Structures of μOconotoxins from Conusmarmoreus. Inhibitors of tetrodotoxin (TTX)-sensitive and TTX-resistant sodium channels in mammalian sensory neurons

The μO-conotoxins are an intriguing class of conotoxins targeting various voltage-dependent sodium channels and molluscan calcium channels. In the current study, we have shown MrVIA and MrVIB to be the first known peptidic inhibitors of the transient tetrodotoxin-resistant (TTX-R) Na+ current in rat dorsal root ganglion neurons, in addition to inhibiting tetrodotoxin-sensitive Na+ currents. Human TTX-R sodium channels are a therapeutic target for indications such as pain, highlighting the importance of the μO-conotoxins as potential leads for drug development. Furthermore, we have used NMR spectroscopy to provide the first structural information on this class of conotoxins. MrVIA and MrVIB are hydrophobic peptides that aggregate in aqueous solution but were solubilized in 50% acetonitrile/water. The three-dimensional structure of MrVIB consists of a small β-sheet and a cystine knot arrangement of the three-disulfide bonds. It contains four backbone “loops” between successive cysteine residues that are exposed to the solvent to varying degrees. The largest of these, loop 2, is the most disordered part of the molecule, most likely due to flexibility in solution. This disorder is the most striking difference between the structures of MrVIB and the known δ- and ω-conotoxins, which along with the μO-conotoxins are members of the O superfamily. Loop 2 of ω-conotoxins has previously been shown to contain residues critical for binding to voltage-gated calcium channels, and it is interesting to speculate that the flexibility observed in MrVIB may accommodate binding to both sodium and molluscan calcium channels.

Coordination polymeric structures in the sodium salt of 4-chloro-3-nitrobenzoic acid and the sodium and potassium salts of 4-nitroanthranilic acid

The structures of the hydrated sodium salts of 4-chloro-3-nitrobenzoic acid {poly[aqua(μ4-4-chloro-3-nitrobenzoato)sodium(I)], [Na(C7H3ClNO4)(H2O)]n, (I)} and 2-amino-4-nitrobenzoic acid {poly[μ-aqua-aqua(μ3-2-amino-4-nitrobenzoato)sodium(I)], [Na(C7H5N2O4)(H2O)2]n, (II)}, and the hydrated potassium salt of 2-amino-4-nitrobenzoic acid {poly[μ-aqua-aqua(μ5-2-amino-4-nitrobenzoato)potassium(I)], [K(C7H5N2O4)(H2O)]n, (III)} have been determined and their complex polymeric structures described. All three structures are stabilized by intra- and intermolecular hydrogen bonding and strong π–π ring interactions. In the structure of (I), the distorted trigonal bipyrimidal NaO5 coordination polyhedron comprises a monodentate water molecule and four bridging carboxylate O-atom donors, generating a two-dimensional polymeric structure lying parallel to (001). Intra-layer hydrogen-bonding associations and strong inter-ring π–π interactions are present. Structure (II) has a distorted octahedral NaO6 stereochemistry, with four bridging O-atom donors, two from a single carboxylate group and two from a single nitro group and three from the two water molecules, one of which is bridging. Na centres are linked through centrosymmetric four-membered duplex water bridges and through 18-membered duplex head-to-tail ligand bridges. Similar centrosymmetric bridges are found in the structure of (III), and in both (II) and (III) strong inter-ring π–π interactions are found. A two-dimensional layered structure lying parallel to (010) is generated in (II), whereas in (III) the structure is three-dimensional. With (III), the irregular KO7 coordination polyhedron comprises a doubly bridging water molecule, a single bidentate bridging carboxylate O-atom donor and three bridging O-atom donors from the two nitro groups. A three-dimensional structure is generated. These coordination polymer structures are among the few examples of metal complexes of any type with either 4-chloro-3-nitrobenzoic acid or 4-nitroanthranilic acid.

Chemical and bioanalytical assessment of coal seam gas associated water

A comprehensive study was undertaken involving chemical (inorganic and organic) and bioanalytical (a suite of 14 in vitro bioassays) assessments of coal seam gas (coal bed methane) associated water (CSGW) in Queensland, Australia. CSGW is a by-product of the gas extraction process and is generally considered as water of poor quality. This was done to better understand what is known about the potential biological and environmental effects associated with the organic constituents of CSGW in Australia. In Queensland, large amounts of associated water must be withdrawn from coal seams to allow extraction of the gas. CSGW is disposed of via release to surface water, reinjected to groundwater or reused for irrigation of crops or pasture, supplied for power station cooling and or reinjected specifically to augment drinking water aquifers. Groundwater samples were collected from private wells tapping into the Walloon Coal Measures, the same coal aquifer exploited for coal seam gas production in the Surat Basin, Australia. The inorganic characteristics of these water samples were almost identical to the CSGW entering the nearby gas company operated Talinga-Condabri Water Treatment Facility. The water is brackish with a pH of 8 to 9, high sodium, bicarbonate and chloride concentrations but low calcium, magnesium and negligible sulphate concentrations. Only low levels of polyaromatic hydrocarbons (PAHs) were detected in the water samples, and neither phenols nor volatile organic compounds were found. Results from the bioassays showed no genotoxicity, protein damage, or activation of hormone receptors (with the exception of the estrogen receptor). However, five of the 14 bioassays gave positive responses: an arylhydrocarbon-receptor gene activation assay (AhR-CAFLUX), estrogenic endocrine activity (ERα-CALUX), oxidative stress response (AREc32), interference with cytokine production (THP1-CPA) and non-specific toxicity (Microtox). The observed effects were benchmarked against known water sources and were similar to secondary treated wastewater effluent, stormwater and surface water. As mixture toxicity modelling demonstrated, the detected PAHs explained less than 5% of the observed biological effects.

Crystal structure of poly[[di-mu2-aqua-aquasodium] 4-amino-3,5,6-trichloropyridine-2-carboxylate trihydrate], the sodium salt of the herbicide picloram

In the structure of the title complex [[Na(H2O)3]+ (C6H2Cl3N2O2)-^ . 3(H2O)]n, the Na salt of the herbicide picloram, the cation is a polymeric chain structure, based on doubly water-bridged NaO5 trigonal bipyramidal complex units which have in addition, a singly-bonded monodentate water molecule. Each of the bridges within the chain which lies along the a cell direction is centrosymmetric with Na...Na separations of 3.4807(16) and 3.5109(16)Ang. In the crystal, there are three water molecules of solvation and these, as well as the coordinated water molecules and the amino group of the 4-amino-3,5,6-trichloropicolinate anion are involved in extensive inter-species hydrogen-bonding interactions with carboxyl and water O-atoms as well as the pyridine N-atom. Among these association is a centrosymmetric cyclic tetra-water R4/4(8) ring , resulting in an overall three-dimensional structure.

The three-dimensional hydrogen-bonded structures in the ammonium and sodium salt hydrates of 4-aminophenylarsonic acid

The structures of two hydrated salts of 4-aminophenylarsonic acid (p-arsanilic acid), namely ammonium 4-aminophenylarsonate monohydrate, NH4(+)·C6H7AsNO3(-)·H2O, (I), and the one-dimensional coordination polymer catena-poly[[(4-aminophenylarsonato-κO)diaquasodium]-μ-aqua], [Na(C6H7AsNO3)(H2O)3]n, (II), have been determined. In the structure of the ammonium salt, (I), the ammonium cations, arsonate anions and water molecules interact through inter-species N-H...O and arsonate and water O-H...O hydrogen bonds, giving the common two-dimensional layers lying parallel to (010). These layers are extended into three dimensions through bridging hydrogen-bonding interactions involving the para-amine group acting both as a donor and an acceptor. In the structure of the sodium salt, (II), the Na(+) cation is coordinated by five O-atom donors, one from a single monodentate arsonate ligand, two from monodentate water molecules and two from bridging water molecules, giving a very distorted square-pyramidal coordination environment. The water bridges generate one-dimensional chains extending along c and extensive interchain O-H...O and N-H...O hydrogen-bonding interactions link these chains, giving an overall three-dimensional structure. The two structures reported here are the first reported examples of salts of p-arsanilic acid.

Evaluation of electrocoagulation for the pre-treatment of coal seam water

This work explored the applicability of electrocoagulation (EC) using aluminium electrodes for the removal of contaminants which can scale and foul reverse osmosis membranes from a coal seam (CS) water sample, predominantly comprising sodium chloride, and sodium bicarbonate. In general, the removal efficiency of species responsible for scaling and fouling was enhanced by increasing the applied current density/voltage and contact times (30–60 s) in the EC chamber. High removal efficiencies of species potentially responsible for scale formation in reverse osmosis units such as calcium (100%), magnesium (87.9%), strontium (99.3%), barium (100%) and silicates (98.3%) were achieved. Boron was more difficult to eliminate (13.3%) and this was postulated to be due to the elevated solution pH. Similarly, fluoride removal from solution (44%) was also inhibited by the presence of hydroxide ions in the pH range 9–10. Analysis of produced flocs suggested the dominant presence of relatively amorphous boehmite (AlOOH), albeit the formation of Al(OH)3 was not ruled out as the drying process employed may have converted aluminium hydroxide to aluminium oxyhydroxide species. Evidence for adsorption of contaminants on floc surface sites was determined from FTIR studies. The quantity of aluminium released during the electrocoagulation process was higher than the Faradaic amount which suggested that the high salt concentrations in the coal seam water had chemically reacted with the aluminium electrodes.

Index properties of illite-bentonite mixtures in electrolyte solutions

Bentonite, commonly used for liner constructions in waste containment systems, possesses many limitations. Illite or illite containing bentonite has been proposed as an alternative material for liner construction. Their properties in different types of pore fluids are important to assess the long-term performance of the liner. Further, the illite-bentonite interaction occurs and changes their properties. The effect of these interactions is known when the pore fluid is only water. How their properties are modified in electrolyte solutions has been brought out in this paper. The index properties have been studied since they give an indication of their engineering properties. Due to reduction in the thickness of the diffused double layer and consequent particle aggregation in bentonite, the effect of clay-clay interaction reduces in electrolyte solutions. In electrolyte solutions, the liquid limit, the plasticity index, and free swell index of bentonite are lower than illite. The plasticity index of bentonite is further reduced in KCI solution. Clays with a higher plasticity index perform better to retain pollutants and reduce permeability. Hence, the presence of both illite and bentonite ensures better performance of the liner in different fluids.

ESR measurements of the partitioning of some new spin probes in n-octanol-water

The stable free radical 1,1,3,3-tetramethylisoindolin-2-yloxyl (TMIO) has proved to be very suitable for use as a spin probe for a number of applications. Because it is soluble mainly in non-polar liquids, there is a need for new derivatives that can be used in a variety of environments. This has been done by introducing substituents in the 5-position of the aromatic ring, namely carboxyl (CTMIO), trimethylamino (TMTMIOI) and sodium sulphonate (NaTMIOS). An accurate ESR method was developed for the measurement of partition coefficients in n-octanol–water. For comparison purposes the method was also applied to some Tempo derivatives. The effect of temperature on the rotational correlation times and the nitrogen-14 hyperfine coupling constant of some of the spin probes was investigated. There is evidence for dimerization of CTMIO to form a biradical

High subsoil chloride concentrations reduce soil water extraction and crop yield on Vertosols in north-eastern Australia

Salinity, sodicity, acidity, and phytotoxic levels of chloride (Cl) in subsoils are major constraints to crop production in many soils of north-eastern Australia because they reduce the ability of crop roots to extract water and nutrients from the soil. The complex interactions and correlations among soil properties result in multi-colinearity between soil properties and crop yield that makes it difficult to determine which constraint is the major limitation. We used ridge-regression analysis to overcome colinearity to evaluate the contribution of soil factors and water supply to the variation in the yields of 5 winter crops on soils with various levels and combinations of subsoil constraints in the region. Subsoil constraints measured were soil Cl, electrical conductivity of the saturation extract (ECse), and exchangeable sodium percentage (ESP). The ridge regression procedure selected several of the variables used in a descriptive model, which included in-crop rainfall, plant-available soil water at sowing in the 0.90-1.10 m soil layer, and soil Cl in the 0.90-1.10 m soil layer, and accounted for 77-85% of the variation in the grain yields of the 5 winter crops. Inclusion of ESP of the top soil (0.0-0.10 m soil layer) marginally increased the descriptive capability of the models for bread wheat, barley and durum wheat. Subsoil Cl concentration was found to be an effective substitute for subsoil water extraction. The estimates of the critical levels of subsoil Cl for a 10% reduction in the grain yield were 492 mg cl/kg for chickpea, 662 mg Cl/kg for durum wheat, 854 mg Cl/kg for bread wheat, 980 mg Cl/kg for canola, and 1012 mg Cl/kg for barley, thus suggesting that chickpea and durum wheat were more sensitive to subsoil Cl than bread wheat, barley, and canola.

Subsoil constraints in Vertosols: Crop water use nutrient concentration, and grain yields of bread wheat, durum wheat, barley, chickpea and canola

Single or multiple factors implicated in subsoil constraints including salinity, sodicity, and phytotoxic concentrations of chloride (Cl) are present in many Vertosols including those occurring in Queensland, Australia. The variable distribution and the complex interactions that exist between these constraints limit the agronomic or management options available to manage the soil with these subsoil constraints. The identification of crops and cultivars adapted to these adverse subsoil conditions and/or able to exploit subsoil water may be an option to maintain productivity of these soils. We evaluated relative performance of 5 winter crop species, in terms of grain yields, nutrient concentration, and ability to extract soil water, grown on soils with various levels and combinations of subsoil constraints in 19 field experiments over 2 years. Subsoil constraints were measured by levels of soil Cl, electrical conductivity of the saturation extract (ECse), and exchangeable sodium percentage (ESP). Increasing levels of subsoil constraints significantly decreased maximum depth of water extraction, grain yield, and plant-available water capacity for all the 5 crops and more so for chickpea and durum wheat than bread wheat, barley, or canola. Increasing soil Cl levels had a greater restricting effect on water availability than did ECse and ESP. We developed empirical relationships between soil Cl, ECse, and ESP and crop lower limit (CLL) for estimating subsoil water extraction by 5 winter crops. However, the presence of gypsum influenced the ability to predict CLL based on the levels of ECse. Stronger relationships between apparent unused plant-available water (CLL - LL15; LL15 is lower limit at -1.5 MPa) and soil Cl concentrations than ESP or ECse suggested that the presence of high Cl in these soils most likely inhibited the subsoil water extraction by the crops. This was supported by increased sodium (Na) and Cl concentration with a corresponding decrease in calcium (Ca) and potassium (K) in young mature leaf of bread wheat, durum wheat, and chickpea with increasing levels of subsoil constraints. Of the 2 ions, Na and Cl, the latter appears to be more damaging than the former, resulting in plant dieback and reduced grain yields.

Interfacial area measurement in a gas - liquid ejector for a sodium chloride - air system

Interfacial area measurement has been carried out experimentally by measuring the bubble size and holdup for air-sodium chloride solution system. The size of the bubble is predominantly established by the air hold up. High speed photography technique for bubble size measurement and gamma ray attenuation method for holdup measurements are followed. The measured values are compared with the theoretically predicted values. Interracial area as a function of the liquid flow rate and also its distance from the nozzle of the ejector has been reported in this paper. The results obtained for this non-reactive system are also compared with those of air-water system.

Biodegradation of 1080: Testing soils in south-eastern Australia for sodium fluoroacetate-degrading micro-organisms

Sodium fluoroacetate (1080) is a vertebrate poison commonly used for the control of vertebrate pests in Australia. Long-term environmental persistence of 1080 from baiting operations has likely nontarget species and environmental impacts and is a matter of public concern. Defluorinating micro-organisms have been detected in soils of Western and central Australia, and Queensland, but not in south-eastern Australia. The presence or absence of defluorinating micro-organisms in soils from south-eastern Australia will assist in determining whether long-term environmental persistence of 1080 is or is not occurring. Soils from the Central West Slopes and Plains and Central Tablelands of New South Wales were sampled to investigate the presence and capability of 1080 defluorinating soil micro-organisms. Thirty-one species of micro-organisms were isolated from soils from each site after 10 days incubation in a 20 mM 1080 solution. Of these, 13 isolates showed measurable defluorinating ability when grown in a 1080 and sterile soil suspension. Two species, the bacteria Micromonospora, and the actinomycete Streptosporangium, have not been previously reported for their defluorinating ability. These results indicate that defluorinating micro-organisms are present in soils in south-eastern Australia, which adds weight to other studies that found that 1080 is subject to microbiological degradative processes following removal from the bait substrate. Soil micro-organism defluorination, in combination with physical breakdown and uptake by plants, indicates that fluoroacetate in soils and natural water ways is unlikely to persist. This has implications for the better informed use of 1080 in pest animal management programmes in south-eastern Australia.

Vibrational spectra and ferroelectric transition in sodium ammonium selenate dihydrate

The Raman and infrared absorption spectra of sodium ammonium selenate dihydrate (SASD) have been recorded both above and below the ferroelectric transition temperature. The deuterated SASD has also been investigated. The results support the view that while there is only one type of NH4+ ions in the para electric phase, there are two types of NH4+ ions below Tc. The water molecules undergo considerable change and non-equivalent O-H bonds are produced below Tc. The SeO2/4- ions undergo very little change.

Bentonite can decrease ammonia volatilisation losses from poultry litter: laboratory studies

Ammonia volatilisation from manure materials within poultry sheds can adversely affect production, and also represents a loss of fertiliser value from the spent litter. This study sought to compare the ability of alum and bentonite to decrease volatilisation losses of ammonia from spent poultry litter. An in-vessel volatilisation trial with air flushing, ammonia collection, and ammonia analysis was conducted over 64 days to evaluate the mitigation potential of these two materials. Water-saturated spent litter was incubated at 25°C in untreated condition (control) or with three treatments: an industry-accepted rate of alum [4% Al2(SO4)3·18H2O by dry mass of litter dry mass; ALUM], air-dry bentonite (127% by dry mass; BENT), or water-saturated bentonite (once again at 127% by dry mass; SATBENT). A high proportion of the nitrogen contained in the untreated spent litter was volatilised (62%). Bentonite additions were superior to alum additions at retaining spent litter ammonia (nitrogen losses: 15%, SATBENT; 34%, BENT; 54%, ALUM). Where production considerations favour comparable high rates of bentonite addition (e.g. where the litter is to be re-formulated as a fertiliser), this clay has potential to decrease ammonia volatilisation either in-shed or in spent litter stockpiles or formulated products, without the associated detrimental effect of alum on phosphorus availability.