Influence of Hydrophilic Surface Specificity on the Structural Properties of Confined Water

The influence of chemical specificity of hydrophilic surfaces on the structure of confined water in the subnanometer regime is investigated using grand canonical Monte Carlo Simulations. The structural variations for water confined between hydroxylated silica surfaces are contrasted with water confined between mica surfaces. Although both surfaces are hydrophilic, our Study shows that hydration of potassium ions on the mica surface has a strong influence on the water Structure and solvation force response of confined water. In contrast to the disrupted hydrogen bond network observed for water confined between Mica Surfaces, water between silica surfaces retains its hydrogen bond network displaying bulklike structural features down to surface separations as small as 0.45 nm. Hydrogen bonding of all invariant contact water layer with the surface silanol groups aids in maintaining a constant number of hydrogen bonds per water molecule for the silica surfaces. As a consequence water depletion and rearrangement upon decreasing confinement is a strong function of the hydrophilic surface specificity, particularly at smaller separations. An oscillatory solvation force response is only observed for water confined between Silica surfaces, and bulklike features are observed for both Surfaces above a surface separation of about 1.2 nm. We evaluate and contrast the water density, dipole moment distributions, pi pair correlation functions, and solvation forces as a function of the surface separation.

Purification and properties of protocatechuate-3,4-dioxygenase from Tecoma stans L

Protocatechuate-3,4-dioxygenase from the leaves of Tecoma stans was purified to near homogeneity and some of its properties studied. It was optimally active at pH 5.2 and at 40°C. Its molecular weight of approx. 150 000 was determined by gel filtration on a Sephadex G-150 column. The Km value for protocatechuate was found to be 330 μM and for ferrous sulfate, 40 μM. The enzyme was highly specific for protocatechuate and did not attack any of the substrate analogues. None of the substrate analogues tested inhibited the enzyme activity. Sulfhydryl reagents inhibited the enzyme activity which could be partially reversed by sulfhydryl compounds. The dioxygenase activity was not associated with polyphenol oxidase activity.

Phylogeography and hybrid swarms: history of brackish water bivalve diversity in North European marginal seas

This study addressed the large-scale molecular zoogeography in two brackish water bivalve molluscs, Macoma balthica and Cerastoderma glaucum, and genetic signatures of the postglacial colonization of Northern Europe by them. The traditional view poses that M. balthica in the Baltic, White and Barents seas (i.e. marginal seas) represent direct postglacial descendants of the adjacent Northeast Atlantic populations, but this has recently been challenged by observations of close genetic affinities between these marginal populations and those of the Northeast Pacific. The primary aim of the thesis was to verify, quantify and characterize the Pacific genetic contribution across North European populations of M. balthica and to resolve the phylogeographic histories of the two bivalve taxa in range-wide studies using information from mitochondrial DNA (mtDNA) and nuclear allozyme polymorphisms. The presence of recent Pacific genetic influence in M. balthica of the Baltic, White and Barents seas, along with an Atlantic element, was confirmed by mtDNA sequence data. On a broader temporal and geographical scale, altogether four independent trans-Arctic invasions of Macoma from the Pacific since the Miocene seem to have been involved in generating the current North Atlantic lineage diversity. The latest trans-Arctic invasion that affected the current Baltic, White and Barents Sea populations probably took place in the early post-glacial. The nuclear genetic compositions of these marginal sea populations are intermediate between those of pure Pacific and Atlantic subspecies. In the marginal sea populations of mixed ancestry (Barents, White and Northern Baltic seas), the Pacific and Atlantic components are now randomly associated in the genomes of individual clams, which indicates both pervasive historical interbreeding between the previously long-isolated lineages (subspecies), and current isolation of these populations from the adjacent pure Atlantic populations. These mixed populations can be characterized as self-supporting hybrid swarms, and they arguably represent the most extensive marine animal hybrid swarms so far documented. Each of the three swarms still has a distinct genetic composition, and the relative Pacific contributions vary from 30 to 90 % in local populations. This diversity highlights the potential of introgressive hybridization to rapidly give rise to new evolutionarily and ecologically significant units in the marine realm. In the south of the Danish straits and in the Southern Baltic Sea, a broad genetic transition zone links the pure North Sea subspecies M. balthica rubra to the inner Baltic hybrid swarm, which has about 60 % of Pacific contribution in its genome. This transition zone has no regular smooth clinal structure, but its populations show strong genotypic disequilibria typical of a hybrid zone maintained by the interplay of selection and gene flow by dispersing pelagic larvae. The structure of the genetic transition is partly in line with features of Baltic water circulation and salinity stratification, with greater penetration of Atlantic genes on the Baltic south coast and in deeper water populations. In all, the scenarios of historical isolation and secondary contact that arise from the phylogeographic studies of both Macoma and Cerastoderma shed light to the more general but enigmatic patterns seen in marine phylogeography, where deep genetic breaks are often seen in species with high dispersal potential.

Sediment resuspension as a water quality regulator in lakes

Sediment resuspension, the return of the bottom material into the water column, is an important process that can have various effects on a lake ecosystem. Resuspension caused by wind-induced wave disturbance, currents, turbulent fluctuations and bioturbation affects water quality characteristics such as turbidity, light conditions, and concentrations of suspended solids (SS) and nutrients. Resuspension-mediated increase in turbidity may favour the dominance of phytoplankton over macrophytes. The predator-prey interactions contributing to the trophic state of a lake may also be influenced by increasing turbidity. Directly, the trophic state of a lake can be influenced by the effect of sediment resuspension on nutrient cycling. Resuspension enhances especially the cycling of phosphorus by bringing the sedimentary nutrients back into the water column and may thereby induce switches between phosphorus and nitrogen limitation. The contribution of sediment resuspension to gross sedimentation, turbidity, and concentration of SS and nutrients was studied in a small, deep lake as well as in a multibasin lake with deep and shallow areas. The effect of ice cover on sediment resuspension and thereby on phosphorus concentrations was also studied. The rates of gross sedimentation and resuspen¬sion were estimated with sediment traps and the associations between SS and nutrients were considered. Sediment resuspension, caused by wind activity, comprised most of the gross sedimenta¬tion and strongly contributed to the concentration of SS and turbidity in the lakes studied. Additionally, via the influence on SS, resuspension affected the concentration of total phosphorus (TP) and soluble reactive phosphorus (SRP), as well as the total nitrogen to total phosphorus (TN:TP) ratio. Although contrasting results concerning the dependence between the SS and SRP concentrations were observed, it could be concluded that sediment resuspension during strong algal blooms (pH > 9) led to aerobic release of P. The main findings of this thesis were that in the course of the growing season, sediment resuspension coupled with phytoplankton succession led to liberation of P from resuspended particles, which in turn resulted in high TP concentrations and low TN:TP ratios. This development was likely a cause of strong cyanobacterial blooms in midsummer.

Ion exchange of sodium chloride and sodium bicarbonate solutions using strong acid cation resins in relation to coal seam water treatment

Coal seam gas production has resulted in the production of large volumes of associated water which contains dissolved salts dominated by sodium chloride and sodium bicarbonate. Ion exchange using synthetic resins has been proposed as a method for desalination of coal seam water to make it suitable for various beneficial reuse options. This study investigated the behaviour of solutions of sodium chloride and sodium bicarbonate with respect to exchange with Lanxess S108H strong acid cation (SAC) resin. Equilibrium isotherms were created for solutions of NaCl and NaHCO3 and an actual sample of coal seam water from the Surat Basin in southern Queensland. The exchange of sodium ions arising from sodium bicarbonate was found to be considerably more favourable than exchange of sodium ions from sodium chloride solutions. This latter behaviour was attributed to the secondary decomposition of bicarbonate species under acidic conditions which resulted in the evolution of carbon dioxide and formation of water. The isotherm profiles could not be satisfactorily fitted by a single isotherm model such as the Langmuir expression. Instead, two Langmuir equations had to be simultaneously applied in order to fit the sections of the isotherm attributable to sodium ion exchange from sodium bicarbonate and sodium chloride. The shape of the isotherm profile was dependent upon the ratio of sodium chloride to sodium bicarbonate in solution and there was a high degree of correlation between simulated and actual coal seam water solutions.

Behaviour of natural zeolites used for the treatment of simulated and actual coal seam gas water

Coal seam gas operations produce significant quantities of associated water which often require demineralization. Ion exchange with natural zeolites has been proposed as a possible approach. The interaction of natural zeolites with solutions of sodium chloride and sodium bicarbonate in addition to coal seam gas water is not clear. Hence, we investigated ion exchange kinetics, equilibrium, and column behaviour of an Australian natural zeolite. Kinetic tests suggested that the pseudo first order equation best simulated the data. Intraparticle diffusion was part of the rate limiting step and more than one diffusion process controlled the overall rate of sodium ion uptake. Using a constant mass of zeolite and variable concentration of either sodium chloride or sodium bicarbonate resulted in a convex isotherm which was fitted by a Langmuir model. However, using a variable mass of zeolite and constant concentration of sodium ions revealed that the exchange of sodium ions with the zeolite surface sites was in fact unfavourable. Sodium ion exchange from bicarbonate solutions (10.3 g Na/kg zeolite) was preferred relative to exchange from sodium chloride solutions (6.4 g Na/kg zeolite). The formation of calcium carbonate species was proposed to explain the observed behaviour. Column studies of coal seam gas water showed that natural zeolite had limited ability to reduce the concentration of sodium ions (loading 2.1 g Na/kg zeolite) with rapid breakthrough observed. It was concluded that natural zeolites may not be suitable for the removal of cations from coal seam gas water without improvement of their physical properties.

Purification and some of the properties of a novel secondary alcohol dehydrogenase from Alcaligenes eutrophus

Alcaligenes eutrophus utilizing nerolidol, a sesquiterpene alcohol,as the sole source of carbon contains an inducible NAD(P)+-linked secondary alcohol dehydrogenase (SADH). The enzyme was purified to homogeneity by a combination of salt precipitation, ion exchange and affinity matri chromatographies. The apparent molecular mass of the enzyme was estimated to be 139 KDa with four identical subunits of 38.5 KDa. The enzyme carried out both oxidation and reduction reactions. At pH 5.5, enzyme catalyzed the stereospecific reduction of prochiral ketones to secondary alcohols. The pH optimum for the oxidation reaction was 9.5. NADP+ and NADPH were respectively preferred over NAD+ and NADH for oxidation and reduction reactions. Some of the properties of this enzyme were found to be significantly different from those thus far described.

Vitrification, relaxation and free volume in glycerol-water binary liquid mixture:Spin probe ESR studies

Glass transition and relaxation of the glycerol-water (G-W) binary mixture system have been studied over the glycerol concentration range of 5-85 mol% by using the highly sensitive technique of electron spin resonance (ESR). For the water rich mixture the glass transition,sensed by the dissolved spin probe, arises from the vitrified mesoscopic portion of the binary system. The concentration dependence of the glass transition temperature manifests a closely related molecular level cooperativity in the system. A drastic change in the mesoscopic structure of the system at the critical concentration of 40 mol is confirmed by an estimation of the spin probe effective volume in a temperature range where the tracer reorientation is strongly coupled to the system dynamics.

Purification of RNA polymerase from mycobacteria for optimized promoter-polymerase interactions

In vitro transcription analysis is important to understand the mechanism of transcription. Various assays for the analysis of initiation, elongation and termination form the basis for better understanding of the process. Purified RNA polymerase (RNAP) with high specific activity is necessary to carry out variety of these specific reactions. The RNAP purified from Mycobacterium smegmatis from exponential phase showed low promoter specificity in promoter-polymerase interaction studies. This is due to the presence of a large number of sigma factors during exponential phase and under-representation of sigma(A) required for house-keeping transcription. We describe an in vivo reconstitution of RNAP holoenzyme with sigma(A) and its purification, which resulted in holoenzyme with stoichiometric sigma(A) content. The reconstituted holoenzyme showed enhanced promoter-specific binding and promoter-specific-transcription activity compared to the enzyme isolated using standard procedure. Such in vivo reconstitution of stoichiometric holoenzyme could facilitate promoter-specific transcription assays, especially in organisms which encode a large number of sigma factors.

A shallow water AUV for benthic and water column observations

Autonomous underwater vehicles (AUVs) are becoming commonplace in the study of inshore coastal marine habitats. Combined with shipboard systems, scientists are able to make in-situ measurements of water column and benthic properties. In CSIRO, autonomous gliders are used to collect water column data, while surface vessels are used to collect bathymetry information through the use of swath mapping, bottom grabs, and towed video systems. Although these methods have provided good data coverage for coastal and deep waters beyond 50m, there has been an increasing need for autonomous in-situ sampling in waters less than 50m deep. In addition, the collection of benthic and water column data has been conducted separately, requiring extensive post-processing to combine data streams. As such, a new AUV was developed for in-situ observations of both benthic habitat and water column properties in shallow waters. This paper provides an overview of the Starbug X AUV system, its operational characteristics including vision-based navigation and oceanographic sensor integration.

Ce0.67Cr0.33O2.11: A New Low-Temperature O-2 Evolution Material and H-2 Generation Catalyst by Thermochemical Splitting of Water

Ce0.67Cr0.33O2.11 was synthesized by hydrothermal method using diethylenetriamine as complexing agent (Chem. Mater. 2008, 20, 7268). Ce0.67Cr0.33O2.11 being the only compound likes UO2+delta to have excess oxygen, it releases a large proportion of its lattice oxygen (0.167 M [O]/mole of compound) at relatively low temperature (465 degrees C) directly and it has been utilized for generation of H-2 by thermo-splitting of water. An almost stoichiometric amount of H-2 (0.152 M/Mole of compound) is generated at much lower temperature (65 degrees C). There is an almost comparable amount of oxygen release and hydrogen generation over this material at very low temperature comparedto other CeO2-MOx (Mn, Fe, Cu, and Ni) mixed-oxide solid solutions (O-2 evolution >= 1300 degrees C and H-2 generation at 1000 degrees C). The reversible nature of oxygen release and intake of this material is attributed to its fluorite Structure and coupling between the Ce4+/Ce3+ and Cr4+/6+/Cr3+ redox couples. Compound shows reversible oxygen release and intake by H2O absorption and subsequent hydrogen release to gain parent structure and hence this material can be utilized for generation of H-2 at very low temperature by thermo-chemical splitting of water.

Expression, purification and X-ray analysis of 1,3-propanediol dehydrogenase (Aq_1145) from Aquifex aeolicus VF5

1,3-Propanediol dehydrogenase is an enzyme that catalyzes the oxidation of 1,3-propanediol to 3-hydroxypropanal with the simultaneous reduction of NADP(+) to NADPH. SeMet-labelled 1,3-propanediol dehydrogenase protein from the hyperthermophilic bacterium Aquifex aeolicus VF5 was overexpressed in Escherichia coli and purified to homogeneity. Crystals of this protein were grown from an acidic buffer with ammonium sulfate as the precipitant. Single-wavelength data were collected at the selenium peak to a resolution of 2.4 angstrom. The crystal belonged to space group P3(2), with unit-cell parameters a = b = 142.19, c = 123.34 angstrom. The structure contained two dimers in the asymmetric unit and was solved by the MR-SAD approach.

Effect of Bottom Bubbling Conditions on Surface Reaction Rate in Oxygen-Water System

In secondary steelmaking, the enhancement of the reaction rate in the low carbon period during the decarburization of steel is considered the most effective method to produce ultralow carbon steel. In a previous study, it was revealed that the surface reaction is dominant during the final stage of the actual refining process. In order to improve the surface reaction rate, it is necessary to enlarge the reaction region, which is usually achieved by increasing the plume eye area. In this study, water model experiments were carried out to estimate the influence of bottom stirring conditions on the gas-liquid reaction rate; for this purpose, the deoxidation rate during the bottom bubbling process was measured. Five types of nozzle configurations were used to study the effect of the plume eye area on the reaction rate at various gas flow rates. The results reveal that the surface reaction rate is influenced by the gas flow rate and the plume eye area. An empirical correlation was developed for the reaction rate and the plume eye area. This correlation was applied to estimate the gas-liquid reaction rate mat the bath surface.