Bile-salt-induced aggregation of poly(N-isopropylacrylamide) and lowering of the lower critical solution temperature in aqueous solutions

The effect of sodium cholate (NaC; concentration 1-16 mM), a biological surfactant, on the aggregation behavior of 1% (w/v, 2.2 × 10(-3) M) poly(N-isopropylacrylamide) (PNIPAM) aqueous solutions was studied as a function of temperature. From turbidity, dynamic light scattering, viscosity, and fluorescence measurements, it was observed that (i) there is NaC-induced nanoscale aggregation of PNIPAM in its sol state and (ii) the lower critical solution temperature corresponding to sol-gel transition shifts to a lower temperature by about 2 °C.

Hypervalent iodine in synthesis 64:Syntheses of diaryl selenides and alkyl aryl selenides by palladium-catalyzed arylation of areneselenyl or alkaneselenyl magnesium bromide with diaryliodonium salt

Areneselenyl or alkaneselenyl magnesium bromide reacts rapidly with diaryliodonium salt to give the corresponding diaryl or alkyl aryl selenide in the presence of catalytic amounts of Pd-(PPh3)4 in good yield.

Renal dopamine and salt-retaining states

Although generally regarded as a neurotransmitter, dopamine is also known to be secreted by the kidney whereby it promotes sodium excretion in its role as a natriuretic honnone. Peripheral dopamine may be formed by two alternative pathways; the decarboxylation of circulating L-Dopa by L-aromatic amino acid decarboxylase (LAAAD), and the desulphation of dopamine sulphate by arylsulphatase A (ASA), the latter being poorly represented in the literature. In many conditions and diseases with which sodium retention is associated, a reduced urinary excretion of dopamine has been noted implicating the involvement of dopamine in the maintenance of sodium homeostasis.This study investigates renal dopamine production via the desulphation of dopamine sulphate in a sample cohort during normal unregulated dietary sodium intake and following a low sodium regimen. After dietary salt restriction urinary dopamine sulphate levels were significantly increased, indicating that dopamine sulphate is indeed a physiological reservoir of active free dopamine, the necessity for which is reduced during self depletion. This confirmed the dopamine/dopamine sulphate pathway as one which may be relevant to the maintenance of sodium homeostasis. The activity of urinary ASA was investigated in diabetes mellitus as an example of a sodium-retaining state, and compared with that in a matched normal control group. A decreased ASA activity was anticipated, given the blunted dopamine excretion observed in many sodium-retaining states, however an unexpected increase in activity in the diabetic group was observed. Enzyme kinetic analysis of ASA showed that this was not due to the existence of an isoform having an altered affinity for dopamine sulphate. This rather paradoxical situation, that urinary-dopamine is decreased while ASA activity is increased, may be explained by the sequestering of free dopamine by autoxidation to 6-hydroxydopamine as has been hypothesised recently to occur in diabetes mellitus. To confirm the homogeneity of ASA in the normal and diabetic groups, four amplicons spanning the 3637bp intronic and exonic regions of the gene were generated by PCR. These were sequence utilising a fluorescent-dye terminator reaction using the forward PCR primer as sequencing primer. Although single nucleotide polymorphisms were observed between the two groups these occurred either in intronic regions or, when exonic, generated silent mutations, supporting the enzyme kinetic data. The expression of ASA was investigated to determine the basis of the increased activity observed in diabetes mellitus. Although a validated comparative RT-PCR assay was developed for amplification of arsa transcripts from fresh blood samples, expression analysis from archived paraffin-embedded renal tissue was complicated by the low yield and degradation of unprotected mRNA. Suggestions for the development of this work using renal cell-culture are discussed.

Improving the solubility and dissolution of poorly soluble drugs by salt formation and the consequent effect on mechanical properties

The bioavailability of BCS II compounds may be improved by an enhanced solubility and dissolution rate. Four carboxylic acid drugs were selected, which were flurbiprofen, etodolac, ibuprofen and gemfibrozil. The drugs were chosen because they are weak acids with poor aqueous solubility and should readily form salts. The counterions used for salt formation were: butylamine, pentylamine, hexylamine, octylamine, benzylamine, cyclohexylamine, tert-butylamine, 2-amino-2-methylpropan­2-ol, 2-amino-2-methyl propan-1,3-ol and tromethamine. Solubility was partially controlled by the saturated solution pH with the butylamine counterion increasing the solution pH and solubility and dissolution to the greatest extent. As the chain length increased, solubility was reduced due to the increasing lipophilic nature of the counterion. The benzylamine and cyclohexylamine counterions produced crystalline, stable salts but did not improve solubility and dissolution significantly compared to the parent compound. The substitution of hydroxyl groups to tert-butylamine counterions produced an increase in solubility and dissolution. AMP2 resulted in the most enhanced solubility and dissolution compared to the parent drug but using the tris salt did not further improve solubility due to a very stable crystal lattice structure. The parent drugs were very difficult to compress due to orientation effects and lamination. Compacts were prepared of each parent drug and salt and their modulus of elasticity values were measured using a three-point bend (Young’s modulus, E0) were extrapolated to zero porosity and compared. Compressibility and E0 were improved with the butylamine, tert-butylamine, cyclohexylamine and AMP2 counterions. The most significant improvement in compression and E0 was with the AMP2 salts. Mechanical properties were related to the hydrogen bonding within the crystal lattice structure for the gemfibrozil salt series.

A greenhouse integrating desalination, water saving and rainwater harvesting for use in salt-affected inland regions

This study proposes a new type of greenhouse for water re-use and energy saving for agriculture in arid and semi-arid inland regions affected by groundwater salinity. It combines desalination using reverse osmosis (RO), re-use of saline concentrate rejected by RO for cooling, and rainwater harvesting. Experimental work was carried at GBPUAT, Pantnagar, India. Saline concentrate was fed to evaporative cooling pads of greenhouse and found to evaporate at similar rates as conventional freshwater. Two enhancements to the system are described: i) A jet pump, designed and tested to use pressurized reject stream to re-circulate cooling water and thus maintain uniform wetness in cooling pads, was found capable of multiplying flow of cooling water by a factor of 2.5 to 4 while lifting water to a head of 1.55 m; and ii) Use of solar power to drive ventilation fans of greenhouse, for which an electronic circuit has been produced that uses maximum power-point tracking to maximize energy efficiency. Re-use of RO rejected concentrate for cooling saves water (6 l d-1 m-2) of greenhouse floor area and the improved fan could reduce electricity consumption by a factor 8.

Molecular mechanisms of salt effects on carbon nanotube dispersions in an organic solvent (N-methyl-2-pyrrolidone)

We consider the effects of salt (sodium iodide) on pristine carbon nanotube (CNT) dispersions in an organic solvent, N-methyl-2-pyrrolidone (NMP). We investigate the molecular-scale mechanisms of ion interactions with the nanotube surface and we show how the microscopic ion-surface interactions affect the stability of CNT dispersions in NMP. In our study we use a combination of fully atomistic Molecular Dynamics simulations of sodium and iodide ions at the CNT-NMP interface with direct experiments on the CNT dispersions. In the experiments we analyze the effects of salt on the stability of the dispersions by photoluminescence (PL) and optical absorption spectroscopy of the samples as well as by visual inspection. By fully atomistic Molecular Dynamics simulations we investigate the molecular-scale mechanisms of sodium and iodide ion interactions with the nanotube surface. Our simulations reveal that both ions are depleted from the CNT surface in the CNT-NMP dispersions mainly due to the two reasons: (1) there is a high energy penalty for the ion partial desolvation at the CNT surface; (2) NMP molecules form a dense solvation layer at the CNT surface that prevents ions to come close to the CNT surface. As a result, an increase of the salt concentration increases the "osmotic" stress in the CNT-NMP system and, thus, decreases the stability of the CNT dispersions in NMP. Direct experiments confirm the simulation results: addition of NaI salt into the NMP dispersions of pristine CNTs leads to precipitation of CNTs (bundle formation) even at very small salt concentration (∼10 -3 mol L -1). In line with the simulation predictions, the effect increases with the increase of the salt concentration. Overall, our results show that dissolved salt ions have strong effects on the stability of CNT dispersions. Therefore, it is possible to stimulate the bundle formation in the CNT-NMP dispersions and regulate the overall concentration of nanotubes in the dispersions by changing the NaI concentration in the solvent. © 2012 The Royal Society of Chemistry.

Efficient 1,4-addition of enones and boronic acids catalyzed by a Ni-Zn hydroxyl double salt-intercalated anionic rhodium(III) complex

Intercalation of an in situ prepared [Rh(OH)6]3- complex into an anion exchangeable Ni-Zn layered hydroxy double salt (Rh/NiZn) was demonstrated. The resulting Rh/NiZn effectively catalyzed the 1,4-addition of diverse enones and phenylboronic acids to their corresponding β-substituted carbonyl compounds. In the case of 2-cyclohexen-1-one and phenylboronic acid, a turnover frequency (TOF) of 920 h-1 based on Rh was achieved. The [Rh(OH)6]3- complex maintained its original monomeric trivalent state within the NiZn interlayer following catalysis, attributable to a strong electrostatic interaction between the NiZn host and anionic Rh(III) complex.

Hydrophenylation of internal alkynes with boronic acids catalysed by a Ni–Zn hydroxy double salt-intercalated anionic rhodium(III) complex

[Rh(OH)6]3− intercalated Ni–Zn mixed basic salt (Rh/NiZn) acts as an efficient catalyst for the hydrophenylation of internal alkynes with arylboronic acids under mild conditions. The turnover number per Rh site approached 740 in the reaction between 4-octyne and phenylboronic acid. The catalytic monomeric Rh(III) complex is stabilised within the NiZn interlayers, attributable to a strong electrostatic interaction, promoting its re-use.

Quantifying nitrogen cycling rates in freshwater marshes of the southern Everglades using nitrogen-15 tracer techniques

This dissertation research project addressed the question of how hydrologic restoration of the Everglades is impacting the nutrient dynamics of marsh ecosystems in the southern Everglades. These effects were analyzed by quantifying nitrogen (N) cycle dynamics in the region. I utilized stable isotope tracer techniques to investigate nitrogen uptake and cycling between the major ecosystem components of the freshwater marsh system. I recorded the natural isotopic signatures (δ15N and δ 13C) for major ecosystem components from the three major watersheds of the Everglades: Shark River Slough, Taylor Slough, and C-111 basin. Analysis of δ15 N and δ13C natural abundance data were used to demonstrate the spatial extent to which nitrogen from anthropogenic or naturally enriched sources is entering the marshes of the Everglades. In addition, I measured the fluxes on N between various ecosystem components at both near-canal and estuarine ecotone locations. Lastly, I investigated the effect of three phosphorus load treatments (0.00 mg P m-2, 6.66 mg P m-2, and 66.6 mg P m-2) on the rate and magnitude of ecosystem N-uptake and N-cycling. The δ15N and δ13C natural abundance data supported the hypothesis that ecosystem components from near-canal sites have heavier, more enriched δ 15N isotopic signatures than downstream sites. The natural abundance data also showed that the marshes of the southern Everglades are acting as a sink for isotopically heavier, canal-borne dissolved inorganic nitrogen (DIN) and a source for "new" marsh derived dissolved organic nitrogen (DON). In addition, the 15N mesocosm data showed the rapid assimilation of the 15N tracer by the periphyton component and the delayed N uptake by soil and macrophyte components in the southern Everglades.

Spatial scale and abundance patterns of large fish communities in freshwater marshes of the Florida Everglades

Anthropogenic habitat alterations and water-management practices have imposed an artificial spatial scale onto the once contiguous freshwater marshes of the Florida Everglades. To gain insight into how these changes may affect biotic communities, we examined whether variation in the abundance and community structure of large fishes (SL . 8 cm) in Everglades marshes varied more at regional or intraregional scales, and whether this variation was related to hydroperiod, water depth, floating mat volume, and vegetation density. From October 1997 to October 2002, we used an airboat electrofisher to sample large fishes at sites within three regions of the Everglades. Each of these regions is subject to unique watermanagement schedules. Dry-down events (water depth , 10 cm) occurred at several sites during spring in 1999, 2000, 2001, and 2002. The 2001 dry-down event was the most severe and widespread. Abundance of several fishes decreased significantly through time, and the number of days post-dry-down covaried significantly with abundance for several species. Processes operating at the regional scale appear to play important roles in regulating large fishes. The most pronounced patterns in abundance and community structure occurred at the regional scale, and the effect size for region was greater than the effect size for sites nested within region for abundance of all species combined, all predators combined, and each of the seven most abundant species. Non-metric multi-dimensional scaling revealed distinct groupings of sites corresponding to the three regions. We also found significant variation in community structure through time that correlated with the number of days post-dry-down. Our results suggest that hydroperiod and water management at the regional scale influence large fish communities of Everglades marshes.

Responses of sawgrass and spikerush to variation in hydrologic drivers and salinity in Southern Everglades marshes

Aboveground net primary production (ANPP) by the dominant macrophyte and plant community composition are related to the changing hydrologic environment and to salinity in the southern Everglades, FL, USA. We present a new non-destructive ANPP technique that is applicable to any continuously growing herbaceous system. Data from 16 sites, collected from 1998 to 2004, were used to investigate how hydrology and salinity controlled sawgrass (Cladium jamaicense Crantz.) ANPP. Sawgrass live biomass showed little seasonal variation and annual means ranged from 89 to 639 gdw m)2. Mortality rates were 20–35% of live biomass per 2 month sampling interval, for biomass turnover rates of 1.3–2.5 per year. Production by C. jamaicense was manifest primarily as biomass turnover, not as biomass accumulation. Rates typically ranged from 300 to 750 gdw m)2 year)1, but exceeded 1000 gdw m)2 year)1 at one site and were as high as 750 gdw m)2 year)1 at estuarine ecotone sites. Production was negatively related to mean annual water depth, hydroperiod, and to a variable combining the two (depth-days). As water depths and hydroperiods increased in our southern Everglades study area, sawgrass ANPP declined. Because a primary restoration goal is to increase water depths and hydroperiods for some regions of the Everglades, we investigated how the plant community responded to this decline in sawgrass ANPP. Spikerush (Eleocharis sp.) was the next most prominent component of this community at our sites, and 39% of the variability in sawgrass ANPP was explained by a negative relationship with mean annual water depth, hydroperiod, and Eleocharis sp. density the following year. Sawgrass ANPP at estuarine ecotone sites responded negatively to salinity, and rates of production were slow to recover after high salinity years. Our results suggest that ecologists, managers, and the public should not necessarily interpret a decline in sawgrass that may result from hydrologic restoration as a negative phenomenon.

Water Uptake Patterns of an Invasive Exotic Plant in Coastal Saline Habitats

Schinus terebinthifolius Raddi (Schinus) is one of the most widely found woody exotic species in South Florida. This exotic is distributed across environments with different hydrologic regimes, from upland pine forests to the edges of sawgrass marshes and into saline mangrove forests. To determine if this invasive exotic had different physiological attributes compared to native species in a coastal habitat, we measured predawn xylem water potentials (Ψ), oxygen stable isotope signatures (δ18O), and sodium (Na+) and potassium (K+) contents of sap water from plants within: (1) a transition zone (between a mangrove forest and upland pineland) and (2) an upland pineland in Southwest Florida. Under dynamic salinity and hydrologic conditions, Ψ of Schinus appeared less subject to fluctuations caused by seasonality when compared with native species. Although stem water δ18O values could not be used to distinguish the depth of Schinus and native species' water uptake in the transition zone, Ψ and sap Na+/K+ patterns showed that Schinus was less of a salt excluder relative to the native upland species during the dry season. This exotic also exhibited Na+/K+ ratios similar to the mangrove species, indicating some salinity tolerance. In the upland pineland, Schinus water uptake patterns were not significantly different from those of native species. Differences between Schinus and native upland species, however, may provide this exotic an advantage over native species within mangrove transition zones.

Spatial patterns of fish communities along two estuarine gradients in southern Florida

In tropical and subtropical estuaries, gradients of primary productivity and salinity are generally invoked to explain patterns in community structure and standing crops of fishes. We documented spatial and temporal patterns in fish community structure and standing crops along salinity and nutrient gradients in two subtropical drainages of Everglades National Park, USA. The Shark River drains into the Gulf of Mexico and experiences diurnal tides carrying relatively nutrient enriched waters, while Taylor River is more hydrologically isolated by the oligohaline Florida Bay and experiences no discernable lunar tides. We hypothesized that the more nutrient enriched system would support higher standing crops of fishes in its mangrove zone. We collected 50 species of fish from January 2000 to April 2004 at six sampling sites spanning fresh to brackish salinities in both the Shark and Taylor River drainages. Contrary to expectations, we observed lower standing crops and density of fishes in the more nutrient rich tidal mangrove forest of the Shark River than in the less nutrient rich mangrove habitats bordering the Taylor River. Tidal mangrove habitats in the Shark River were dominated by salt-tolerant fish and displayed lower species richness than mangrove communities in the Taylor River, which included more freshwater taxa and yielded relatively higher richness. These differences were maintained even after controlling for salinity at the time of sampling. Small-scale topographic relief differs between these two systems, possibly created by tidal action in the Shark River. We propose that this difference in topography limits movement of fishes from upstream marshes into the fringing mangrove forest in the Shark River system, but not the Taylor River system. Understanding the influence of habitat structure, including connectivity, on aquatic communities is important to anticipate effects of construction and operational alternatives associated with restoration of the Everglades ecosystem.