On uniquely determining cell-wall material properties with the compression experiment

A finite element model (FEM) of the cell-compression experiment has been developed in dimensionless form to extract the fundamental cell-wall-material properties (i.e. the constitutive equation and its parameters) from experiment force-displacement data. The FEM simulates the compression of a thin-walled, liquid-filled sphere between two flat surfaces. The cell-wall was taken to be permeable and the FEM therefore accounts for volume loss during compression. Previous models assume an impermeable wall and hence a conserved cell volume during compression. A parametric study was conducted for structural parameters representative of yeast. It was shown that the common approach of assuming reasonable values for unmeasured parameters (e.g. cell-wall thickness, initial radial stretch) can give rise to nonunique solutions for both the form and constants in the cell-wall constitutive relationship. Similarly, measurement errors can also lead to an incorrectly defined cell-wall constitutive relationship. Unique determination of the fundamental wall properties by cell compression requires accurate and precise measurement of a minimum set of parameters (initial cell radius, initial cell-wall thickness, and the volume loss during compression). In the absence of such measurements the derived constitutive relationship may be in considerable error, and should be evaluated against its ability to predict the outcome of other mechanical experiments. (C) 1998 Elsevier Science Ltd. All rights reserved.

Development of composite adsorbents of carbon and intercalated clay for N2 and O2 adsorption: A preliminary study

Composite adsorbents of carbon and alumina intercalated montmorillonite were prepared and characterized by adsorption of N-2 and O-2 at various temperatures. The effects of pyrolysis, temperature, heating rate, subsequent degassing, and doping of cations and anions were investigated. The adsorption capacities of the composite adsorbents developed at higher temperatures (0 and -79 degrees C) are found to be larger than those of normal alumina pillared clays. The experimental results showed that the framework of these adsorbents is made of alumina particles and clay sheets while the pyrolyzed carbon distributes in the space of interlayers and interpillars. The pores between the carbon particles, clay sheets, and alumina pillars are very narrow with very strong adsorption forces, leading to enhanced adsorption capacities at 0 and -79 degrees C. The composite adsorbents exhibit features similar to those of carbonaceous adsorbents. Their pore structures, adsorption capacities, and selectivities to oxygen can be tailored by a controlled degassing procedure. Meanwhile, ions can be doped into the adsorbents to modify their adsorption properties, as usually observed for oxide adsorbents like zeolite and pillared clays. Such flexibility in pore structure tailoring is a potential advantage of the composite adsorbents developed for their adsorption and separation applications. (C) 1999 Academic Press.

A simplified, sequential, phosphorus fractionation method

Hedley er al. (1982) developed what has become the most widely used land modified), phosphorus (P) fractionation technique. It consists of sequential extraction of increasingly less phytoavailable P pools. Extracts are centrifuged at up to 25000 g (RCF) and filtered to 0.45 mu m to ensure that soil is not lost between extractions. In attempting to transfer this method to laboratories with limited facilities, it was considered that access to high-speed centrifuges, and the cost of frequent filtration may prevent adoption of this P fractionation technique. The modified method presented here was developed to simplify methodology, reduce cost, and therefore increase accessibility of P fractionation technology. It provides quantitative recovery of soil between extractions, using low speed centrifugation without filtration. This is achieved by increasing the ionic strength of dilute extracts, through the addition of NaCl, to flocculate clay particles. Addition of NaCl does not change the amount of P extracted. Flocculation with low speed centrifugation produced extracts comparable with those having undergone filtration (0.025 mu m). A malachite green colorimetric method was adopted for inorganic P determination, as this simple manual method provides high sensitivity with negligible interference from other anions. This approach can also be used for total P following digestion, alternatively non-discriminatory methods, such as inductively coupled plasma atomic emission spectroscopy, may be employed.

trans-Cyano(6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine)cobalt(III) bis(perchlorate) hydrate and trans-hydroxo(6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine)cobalt(III) bis(perchlorate)

The crystal structures of a pair of closely related macrocyclic cyano- and hydroxopentaaminecobalt(III) complexes, as their perchlorate salts, are reported. Although the two complexes, [Co(CN)(C11H27N5)](ClO4)2.H2O and [Co(OH)(C11H27N5)](ClO4)(2), exhibit similar conformations, significant differences in the Co-N bond lengths arise from the influence of the sixth ligand (cyano as opposed to hydroxo). The ensuing hydrogen-bonding patterns are also distinctly different. Disorder in the perchlorate anions was clearly resolved and this was rationalized on the basis of distinct hydrogen-bonding motifs involving the anion O atoms and the N-H and O-H donors.

Synthesis of (Z)-1-Organylthiobut-1-en-3-ynes: Hydrothiolation of Symmetrical and Unsymmetrical Buta-1,3-diynes

Hydrothiolation of 1-organylbuta-1,3-diynes and 1,4-diorganylbuta-1,3-diynes with the sodium organylthiolate anions, which were generated in situ by reacting diphenyl and dibutyl disulfide with NaBH(4) in ethanol, results in the regio-, stereo-, and chemoselective formation of (Z)-1-organylthio-4-organylbut-1-en-3-ynes and (Z)-1-organylthio-1,4-diorganylbut-1-en-3-ynes, respectively.

One-pot synthesis of mixed (Z)-1,2-bis(organylchalcogene)-1-alkenes precursors of the novel beta-organylthio vinyllithium intermediates

One-pot hydrochalcogenation of 1-phenylthioacetylenes using organylselenolate and organyltellurolate anions generated by the insertions of selenium and tellurium in n-organyl lithium produced (Z)-1,2-bis(organylchalcogene)-1-alkenes. The chemical reactivity of these mixed 1,2-bis(organylchalcogene)-1-alkenes was studied by Te/Li and Se/Li stereoretentive exchanges carried out with n-butyl lithium, furnishing the new intermediate species (Z)-beta-organylthio vinyllithium anions, which were trapped with aldehydes, to give the (Z)-3-hydroxy vinyl thioethers with total control of the regio- and stereochemistry. (c) 2010 Elsevier Ltd. All rights reserved.

Wet deposition of major ions in a rural area impacted by biomass burning emissions

This work concerns the influence of industrialized agriculture in the tropics on precipitation chemistry. A total of 264 rain events were sampled using a wet-only collector in central Sao Paulo State, Brazil, between January 2003 and July 2007. Electroneutrality balance calculations (considering H(+), K(+), Na(+), NH(4)(+), Ca(2)(+), Mg(2)(+), Cl(-), NO(3)(-), SO(4)(2-), F(-), PO(4)(3-), H(3)CCOO(-), HCOO(-), C(2)O(4)(2-) and HCO(3)(-)) showed that there was an excess of cations (similar to 15%), which was attributed to the presence of unmeasured organic anion species originating from biomass burning and biogenic emissions. On average, the three ions NH(4)(+), NO(3)(-) and H(+) were responsible for >55% of the total ion concentrations in the rainwater samples. Concentrations (except of H(+)) were significantly higher (t-test; P = 0.05), by between two to six-fold depending on species, during the winter sugar cane harvest period, due to the practice of pre-harvest burning of the crop. Principal component analysis showed that three components could explain 88% of the variance for measurements made throughout the year: PC1 (52%, biomass burning and soil dust resuspension); PC2 (26%, secondary aerosols); PC3 (10%, road transport emissions). Differences between harvest and non-harvest periods appeared to be mainly due to an increased relative importance of road transport/industrial emissions during the summer (non-harvest) period. The volume-weighted mean (VWM) concentrations of ammonium (23.4 mu mol L(-1)) and nitrate (17.5 mu mol L(-1)) in rainwater samples collected during the harvest period were similar to those found in rainwater from Sao Paulo city, which emphasizes the importance of including rural agro-industrial emissions in regional-scale atmospheric chemistry and transport models. Since there was evidence of a biomass burning source throughout the year, it appears that rainwater composition will continue to be affected by vegetation fires, even after sugar cane burning is phased out as envisaged by recent Sao Paulo State legislation. (C) 2011 Elsevier Ltd. All rights reserved.

An investigation into the synthesis of polycarbazole squaraine derivatives

The polycondensation of squaric acid with 1,2-(9-Ethylcarbazol-3-yl)ethene and N-ethyliminostilbene in polyphosphoric acid yielded insoluble polymers which included substituted phosphate groups on the phenyl rings. The presence of phosphorus in these polymers was identified using solid-state P-31 NMR and EDAX techniques. Furthermore the phosphate groups were not ionic, hence no charge-balancing anions were present; Both polymers did not electrically conduct but exhibited dielectric breakdown values of 0.1 and 0.06 MV cm(-1) respectively.

An examination of male and female odds ratios by BMI, cigarette smoking, and alcohol consumption for cancers of the oral cavity, pharynx, and larynx in pooled data from 15 case-control studies

Greater tobacco smoking and alcohol consumption and lower body mass index (BMI) increase odds ratios (OR) for oral cavity, oropharyngeal, hypopharyngeal, and laryngeal cancers; however, there are no comprehensive sex-specific comparisons of ORs for these factors. We analyzed 2,441 oral cavity (925 women and 1,516 men), 2,297 oropharynx (564 women and 1,733 men), 508 hypopharynx (96 women and 412 men), and 1,740 larynx (237 women and 1,503 men) cases from the INHANCE consortium of 15 head and neck cancer case-control studies. Controls numbered from 7,604 to 13,829 subjects, depending on analysis. Analyses fitted linear-exponential excess ORs models. ORs were increased in underweight (< 18.5 BMI) relative to normal weight (18.5-24.9) and reduced in overweight and obese categories (a parts per thousand yen25 BMI) for all sites and were homogeneous by sex. ORs by smoking and drinking in women compared with men were significantly greater for oropharyngeal cancer (p < 0.01 for both factors), suggestive for hypopharyngeal cancer (p = 0.05 and p = 0.06, respectively), but homogeneous for oral cavity (p = 0.56 and p = 0.64) and laryngeal (p = 0.18 and p = 0.72) cancers. The extent that OR modifications of smoking and drinking by sex for oropharyngeal and, possibly, hypopharyngeal cancers represent true associations, or derive from unmeasured confounders or unobserved sex-related disease subtypes (e.g., human papillomavirus-positive oropharyngeal cancer) remains to be clarified.

An evaluation of a suburban railway pedestrian crossing safety programme

This study evaluated a programme of educational and environmental (access prevention) interventions designed to reduce the incidence of illegal and unsafe crossing of the rail corridor at a suburban station in Auckland, New Zealand. Immediately after the programme of interventions, the proportion of those crossing the rail corridor by walking across the tracks directly rather than using the nearby overbridge had decreased substantially. Three months later, the decrease was even greater. However, the educational and environmental interventions were introduced simultaneously so that the effects of each could not be separated, nor could other unmeasured factors be ruled out. Anonymous surveys administered immediately before and 3 months after the interventions indicated that while awareness of the illegality of walking across the tracks had increased slightly, perception of risk had not changed. This suggests that the educational interventions may have had less effect than the access prevention measures. (C) 2001 Elsevier Science Ltd. All rights reserved.

Adaptive multiscale principal components analysis for online monitoring of wastewater treatment

Fault detection and isolation (FDI) are important steps in the monitoring and supervision of industrial processes. Biological wastewater treatment (WWT) plants are difficult to model, and hence to monitor, because of the complexity of the biological reactions and because plant influent and disturbances are highly variable and/or unmeasured. Multivariate statistical models have been developed for a wide variety of situations over the past few decades, proving successful in many applications. In this paper we develop a new monitoring algorithm based on Principal Components Analysis (PCA). It can be seen equivalently as making Multiscale PCA (MSPCA) adaptive, or as a multiscale decomposition of adaptive PCA. Adaptive Multiscale PCA (AdMSPCA) exploits the changing multivariate relationships between variables at different time-scales. Adaptation of scale PCA models over time permits them to follow the evolution of the process, inputs or disturbances. Performance of AdMSPCA and adaptive PCA on a real WWT data set is compared and contrasted. The most significant difference observed was the ability of AdMSPCA to adapt to a much wider range of changes. This was mainly due to the flexibility afforded by allowing each scale model to adapt whenever it did not signal an abnormal event at that scale. Relative detection speeds were examined only summarily, but seemed to depend on the characteristics of the faults/disturbances. The results of the algorithms were similar for sudden changes, but AdMSPCA appeared more sensitive to slower changes.

The radiation chemistry of ultem at 77 K as revealed by ESR spectroscopy

Radical formation in ultem following gamma-radiolysis has been reassessed, and the G(R*) values at different temperatures have been determined by ESR spectroscopy. The radical assignment and radical reactivity have been re-examined by photobleaching and thermal annealing studies. Photobleachable radical anions were found to comprise approximate to40% of the total number of radicals formed on radiolysis at 77 K. Spectral subtraction methods, ESR spectral simulations, measurement of g-values and the hyperfine splitting constants were used to identify the other radical intermediates. The principal chain scission radicals are formed due to scission of the main-chain at (i) the ether linkage, (ii) the isopropylidene group and (iii) the imide ring in the main chain. The side chain methyl groups of the isopropylidine units also lose hydrogen to form methylene radicals. The five-line spectrum observed to decay in the temperature range 370-430 K, which has not been assigned previously, has been identified as being characteristic of a di-substituted benzyl radical. (C) 2002 Elsevier Science Ltd. All rights reserved.

Enterohepatic circulation - Physiological, pharmacokinetic and clinical implications

Enterohepatic recycling occurs by biliary excretion and intestinal reabsorption of a solute, sometimes with hepatic conjugation and intestinal deconjugation. Cycling is often associated with multiple peaks and a longer apparent half-life in a plasma concentration-time profile. Factors affecting biliary excretion include drug characteristics (chemical structure, polarity and molecular size), transport across sinusoidal plasma membrane and canniculae membranes, biotransformation and possible reabsorption from intrahepatic bile ductules. Intestinal reabsorption to complete the enterohepatic cycle may depend on hydrolysis of a drug conjugate by gut bacteria. Bioavailability is also affected by the extent of intestinal absorption, gut-wall P-glycoprotein efflux and gut-wall metabolism. Recently, there has been a considerable increase in our understanding of the role of transporters, of gene expression of intestinal and hepatic enzymes, and of hepatic zonation. Drugs, disease and genetics may result in induced or inhibited activity of transporters and metabolising enzymes. Reduced expression of one transporter, for example hepatic canalicular multidrug resistance-associated protein (MRP) 2, is often associated with enhanced expression of others, for example the usually quiescent basolateral efflux MRP3, to limit hepatic toxicity. In addition, physiologically relevant pharmacokinetic models, which describe enterohepatic recirculation in terms of its determinants (such as sporadic gall bladder emptying), have been developed. In general, enterohepatic recirculation may prolong the pharmacological effect of certain drugs and drug metabolites. Of particular importance is the potential amplifying effect of enterohepatic variability in defining differences in the bioavailability, apparent volume of distribution and clearance of a given compound. Genetic abnormalities, disease states, orally administered adsorbents and certain coadministered drugs all affect enterohepatic recycling.

Transcriptional regulation of the sodium-sulfate cotransporter NaSi-1 gene

Inorganic sulfate is one of the most abundant anions in mammalian plasma and is essential for proper cell growth and development, as well as detoxification and activation of many biological compounds. To date, little is understood how physiological levels of sulfate are maintained in the body. Our studies, and of others, have identified the NAS(i)-1 protein to be a functional sulfate transporter in the kidney and intestine, and due to this localization, constitutes a strong candidate gene for maintaining body sulfate homeostasis. Several factors, including hormones and metabolic conditions, have been shown to alter NAS(i)-1 mRNA and protein levels in vivo. In this study, we describe the transcriptional regulation of NaSi-1, with a focus on the mouse NaSi-1 gene (Nas1) that was recently cloned in our laboratory. Vitamin D (1,25-(OH)(2)D-3) and thyroid hormone (T-3) led to an increase in Nas1 promoter activity in OK cells. Mutational analysis of the Nas1 promoter resulted in identification of a direct repeat 6-type vitamin-D-responsive element (DR6 VDRE) at -525 to -508 and an imperfect inverted repeat 0-type T-3 responsive element (IRO T3RE) at -426 to -425 which conferred 1,25-(OH)(2)D-3 and T-3 responsiveness respectively. These findings suggest for vitamin D and thyroid hormone regulation of NaSi-1, may provide important clues to the physiological control of sulfate homeostasis.

Chemical characterisation of deep profile Ferrosols under sugarcane in wet tropical northern Queensland

The chemical properties of deep profile samples ( up to 12 m) of Ferrosols from northern Queensland were investigated to provide an understanding of the accumulation of nitrate ( NO3) within these soil profiles. The influence of other cations and anions present in the soil solution or on the exchange and the charge chemistry of the profiles were examined with respect to the NO3 accumulations. The major ions in the soil solution were Na, NO3, and chloride ( Cl). Distinct regions of anion accumulation were observed; SO4 accumulated in the upper profile of all cores, whereas NO3 and Cl accumulations were restricted to the lower profile of cores with appreciable AEC (> 1 cmol(c)/kg). Gaines-Thomas selectivity coefficients were used to indicate exchange preference for cations and anions, and are as follows: Al > Ca similar to Mg > K > Na and sulfate (SO4) > Cl similar to NO3. The selectivity of SO4 increased and the extractable SO4 decreased in the lower profile of all cores. This has important implications for the adsorption of NO3 and Cl. The NO3 and Cl accumulations were shown to correspond to a region of low SO4 occupancy of the exchange sites in the lower profile. Along with the high SO4 selectivity, this suggests that SO4 may control the positioning of the NO3 accumulations. It was concluded that the NO3 accumulations were relatively stable under current management practices, although the reduction in NO3 inputs would likely see the gradual replacement of NO3 with Cl as a result of their comparable selectivity for exchange sites.