A 1D- and 2D-NMR Study of an Anionic Surfactant/Neutral Polymer Complex

NMR chemical shifts and linewidth measurements were examined for mixtures of sodium 10-phenyldecanoate (Na ω-PhDec) in deuterated aqueous solutions in the presence of varying compositions of poly(ethylene oxide) (PEO) polymers of 2000 and 4000 molecular weight. In addition, variable temperature NMR spectra and NMR spin lattice relaxation times (T ₁) were obtained for the PEO-4000/Na ω-PhDec system as a function of varying polymer concentrations. As expected, the polymer/surfactant systems exhibit the behaviour typical of that of an anionic surfactant/neutral polymer system with well defined critical aggregation concentrations (CMC) corresponding to the formation of polymer/surfactant complexes below the CMC of the free surfactant. The ¹H-NMR linewidths acquired for the Na ω-PhDec/PEO-4000 system before and after the CMC region of the surfactant indicate that the maximum in the linewidth of the PEO proton peak is reached at approximately twice the CMC of the free surfactant. 2D-NMR NOESY measurements on this system exhibit cross peaks between the PEO protons and the protons on the surfactant backbone, consistent with the location of the phenyl group in the micellar interior. All these NMR experiments are interpreted in terms of the structure of the polymer/surfactant complexes as a function of the system composition.

Evaluation of the effect of tracer pH on the sealing ability of glass ionomer cement and mineral trioxide aggregate

OBJECTIVES: The aim of this study was to evaluate the sealing ability and physical and chemical properties of glass ionomer cement (GIC) and mineral trioxide aggregate (MTA) using Rhodamine B at different pHs as tracer. METHODS: Chemical analysis, pH and micro-hardness of GIC and MTA were performed. In addition dye leakage was assessed by tracer leakage using Tandem Scanning Confocal Microscope (TSM) after immersion of premolar teeth in a stock and a buffered fluorescent Rhodamine B for 24 h. Ultra-structural changes within the materials were evaluated by viewing under the field emission scanning electron microscope (FESEM). RESULTS: GIC and MTA showed elemental peaks for silicon, aluminium and calcium while MTA also had bismuth. GIC was acidic (P = 0.001) and caused an increase in dye pH (P = 0). Immersion of MTA in any of the test solutions resulted in an increase in the pH of the solution (P < 0.05). Use of a dye solution of lower pH than the material under test increased the cement micro-hardness. GIC demonstrated marginal leakage on TSM and both increase in marginal leakage and material porosity on FESEM. MTA was not affected by the use of acidic dye but showed a tendency to take up dye within the material shown on TSM. CONCLUSIONS: Evaluation of marginal adaptation of dental materials was shown to be dependent on the technique used for viewing the material to tooth interface, the properties of the material under study and the pH of the dye used.     

Diffuse and point sources of silica in the Seine River watershed

Dissolved silica (DSi) is believed to enter aquatic ecosystems primarily through diffuse sources by weathering. Point sources have generally been considered negligible, although recent reports of DSi inputs from domestic and industrial sources suggest otherwise. In addition, particulate amorphous silica (ASi) inputs from terrestrial ecosystems during soil erosion and in vegetation can dissolve and also be a significant source of DSi. We quantify here both point and diffuse sources of DSi and particulate ASi to the Seine River watershed. The total per capita point source inputs of Si (DSi + ASi) were found to be 1.0 and 0.8 g Si inhabitant(-1) d(-1) in raw and treated waters of the Achères wastewater treatment plant, in agreement with calculations based on average food intake and silica-containing washing products consumption. A mass balance of Si inputs and outputs for the Seine drainage network was established for wet and dry hydrological conditions (2001 and 2003, respectively). Diffuse sources of Si are of 1775 kg Si km(-2) y(-1) in wet conditions and 762 kg Si km(-2) y(-1) in dry conditions, with the proportion of ASi around 6%. Point sources of Si from urban discharge can contribute to more than 8% of the total Si inputs at the basin scale in hydrologically dry years. An in-stream retention of 6% of total inputs in dry conditions and 12% in wet conditions is inferred from the budget.     

Disseminated histoplasmosis: 2 cases in patients with human immunodeficiency virus infection in French Guiana

The authors report two cases of disseminated histoplasmosis occurring in HIV-infected patients living in French Guiana. The first case was an acute disseminated histoplasmosis with a rapid fatal evolution. The second case was diagnosed on a mucosal localisation, and improved under itraconazole therapy. These two cases show the diversity of the clinical course of this opportunistic infection. The authors focus on the difficulty of the diagnosis and the need for direct microscopic examination to identify histoplasma and to enable a swift therapeutic intervention.     

Evidence for Novel Action at the Cell‐Binding Site of Human Angiogenin Revealed by Heteronuclear NMR Spectroscopy,in silico and in vivo Studies

A member of the ribonuclease A superfamily, human angiogenin (hAng) is a potent angiogenic factor. Heteronuclear NMR spectroscopy combined with induced‐fit docking revealed a dual binding mode for the most antiangiogenic compound of a series of ribofuranosyl pyrimidine nucleosides that strongly inhibit hAng's angiogenic activity in vivo. While modeling suggests the potential for simultaneous binding of the inhibitors at the active and cell‐binding sites, NMR studies indicate greater affinity for the cell‐binding site than for the active site. Additionally, molecular dynamics simulations at 100 ns confirmed the stability of binding at the cell‐binding site with the predicted protein–ligand interactions, in excellent agreement with the NMR data. This is the first time that a nucleoside inhibitor is reported to completely inhibit the angiogenic activity of hAng in vivo by exerting dual inhibitory activity on hAng, blocking both the entrance of hAng into the cell and its ribonucleolytic activity.     

SENEQUE: a multi-scaling GIS interface to the Riverstrahler model of the biogeochemical functioning of river systems

The Riverstrahler model describes the biogeochemical functioning of an entire river system, from 100 to 100,000 km(2) or more, taking into account the constraints set by the morphology of the drainage network, the meteorological/hydrological conditions, and the inputs of material from point and non-point sources in the watershed. This tool has been applied for research purpose to several river systems differing in terms of hydrological regime and anthropogenic influences. In order to improve its capabilities and its generic dimension, as well as to develop a user-friendly interface allowing its transfer to non-specialist users including managers, the model has been coupled to a GIS interface. This gives the user the possibility to visualize the available geospatial database, to select the best geographical representation of the drainage network, to automatically prepare the corresponding input files required for the model, to pilot the model calculation and to visualize the results. The coupling with a GIS interface has considerably improved the capabilities of the Riverstrahler model. The code of the model is now entirely generic and can be run on any river system for which a suitable database is available. Its spatial resolution can be adapted to the requirement of the relevant problem, from the highest level, where each elementary watershed is individualized, to the lower level, where the whole basin is idealized as one basin with tributaries of each order having the same characteristics. As an illustration of the new potentialities offered by the coupling of Riverstrahler with a GIS through the SENEQUE interface, the results of a same modeling scenario are compared at different spatial resolutions. For the first time, with on-line coupling to a geodatabase, the effect of increasing the spatial resolution of the drainage network representation on the performance of the Riverstrahler model has been examined. At the outlet of the basin, the water quality results were found invariant to a large degree, whatever the details of its representation in the calculations. This result justifies the use of a low resolution representation of the upstream watershed when results are required only at the outlet of the basin.     

Nitrate leaching from organic and conventional arable crop farms in the Seine Basin (France)

In the Seine Basin, characterised by intensive arable crops, most of the surface and groundwater is contaminated by nitrate (NO₃ ^?). The goal of this study is to investigate nitrogen leaching on commercial arable crop farms in five organic and three conventional systems. In 2012–2013, a total of 37 fields are studied on eight arable crop rotations, for three different soil and climate conditions. Our results show a gradient of soil solution concentrations in function of crops, lower for alfalfa (mean 2.8 mg NO₃-N l^?1) and higher for crops fertilised after legumes (15 mg NO₃-N l^?1). Catch crops decrease nitrate soil solution concentrations, below 10 mg NO₃-N l^?1. For a full rotation, the estimated mean concentrations is lower for organic farming, 12 ± 5 mg NO₃-N l^?1 than for conventional farming 24 ± 11 mg NO₃-N l^?1, with however a large range of variability. Overall, organic farming shows lower leaching rates (14–50 kg NO₃-N ha^?1) than conventional farms (32–77 kg NO₃-N ha^?1). Taking into account the slightly lower productivity of organic systems, we show that yield-scaled leaching values are also lower for organic (0.2 ± 0.1 kg N kg^?1 N year^?1) than for conventional systems (0.3 ± 0.1 kg N kg^?1 N year^?1). Overall, we show that organic farming systems have lower impact than conventional farming on N leaching, although there is still room for progress in both systems in commercial farms.     

Nitrous oxide production from soil experiments: denitrification prevails over nitrification

Nitrous oxide is produced in soils and sediments essentially through the processes of nitrification and denitrification, although several rival processes could be competing. This study was undertaken in order to better understand the controlling factors of nitrification, denitrification and associated N₂O production as well as the contribution of these two processes to the average N₂O production by soils and sediments. With this aim, soil and sediment samples were taken in contrasting periods and different land use types, each time at different depths (upper and lower soil horizons). They were incubated in separate batches in specific conditions to promote denitrification and nitrification: (1) a complete anaerobic environment adding KNO₃ for the denitrification assay and (2) an aerobic environment (21 % O₂) with addition of NH₄Cl for the nitrification assay. Potentials of nitrification and denitrification were determined by the rates of nitrate either reduced (for denitrification) or produced (for nitrification). Overall, denitrification potential varied from 70 to 2,540 ng NO ₃ ^— -N g^?1 dry soil h^?1 and nitrification potential from 30 to 1,150 ng NO₃ ^?-N g^?1 dry soil h^?1. Nitrous oxide production by denitrification was significantly (P < 0.05) greater in topsoils (10–30 cm) than in subsoils (90–110 cm), ranging, respectively, from 26 to 250 ng N₂O-N g^?1 dry soil h^?1 versus 1.5 to 31 ng N₂O-N g^?1 dry soil h^?1, i.e., a mean 19.5 versus. 6.0 % of the NO₃ ^? denitrified for the upper and lower horizons, respectively. Considering the N₂O production in relation with the nitrate production (e.g., nitrification), no significant difference (P < 0.05) was found in the soil profile, which ranged from 0.03 to 6 ng N₂O-N g^?1 dry soil h^?1. This production accounts for 0.21 and 0.16 % of the mean of the NO₃ ^? produced for the top and subsoils, respectively. On the basis of the average production by both top- and subsoils, N₂O production by denitrification is clearly greater than by nitrification under the measurement conditions used in this study, from 30- to 100-fold higher. Such a high potential of N₂O emission must be taken into account when reducing nitrate contamination by increasing denitrification is planned as a curative measure, e.g. in rehabilitation/construction of wetlands.     

Nitrous oxide emissions from secondary activated sludge in nitrifying conditions of urban wastewater treatment plants: effect of oxygenation level

In order to better understand the mechanisms of N(2)O emissions from nitrifying activated sludge of urban WWTPs, sludge from the Valenton plant (Paris conurbation) are subjected to lab-scale batch experiments under various conditions of oxygenation. The results show that the highest N(2)O emissions (7.1 microgN-N(2)OgSS(-1) h(-1) in average) occur at a dissolved oxygen (DO) concentration of around 1mgO(2)L(-1). These high emissions at low oxygenation (from 0.1 to 2 mg O(2)L(-1)) are due to two processes: autotrophic nitrifier denitrification and heterotrophic denitrification. Nitrifier denitrification always dominates, representing from 58% to 83% of the N(2)O production. This N(2)O production originating from nitrifying activated sludge becomes 8 times higher when nitrite is added at a DO of 1 mg O(2)L(-1); a decrease is observed both at higher and lower oxygenation. Heterotrophic denitrification represents less than 50% of the N(2)O production, decreasing from 42% to 17% when oxygenation increases from 0.1 to 2 mg O(2) L(-1). We show that ammonium oxidizing bacteria (AOB) can shift to nitrifier denitrification when oxygen is depleted in the environments including in the WWTPs, nitrite then plays the role of oxygen as the final electron acceptor. As opposed to what happens in nitrification, the end products of nitrifier denitrification are gaseous forms of nitrogen, where N(2)O is not negligible compared to N(2). Overall, N(2)O emissions represent 0.1-0.4% of oxidized NH(4)(+), depending on the oxygenation level. N(2)O emissions would range from 0.11 to 0.42 TN-N(2)O day(-1) for a tertiary treatment of the Paris wastewater effluents, consisting exclusively of activated sludge nitrification.