Typhoon effects on DOC dynamics in a phosphate-limited reservoir

To explore typhoon effects on dissolved organic carbon (DOC) dynamics, field investigations (tributary and dam site) and laboratory experiments (bioassay and DOC consumption) were conducted in a subtropical reservoir. A tributary survey indicated that after typhoon disruption, upstream areas were the sources of phosphate (P) but not DOC for the dam site located downstream. Bioassay experiments verified P-limitation on bacteria and phytoplankton during summer stratification, and bacteria showed a faster response than algae to added P. Experiments indicated that DOC consumption was determined by the availability of P. The 4 yr typhoon period (June-September) data of the dam site denoted that DOC concentration (27 to 270 mu M C) and its rate of change (-13 to 24 mu M C d(-1)) varied more dramatically in the weak (2006 and 2007) than in the strong (2004 and 2005) typhoon years. The negative correlation of DOC with the ratio of bacterial production (BP) to primary production (PP) in the euphotic zone (0 to 10 m) signified the interactive effects of auto- and heterotrophic processes on DOC variation. In the aphotic zone, the variation of DOC could be ascribed to the change of BP, which showed a positive correlation with P concentrations. This study documents that DOC concentration in the studied system varied at multiple time scales. Such variation can be explained by the decoupling between BP and PP, which is believed to be a function of the limiting nutrient's availability. More importantly, this study suggests that the P supply introduced by strong typhoons might have substantiated a tighter coupling between BP and PP, so that the amplitude of DOC oscillation during the summer period was effectively reduced.

The effect of variability in the powder/liquid ratio on the strength of zinc phosphate cement

Aim: To investigate (a) variability in powder/liquid proportioning (b) effect of the extremes of any such variability on diametral tensile strength (DTS), in a commercial zinc phosphate cement. Statistical analyses (a = 0.05) were by Student's t-test in the case of powder/liquid ratio and one-way ANOVA and Tukey HSD for for pair-wise comparisons of mean DTS. The Null hypotheses were that (a) the powder-liquid mixing ratios observed would not differ from the manufacturer's recommended ratio (b) DTS of the set cement samples using the extreme powder/liquid ratios observed would not differ from those made using the manufacturer's recommended ratio. Methodology: Thirty-four undergraduate dental students dispensed the components according to the manufacturer's instructions. The maximum and minimum powder/liquid ratios (m/m), together with the manufacturer's recommended ratio (m/m), were used to prepare cylindrical samples (n = 3 x 34) for DTS testing. Results: Powder/liquid ratios ranged from 2.386 to 1.018.The mean ratio (1.644 (341) m/m) was not significantly different from the manufacturer's recommended value of 1.718 (p=0.189). DTS values for the maximum and minimum ratios (m/m), respectively, were both significantly different from each other (p<0.001) and from the mean value obtained from the manufacturer's recommended ratio (m/m) (p<0.001). Conclusions: Variability exists in powder/liquid ratio (m/m) for hand dispensed zinc phosphate cement. This variability can affect the DTS of the set material.

Involvement of incipient hydrous oxide species in electrocatalysis at some metal electrode surfaces

In this thesis a novel theory of electrocatalysis at metal (especially noble metal)/solution interfaces was developed based on the assumption of metal adatom/incipient hydrous oxide cyclic redox transitions. Adatoms are considered as metastable, low coverage species that oxidise in-situ at potentials of often significantly cathodic to the regular metal/metal oxide transition. Because the adatom coverage is so low the electrochemical or spectroscopic response for oxidation is frequently overlooked; however, the product of such oxidation, referred to here as incipient hydrous oxide seems to be the important mediator in a wide variety of electrocatalytically demanding oxidation processes. Conversely, electrocatalytically demanding reductions apparently occur only at adatom sites at the metal/solution interface - such reactions generally occur only at potentials below, i.e. more cathodic than, the adatom/hydrous oxide transition. It was established that while silver in base oxidises in a regular manner (forming initially OHads species) at potentials above 1.0 V (RHE), there is a minor redox transition at much lower potentials, ca. o.35 v (RHE). The latter process is assumed to an adatom/hydrous oxide transition and the low coverage Ag(l) hydrous oxide (or hydroxide) species was shown to trigger or mediate the oxidation of aldehydes, e. g. HCHO. The results of a study of this system were shown to be in good agreement with a kinetic model based on the above assumptions; the similarity between this type of behaviour and enzyme-catalysed processes - both systems involve interfacial active sites - was pointed out. Similar behaviour was established for gold where both Au(l) and Au(lll) hydrous oxide mediators were shown to be the effective oxidants for different organic species. One of the most active electrocatalytic materials known at the present time is platinum. While the classical view of this high activity is based on the concept of activated chemisorption (and the important role of the latter is not discounted here) a vital role is attributed to the adatom/hydrous oxide transition. It was suggested that the well known intermediate (or anomalous) peak in the hydrogen region of the cyclic voltanmogram for platinum region is in fact due to an adatom/hydrous oxide transition. Using potential stepping procedures to minimise the effect of deactivating (COads) species, it was shown that the onset (anodic sweep) and termination (cathodic sweep) potential for the oxidation of a wide variety of organics coincided with the potential for the intermediate peak. The converse was also shown to apply; sluggish reduction reactions, that involve interaction with metal adatoms, occur at significant rates only in the region below the hydrous oxide/adatom transition.

Structure of the polyisoprenyl-phosphate glycosyltransferase GtrB and insights into the mechanism of catalysis.

The attachment of a sugar to a hydrophobic polyisoprenyl carrier is the first step for all extracellular glycosylation processes. The enzymes that perform these reactions, polyisoprenyl-glycosyltransferases (PI-GTs) include dolichol phosphate mannose synthase (DPMS), which generates the mannose donor for glycosylation in the endoplasmic reticulum. Here we report the 3.0 Å resolution crystal structure of GtrB, a glucose-specific PI-GT from Synechocystis, showing a tetramer in which each protomer contributes two helices to a membrane-spanning bundle. The active site is 15 Å from the membrane, raising the question of how water-soluble and membrane-embedded substrates are brought into apposition for catalysis. A conserved juxtamembrane domain harbours disease mutations, which compromised activity in GtrB in vitro and in human DPM1 tested in zebrafish. We hypothesize a role of this domain in shielding the polyisoprenyl-phosphate for transport to the active site. Our results reveal the basis of PI-GT function, and provide a potential molecular explanation for DPM1-related disease.

Pathogenicity of Salmonella: SopE-mediated membrane ruffling is independent of inositol phosphate signals

Studies [Zhou, D. Chen, L.-M. Hernandez, L. Shears, S.B. and Galán, J.E. (2001) A Salmonella inositol polyphosphatase acts in conjunction with other bacterial effectors to promote host-cell actin cytoskeleton rearrangements and bacterial internalization. Mol. Microbiol. 39, 248-259] with engineered Salmonella mutants showed that deletion of SopE attenuated the pathogen's ability to deplete host-cell InsP5 and remodel the cytoskeleton. We pursued these observations: In SopE-transfected host-cells, membrane ruffling was induced, but SopE did not dephosphorylate InsP5, nor did it recruit PTEN (a cytosolic InsP5 phosphatase) for this task. However, PTEN strengthened SopE-mediated membrane ruffling. We conclude SopE promotes host-cell InsP5 hydrolysis only with the assistance of other Salmonella proteins. Our demonstration that Salmonella-mediated cytoskeletal modifications are independent of inositolphosphates will focus future studies on elucidating alternate pathogenic consequences of InsP5 metabolism, including ion channel conductance and apoptosis.

Chitosan derivatives alter release profiles of model compounds from calcium phosphate implants

The aim of the current study was to evaluate the impact of chitosan derivatives, namely N-octyl-chitosan and N-octyl-O-sulfate chitosan, incorporated in calcium phosphate implants to the release profiles of model drugs. The rate and extent of calcein (on M.W. 650 Da) ED, and FITC-dextran (M.W. 40 kDa) on in vitro release were monitored by fluorescence spectroscopy. Results show that calcein release is affected by the type of chitosan derivative used. A higher percentage of model drug was released when the hydrophilic polymer N-octyl-sulfated chitosan was present in the tablets compared with the tablets containing the hydrophobic polymer N-octyl-chitosan. The release profiles of calcein or FD from tablets containing N-octyl-O-sulfate revealed a complete release for FD after 120 h compared with calcein where 20% of the drug was released over the same time period. These results suggest that the difference in the release profiles observed from the implants is dependent on the molecular weight of the model drugs. These data indicate the potential of chitosan derivatives in controlling the release profile of active compounds from calcium phosphate implants. (C) 2009 Elsevier Ltd. All rights reserved.

The kinetics of water loss from zinc phosphate and zinc polycarboxylate dental cements

The water desorption behaviour of three different zinc oxide dental cements (two polycarboxylates, one phosphate) has been studied in detail. Disc-shaped specimens of each material were prepared and allowed to lose water by being subjected to a low humidity desiccating atmosphere over concentrated sulfuric acid. In all three cements, water loss was found to follow Fick's second law for at least 6 h (until M(t)/M(infinity) values were around 0.5), with diffusion coefficients ranging from 6.03 x 10(-8 )cm(2 )s(-1) (for the zinc phosphate) to 2.056 x 10(-7 )cm(2 )s(-1) (for one of the zinc polycarboxylates, Poly F Plus). Equilibration times for desorption were of the order of 8 weeks, and equilibrium water losses ranged from 7.1% for zinc phosphate to 16.9% and 17.4% for the two zinc polycarboxylates.