Observations on catalysis by hammerhead ribozymes are consistent with a two-divalent-metal-ion mechanism

Significant cleavage by hammerhead ribozymes requires activation by divalent metal ions. Several models have been proposed to account for the influence of metal ions on hammerhead activity. A number of recent papers have presented data that have been interpreted as supporting a one-metal-hydroxide-ion mechanism. In addition, a solvent deuterium isotope effect has been taken as evidence against a proton transfer in the rate-limiting step of the cleavage reaction. We propose that these data are more easily explained by a two-metal-ion mechanism that does not involve a metal hydroxide, but does involve a proton transfer in the rate-limiting step.

Studies on the surface properties of biodegradable polymer carriers in respiratory delivery of drug from Dry Powder Inhaler formulations

Dry Powder Inhaler (DPI) technology has a significant impact in the treatment of various respiratory disorders. DPI formulations consist of a micronized drug (<5ìm) blended with an inert coarse carrier, for which lactose is widely used to date. DPIs are one of the inhalation devices which are used to target the delivery of drugs to the lungs. Drug delivery via DPI formulations is influenced by the physico-chemical characteristics of lactose particles such as size, shape, surface roughness and adhesional forces. Commercially available DPI formulations, which utilise lactose as the carrier, are not efficient in delivering drug to the lungs. The reasons for this are the surface morphology, adhesional properties and surface roughness of lactose. Despite several attempts to modify lactose, the maximum efficient drug delivery to the lungs remains limited; hence, exploring suitable alternative carriers for DPIs is of paramount importance. Therefore, the objective of the project was to study the performance of spherical polymer microparticles as drug carriers and the factors controlling their performance. This study aimed to use biodegradable polymer microspheres as alternative carriers to lactose in DPIs for achieving efficient drug delivery into the lungs. This project focused on fabricating biodegradable polymer microparticles with reproducible surface morphology and particle shape. The surface characteristics of polymeric carriers and the adhesional forces between the drug and carrier particles were investigated in order to gain a better understanding of their influence on drug dispersion. For this purpose, two biodegradable polymers- polycaprolactone (PCL) and poly (DL-lactide-co-glycolide) (PLGA) were used as the carriers to deliver the anti-asthmatic drug - Salbutamol Sulphate (SS). The first study conducted for this dissertation was the aerosolization of SS from mixtures of SS and PCL or PLGA microparticles. The microparticles were fabricated using an emulsion technique and were characterized by laser diffraction for particle size analysis, Scanning Electron Microscopy (SEM) for surface morphology and X-ray Photoelectron Spectroscopy (XPS) to obtain surface elemental composition. The dispersion of the drug from the DPI formulations was determined by using a Twin Stage Impinger (TSI). The Fine particle Fraction (FPF) of SS from powder mixtures was analyzed by High Performance Liquid Chromatography (HPLC). It was found that the drug did not detach from the surface of PCL microspheres. To overcome this, the microspheres were coated with anti-adherent agents such as magnesium stearate and leucine to improve the dispersion of the drug from the carrier surfaces. It was found that coating the PCL microspheres helped in significantly improving the FPF of SS from the PCL surface. These results were in contrast to the PLGA microspheres which readily allowed detachment of the SS from their surface. However, coating PLGA microspheres with antiadherent agents did not further improve the detachment of the drug from the surface. Thus, the first part of the study demonstrated that the surface-coated PCL microspheres and PLGA microspheres can be potential alternatives to lactose as carriers in DPI formulations; however, there was no significant improvement in the FPF of the drug. The second part of the research studied the influence of the size of the microspheres on the FPF of the drug. For this purpose, four different sizes (25 ìm, 48 ìm, 100 ìm and 150 ìm) of the PCL and PLGA microspheres were fabricated and characterized. The dispersion of the drug from microspheres of different sizes was determined. It was found that as the size of the carrier increased there was a significant increase in the FPF of SS. This study suggested that the size of the carrier plays an important role in the dispersion of the drug from the carrier surface. Subsequent experiments in the third part of the dissertation studied the surface properties of the polymeric carrier. The adhesion forces existing between the drug particle and the polymer surfaces, and the surface roughness of the carriers were quantified using Atomic Force Microscopy (AFM). A direct correlation between adhesion forces and dispersion of the drug from the carrier surface was observed suggesting that adhesion forces play an important role in determining the detachment potential of the drug from the carrier surface. However, no direct relationship between the surface roughness of the PCL or PLGA carrier and the FPF of the drug was observed. In conclusion, the body of work presented in this dissertation demonstrated the potential of coated PCL microspheres and PLGA microspheres to be used in DPI formulations as an alternative carrier to sugar based carriers. The study also emphasized the role of the size of the carrier particles and the forces of interaction prevailing between the drug and the carrier particle surface on the aerosolization performances of the drug.

Synthesis and characterisation of layered double hydroxides and their application for water purification

Layered doubly hydroxides (LDHs) also known as hydrotalcites or anionic clays are a group of clay minerals that have shown promise for the removal of toxic anions from water through both anion exchange and a process known as the reformation effect. This project has involved the preparation and characterisation of LDH materials as well as the investigation of their ability to remove selected anions from aqueous solutions by the reformation effect. The LDH materials were successfully prepared from magnesium, aluminium, zinc and chromium chloride salts using the co-precipitation method. Samples were characterised using powder X-ray diffraction (XRD) and thermogravimetry (TG) to confirm the presence of LDHs. Powder XRD revealed a characteristic LDH structure for all LDH samples. Thermal Analysis showed decomposition usual occurred through a three or four step process as expected for LDHs. Preliminary investigations of the removal of sulfate, nitrate and fluoride by an Mg/Al LDH were carried out, and the products were characterised using XRD and TG which showed that an LDH material similar to the original hydrotalcite was formed after reformation. A Zn/Al LDH was investigated as a potential sorbent material for the removal of iodine and iodide from water. It was found that the LDH was a suitable adsorbent which is able to remove almost all of the iodine present in the test solutions. Again, the products were characterised by XRD, TG and evolved gas mass spectrometry (EGMS) in an attempt to better understand the iodine removal process. Powder XRD showed successful reformation of the LDH structure and TG/EGMS showed that only a small amount of iodine species were lost during thermal decomposition. Finally, the mineral stichtite a Mg/Cr LDH was successfully synthesised and investigated using XRD, TG and EGMS. Unfortunately, due to lack of time it was not possible to identify any new uses for the mineral stichtite in the current project.

Coal seam gas waters - their geochemical signature and potential environmental implications

Coal Seam Gas (CSG) is a form of natural gas (mainly methane) sorbed in underground coal beds. To mine this gas, wells are drilled directly into an underground coal seam and groundwater (CSG water) is pumped out to the surface. This lowers the downhole piezometric pressure and enables gas desporption from the coal matrix. In the United States, this gas has been extracted commercially since the 1980s. The economic success of US CSG projects has inspired exploration and development in Australia and New Zealand. In Australia, Queensland’s Bowen and Surat basins have been the subject of increased CSG development over the last decade. CSG growth in other Australian basins has not matured to the same level but exploration and development are taking place at an accelerated pace in the Sydney Basin (Illawarra and the Hunter Valley, NSW) and in the Gunnedah Basin. Similarly, CSG exploration in New Zealand has focused in the Waikato region (Maramarua and Huntly), in the West Coast region (Buller, Reefton, and Greymouth), and in Southland (Kaitangata, Mataura, and Ohai). Figure 1 shows a Shcoeller diagram with CSG samples from selected basins in Australia, New Zealand, and the USA. CSG water from all of these basins exhibit the same geochemical signature – low calcium, low magnesium, high bicarbonate, low sulphate and, sometimes, high chloride. This water quality is a direct result of specific biological and geological processes that have taken part in the formation of CSG. In general, these processes include the weathering of rocks (carbonates, dolomite, and halite), cation exchange with clays (responsible for enhanced sodium and depleted calcium and magnesium), and biogenic processes (accounting for the presence of high bicarbonate concentrations). The salinity of CSG waters tends to be brackish (TDS < 30000 mg/l) with a fairly neutral pH. These particular characteristics need to be taken into consideration when assessing water management and disposal alternatives. Environmental issues associated with CSG water disposal have been prominent in developed basins such as the Powder River Basin (PRB) in the United States. When disposed on the land or used for irrigation, water having a high dissolved salts content may reduce water availability to crops thus affecting crop yield. In addition, the high sodium, low calcium and low magnesium concentrations increase the potential to disperse soils and significantly reduce the water infiltration rate. Therefore, CSG waters need to be properly characterised, treated, and disposed to safeguard the environment without compromising other natural resources.

Infrared spectra of Mg-SiO smokes : comparison with analytical electron microscopy studies

An important component of current models for interstellar and circumstellar evolution is the infrared (IR)spectral data collected from stellar outflows around oxygen-rich stars and from the general interstellar medium [1]. IR spectra from these celestial bodies are usually interpreted as showing the general properties of sub-micron sized silicate grains [2]. Two major features at 10 and 20 microns are reasonably attributed to amorphous olivine or pyroxene (e.g. Mg2Si04 or MgSi03) on the basis of comparisons with natural standards and vapor condensed silicates [3-6]. In an attempt to define crystallisation rates for spectrally amorphous condensates, Nuth and Donn [5] annealed experimentally produced amorphous magnesium silicate smokes at 1000K. On analysing these smokes at various annealing times, Nuth and Donn [5] showed that changes in crystallinity measured by bulk X-ray diffraction occured at longer annealing times (days) than changes measured by IR spectra (a few hours). To better define the onset of crystallinity in these magnesium silicates, we have examined each annealed product using a JEOL 1OOCX analytical electron microscope (AEM). In addition, the development of chemical diversity with annealing has been monitored using energy dispersive spectroscopy of individual grains from areas <20nm in diameter. Furthermore, the crystallisation kinetics of these smokes under ambient, room temperature conditions have been examined using bulk and fourier transform infrared (FTIR)spectra.

ESEM study of authigenic chlorite acid sensitivity in sandstone reservoirs

The effect of HCl on authigenic chlorite in three different sandstones has been examined uisng an Environmental Scanning Electron Microscope (ESEM), together with conventional analytical techniques. The ESEM enabled chlorites to be directly observed in situ at high magnifications during HCl treatment, and was particularly effective in allowing the same chlorite areas to be closely compared before and after acid treatment. Chlorites were reacted with 1M to 10M HCl at temperatures up to 80°C and for periods up to five months. After all treatments, chlorites show extensive leaching of iron, magnesium and aluminum, and their crystalline structure is destroyed. However, despite these major compositional and structural changes, chlorites show little or no visible evidence of acid attack, with precise morphological detail of individual plates preserved in all samples following acid treatments. Chlorite dissolution, sensu stricto, did not occur as a result of acidization of the host sandstones. Acid-treated chlorides are likely to exits in a structurally weakened state that may make them susceptible to physical disintegration during fluid flow. Accordingly, fines migration may be a significant engineering problem associated with the acidization of chlorite-bearing sandstones. © 1993.

Assessment of the molecular structure of the borate mineral sakhaite Ca12Mg4(BO3)7(CO3)4Cl(OH)2·H2O using vibrational spectroscopy

The structure of the borate mineral sakhaite Ca12Mg4(BO3)7(CO3)4Cl(OH)2·H2O, a borate–carbonate of calcium and magnesium has been assessed using vibrational spectroscopy. Assignment of bands is undertaken by comparison with the data from other published results. Intense Raman band at 1134 cm−1 with a shoulder at 1123 cm−1 is assigned to the symmetric stretching mode. The Raman spectrum displays bands at 1479, 1524 and 1560 cm−1 which are assigned to the antisymmetric stretching vibrations. The observation of multiple carbonate stretching bands supports the concept that the carbonate units are non-equivalent. The Raman band at 968 cm−1 with a shoulder at 950 cm−1 is assigned to the symmetric stretching mode of trigonal boron. Raman bands at 627 and 651 cm−1 are assigned to the out-of-plane bending modes of trigonal and tetrahedral boron. Raman spectroscopy coupled with infrared spectroscopy enables the molecular structure of the mineral sakhaite to be assessed.

Assessment of the molecular structure of the borate mineral boracite Mg3B7O13Cl using vibrational spectroscopy

Boracite is a magnesium borate mineral with formula: Mg3B7O13Cl and occurs as blue green, colorless, gray, yellow to white crystals in the orthorhombic – pyramidal crystal system. An intense Raman band at 1009 cm−1 was assigned to the BO stretching vibration of the B7O13 units. Raman bands at 1121, 1136, 1143 cm−1 are attributed to the in-plane bending vibrations of trigonal boron. Four sharp Raman bands observed at 415, 494, 621 and 671 cm−1 are simply defined as trigonal and tetrahedral borate bending modes. The Raman spectrum clearly shows intense Raman bands at 3405 and 3494 cm−1, thus indicating that some Cl anions have been replaced with OH units. The molecular structure of a natural boracite has been assessed by using vibrational spectroscopy.

Variability in estimation of self-reported dietary intake data from elite athletes resulting from coding by different sports dietitians

A routine activity for a sports dietitian is to estimate energy and nutrient intake from an athlete's self-reported food intake. Decisions made by the dietitian when coding a food record are a source of variability in the data. The aim of the present study was to determine the variability in estimation of the daily energy and key nutrient intakes of elite athletes, when experienced coders analyzed the same food record using the same database and software package. Seven-day food records from a dietary survey of athletes in the 1996 Australian Olympic team were randomly selected to provide 13 sets of records, each set representing the self-reported food intake of an endurance, team, weight restricted, and sprint/power athlete. Each set was coded by 3-5 members of Sports Dietitians Australia, making a total of 52 athletes, 53 dietitians, and 1456 athlete-days of data. We estimated within- and between- athlete and dietitian variances for each dietary nutrient using mixed modeling, and we combined the variances to express variability as a coefficient of variation (typical variation as a percent of the mean). Variability in the mean of 7-day estimates of a nutrient was 2- to 3-fold less than that of a single day. The variability contributed by the coder was less than the true athlete variability for a 1-day record but was of similar magnitude for a 7-day record. The most variable nutrients (e.g., vitamin C, vitamin A, cholesterol) had approximately 3-fold more variability than least variable nutrients (e.g., energy, carbohydrate, magnesium). These athlete and coder variabilities need to be taken into account in dietary assessment of athletes for counseling and research.

Nature and genesis of clay minerals of the Rustler Formation in the vicinity of the Waste Isolation Pilot Plant in Souteastern New Mexico

Detailed mineralogical studies of the matrix and fracture-fill materials of a large number of samples from the Rustler Formation have been carried out using x-ray diffraction, high-resolution transmission electron microscopy, electron microprobe analysis, x-ray fluorescence, and atomic absorption spectrophotometry. These analyses indicate the presence of four clay minerals: interstratified chlorite/saponite, illite, chlorite, and serpentine. Corrensite (regularly stratified chlorite/saponite) is the dominant clay mineral in samples from the Culebra dolomite and two shale layers of the lower unnamed member of the Rustler Formation. Within other layers of the Rustler Formation, disordered mixed chlorite/saponite is usually the most abundant clay mineral. Studies of the morphology and composition of clay crystallites suggest that the corrensite was formed by the alteration of detrital dioctahedral smectite in magnesium-rich pore fluids during early diagenesis of the Rustler Formation. This study provides initial estimates of the abundance and nature of the clay minerals in the Culebra dolomite in the vicinity of the Waste Isolation Pilot Plant.

Vibrational spectroscopy of the borate mineral kotoite Mg3(BO3)2

Vibrational spectroscopy has been used to assess the structure of kotoite a borate mineral of magnesium which is isostructural with jimboite. The mineral is orthorhombic with point group: 2/m 2/m 2/m. The mineral has the potential as a new memory insulator material. The mineral has been characterised by a combination of Raman and infrared spectroscopy. The Raman spectrum is dominated by a very intense band at 835 cm−1, assigned to the symmetric stretching mode of tetrahedral boron. Raman bands at 919, 985 and 1015 cm−1 are attributed to the antisymmetric stretching modes of tetrahedral boron. Kotoite is strictly an hydrous borate mineral. An intense Raman band observed at 3559 cm−1 is attributed to the stretching vibration of hydroxyl units, more likely to be associated with the borate mineral hydroxyborate. The lack of observation of water bending modes proves the absence of water in the kotoite structure.

A vibrational spectroscopic study of the phosphate mineral zanazziite - Ca2(MgFe2+)(MgFe2+Al)4Be4(PO4)6⋅6(H2O)

Zanazziite is the magnesium member of a complex beryllium calcium phosphate mineral group named roscherite. The studied samples were collected from the Ponte do Piauí mine, located in Itinga, Minas Gerais. The mineral was studied by electron microprobe, Raman and infrared spectroscopy. The chemical formula can be expressed as Ca2.00(Mg3.15,Fe0.78,Mn0.16,Zn0.01,Al0.26,Ca0.14)Be4.00(PO4)6.09(OH)4.00⋅5.69(H2O) and shows an intermediate member of the zanazziite–greinfeinstenite series, with predominance of zanazziite member. The molecular structure of the mineral zanazziite has been determined using a combination of Raman and infrared spectroscopy. A very intense Raman band at 970 cm−1 is assigned to the phosphate symmetric stretching mode whilst the Raman bands at 1007, 1047, 1064 and 1096 cm−1 are attributed to the phosphate antisymmetric stretching mode. The infrared spectrum is broad and the antisymmetric stretching bands are prominent. Raman bands at 559, 568, 589 cm−1 are assigned to the ν4 out of plane bending modes of the PO4 and HPO4 units. The observation of multiple bands supports the concept that the symmetry of the phosphate unit in the zanazziite structure is reduced in symmetry. Raman bands at 3437 and 3447 cm−1 are attributed to the OH stretching vibrations; Raman bands at 3098 and 3256 are attributed to water stretching vibrations. The width and complexity of the infrared spectral profile in contrast to the well resolved Raman spectra, proves that the pegmatitic phosphates are better studied with Raman spectroscopy.

Vibrational spectroscopy of the phosphate mineral kovdorskite – Mg2PO4(OH)⋅3H2O

The mineral kovdorskite Mg2PO4(OH)�3H2O was studied by electron microscopy, thermal analysis and vibrational spectroscopy. A comparison of the vibrational spectroscopy of kovdorskite is made with other magnesium bearing phosphate minerals and compounds. Electron probe analysis proves the mineral is very pure. The Raman spectrum is characterized by a band at 965 cm�1 attributed to the PO3� 4 m1 symmetric stretching mode. Raman bands at 1057 and 1089 cm�1 are attributed to the PO3�4 m3 antisymmetric stretching modes. Raman bands at 412, 454 and 485 cm�1 are assigned to the PO3�4 m2 bending modes. Raman bands at 536, 546 and 574 cm�1 are assigned to the PO3�4 m4 bending modes. The Raman spectrum in the OH stretching region is dominated by a very sharp intense band at 3681 cm�1 assigned to the stretching vibration of OH units. Infrared bands observed at 2762, 2977, 3204, 3275 and 3394 cm�1 are attributed to water stretching bands. Vibrational spectroscopy shows that no carbonate bands are observed in the spectra; thus confirming the formula of the mineral as Mg2PO4(OH)�3H2O.

Mg-based nanocomposites with high capacity and fast kinetics for hydrogen storage

Magnesium and its alloys have shown a great potential in effective hydrogen storage due to their advantages of high volumetric/gravimetric hydrogen storage capacity and low cost. However, the use of these materials in fuel cells for automotive applications at the present time is limited by high hydrogenation temperature and sluggish sorption kinetics. This paper presents the recent results of design and development of magnesium-based nanocomposites demonstrating the catalytic effects of carbon nanotubes and transition metals on hydrogen adsorption in these materials. The results are promising for the application of magnesium materials for hydrogen storage, with significantly reduced absorption temperatures and enhanced ab/desorption kinetics. High level Density Functional Theory calculations support the analysis of the hydrogenation mechanisms by revealing the detailed atomic and molecular interactions that underpin the catalytic roles of incorporated carbon and titanium, providing clear guidance for further design and development of such materials with better hydrogen storage properties.

The role of Ti as a catalyst for the dissociation of hydrogen on a Mg(0001) surface

In this paper, the dissociative chemisorption of hydrogen on both pure and Ti-incorporated Mg(0001) surfaces are studied by ab initio density functional theory (DFT) calculations. The calculated dissociation barrier of hydrogen molecule on a pure Mg(0001) surface (1.05 eV) is in good agreement with comparable theoretical studies. For the Ti-incorporated Mg(0001) surface, the activated barrier decreases to 0.103 eV due to the strong interaction between the molecular orbital of hydrogen and the d metal state of Ti. This could explain the experimentally observed improvement in absorption kinetics of hydrogen when transition metals have been introduced into the magnesium materials.