusually red optical continua among the quasars of this sample, and interpreted this result in terms of extinction by dust. Although the X-ray spectra in general do not show excess absorption, we find that low-redshift optically red quasars have significantly lower soft X-ray luminosities on average than objects with blue optical continua. The difference disappears for higher redshifts, as is expected for intrinsic absorption by cold gas associated with the dust. In addition, the scatter in log(f(x)/f(o)) is consistent with the observed optical extinction, contrary to previous claims based on optically or X-ray selected samples. Although alternative explanations for the red optical continua cannot be excluded with the present X-ray data, we note that the observed X-ray properties are consistent with the idea that dust plays an important role in some of the radio-loud quasars with red optical continua.

Targeting local tissues by transdermal application: Understanding drug physicochemical properties that best exploit protein binding and blood flow effects

The targeting of topically applied drug molecules into tissues below a site of application requires an understanding of the complex interrelationships between the drug, its formulation, the barrier properties of the skin, and the physiological processes occurring below the skin that are responsible for drug clearance from the site, tissue, and/or systemic distribution and eventual elimination. There is still a certain amount of controversy over the ability of topically applied drugs to penetrate into deeper tissues by diffusion or whether this occurs by redistribution in the systemic circulation. The major focus of our work in this area has been in determining how changes in drug structure and physicochemical properties, such as protein binding and lipophilicity, affect drug clearance into the local dermal microcirculation and lymphatics, as well as subsequent distribution into deeper tissues below an application site. The present study outlines our recent thinking on the drug molecule optimal physical attributes, in terms of plasma and tissue partitioning behaviour, that offer the greatest potential for deep tissue targeting. Drug Dev. Res. 46:309-315, 1999. (C) 1999 Wiley-Liss, Inc.

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.

Differentiation of soil properties related to the spatial association of wheat roots and soil macropores

Under certain soil conditions, e.g. hardsetting clay B-horizons of South-Eastern Australia, wheat plants do not perform as well as would be expected given measurements of bulk soil attributes. In such soils, measurement indicates that a large proportion (80%) of roots are preferentially located in the soil within 1 mm of macropores. This paper addresses the question of whether there are biological and soil chemical effects concomitant with this observed spatial relationship. The properties of soil manually dissected from the 1-3 mm wide region surrounding macropores, the macropore sheath, were compared to those that are measured in a conventional manner on the bulk soil. Field specimens of two different soil materials were dissected to examine biological differentiation. To ascertain whether the macropore sheath soil differs from rhizosphere soil, wheat was grown in structured and repacked cores under laboratory conditions. The macropore sheath soil contained more microbial biomass per unit mass than both the bulk soil and the rhizosphere. The bacterial population in the macropore sheath was able to utilise a wider range of carbon substrates and to a greater extent than the bacterial population in the corresponding bulk soil. These differences between the macropore sheath and bulk soil were almost non-existent in the repacked cores. Evidence for larger numbers of propagules of the broad host range fungus Pythium in the macropore sheath soil were also obtained.

Administration of growth hormone or IGF-I to pregnant rats on a reduced diet throughout pregnancy does not prevent fetal intrauterine growth retardation and elevated blood pressure in adult offspring

Increasing evidence from human epidemiological studies suggests that poor growth before birth is associated with postnatal growth retardation and the development of cardiovascular disease in adulthood. We have shown previously that nutritional deprivation in the pregnant rat leads to intrauterine growth retardation (IUGR), postnatal growth failure, changes in the endocrine parameters of the somatotrophic axis, and to increased blood pressure in later life. In the present study, we investigated whether administration of insulin-like growth factor-I (IGF-I) or bovine growth hormone (GH) during pregnancy could prevent IUGR and/or alter long-term outcome. Dams h-om day 1 of pregnancy throughout gestation received a diet of nd libitum available food or a restricted dietary intake of 30% of ad libitum fed dams. From day 10 of gestation, dams were treated for 10 days with three times daily subcutaneous injections of saline (100 mu l), IGF-I (2 mu g/g body weight) or GH (2 mu g/g body weight). Maternal weight gain was significantly increased (P

Variable temperature and pressure study of the aquation reactions of cobalt(III) and chromium(III) penta- and tetra-amines

Preparation of a series of specific penta- and tetra-amine derivatives of Co-III and Cr-III with a neutral leaving ligand has been carried out in order to accomplish a fine tuning of the associativeness/dissociativeness of their substitution reactions. Spontaneous aquation reactions of the neutral ligands have been studied at variable temperature and pressure. Although rate constants and thermal activation parameters show an important degree of scatter, the values determined for the activation volumes of the substitution process illustrate the mechanistic fine tuning that may be achieved for these reactions. In all cases, in the absence of important steric constraints in the molecule, electronic inductive effects seem to be the most important factor accounting for the dissociative shifts observed both for pentaamine (i.e.Delta V double dagger=+4.0 or +14.0 cm(3) mol(-1) and +5.2 or +16.5 cm(3) mol(-1) for the aquation of cis- or trans-[Co(MeNH2)(NH3)(4)(DMF)](3+) and cis- or trans-[CoL15(DMF)](3+) respectively, where L-15 represents a pentaamine macrocyclic ligand), and tetraamine systems (i.e.Delta V double dagger=+4.1 or +8.4 cm(3) mol(-1) and -10.8 or -7.4 cm(3) mol(-1) for the aquation of cis-[Co(NH3)(4)Cl(DMAC)](2+) (DMAC=dimethylacetamide) or cis-[Co(en)(2)Cl(DMAC)](2+) and cis-[Cr(NH3)(4)Cl(DMF)](2+) or cis -[Cr(en)(2)Cl(DMF)](2+)). From the results, clear evidence is obtained which indicates that, only when the situation is borderline I-a/I-d, or the steric demands are increased dramatically, dissociative shifts are observed; in all other cases electronic inductive effects seem to be dominant for such a tuning of the substitution process.

Modeling the optical properties of AlSb, GaSb, and InSb

Optical constants of AlSb, GaSb, and InSb are modeled in the 1-6 eV spectral range. We employ an extension of Adachi's model of the optical constants of semiconductors. The model takes into account transitions at E-0, E-0 + Delta(0), E-1, and E-1 + Delta(1) critical points, as well as higher-lying transitions which are modeled with three damped harmonic oscillators. We do not consider indirect transitions contribution, since it represents a second-order perturbation and its strength should be low. Also, we do not take into account excitonic effects at E-1, E-1 + Delta(1) critical points, since we model the room temperature data. In spite of fewer contributions to the dielectric function compared to previous calculations involving Adachi's model, our calculations show significantly improved agreement with the experimental data. This is due to the two main distinguishing features of calculations presented here: use of adjustable line broadening instead of the conventional Lorentzian one, and employment of a global optimization routine for model parameter determination.

Effect of additives on gelatinization, rheological properties and biodegradability of thermoplastic starch

Effect of additives on the starch gelatinization was governed by the processing conditions. The order-disorder transition of starch in water can occur in more than one way and the effect of polar additives on gelatinization can also be in more than one way. The additives appear to be plasticising thermoplastic starches, resulting in improving rheological properties. The thermoplastic starches with the additives are all biodegradable although the rates of biodegradability are slightly different.

The influence of supra-optimal root-zone temperatures on growth and stomatal conductance in Capsicum annuum L.

Pepper (Capsicum annuum L.) plants were grown aeroponically in a Singapore greenhouse under natural diurnally fluctuating ambient shoot temperatures, but at two different root-zone temperatures (RZTs): a constant 20 +/- 2 degrees C RZT and a diurnally fluctuating ambient (A) (25-40 degrees C) RZT, Plants grown at 20-RZT had more leaves, greater leaf area and dry weight than A-RZT plants. Reciprocal transfer experiments were conducted between RZTs to investigate the effect on plant growth, stomatal conductance (g(s)) and water relations. Transfer of plants from A-RZT to 20-RZT increased plant dry weight, leaf area, number of leaves, shoot water potential (Psi(shoot)), and g(s); while transfer of plants from 20-RZT to A-RZT decreased these parameters. Root hydraulic conductivity was measured in the latter transfer and decreased by 80% after 23 d at A-RZT. Transfer of plants from 20-RZT to A-RZT had no effect on xylem ABA concentration or xylem nitrate concentration, but reduced xylem sap pH by 0.2 units. At both RZTs, g(s) measured in the youngest fully expanded leaves increased with plant development. In plants with the same number of leaves, A-RZT plants had a higher g(s) than 20-RZT plants, but only under high atmospheric vapour pressure deficit. The roles of chemical signals and hydraulic factors in controlling g(s) of aeroponically grown Capsicum plants at different RZTs are discussed.