Ferric reducing antioxidant potential (FRAP) of antioxidants using reaction flow chromatography.

High performance liquid chromatography coupled with post column derivatisation (HPLC-PCD) may be used to profile the antioxidant content of a sample. There are, however, drawbacks in the use of HPLC-PCD setups; namely the high volume reaction coils that are typically used lowering the observed separation efficiency. Reaction flow chromatography has the ability to overcome these inefficiencies by using a more efficient mixing technique inside the outlet fitting itself, post column reaction loops can be removed with resulting improvement in signal to noise response, plus the separation efficiency is maintained. We assessed two methods of HPLC-PCD antioxidant analysis based on the ferric reducing antioxidant power (FRAP) assay in both conventional and reaction flow HPLC-PCD modes. It was found that the reaction flow technique demonstrated significant advantages over the conventional technique in terms of signal to noise, linear range, precision and observed separation efficiency.

Comparing the selectivity and chiral separation of d- and l- fluorenylmethyloxycarbonyl chloride protected amino acids in analytical high performance liquid chromatography and supercritical fluid chromatography; evaluating throughput, economic and environmental impact.

The chiral separation of d- and l- FMOC amino acids was undertaken using the Lux Cellulose-1 polysaccharide based chiral column in HPLC (normal phase and reverse phase) and SFC conditions. This was done to compare the relative selectivity and separation between the three separation modes and to evaluate the potential benefits of SFC separations with regards to resolution, throughput, economic and environmental impact. It was established that the separation of d- and l- FMOC amino acids in SFC displayed behaviours that were similar to both normal phase and reversed phase, rather than distinctly one or the other. Additionally, although reversed phase conditions yielded significantly higher resolution values between enantiomers across the range of amino acids studied, improvements in selectivity in SFC via the introduction of higher concentrations of formic acid in the mobile phase allowed for better resolution per unit of time. Moreover since the SFC mobile phase is composed mostly of recyclable CO2, there is a reduction in organic solvent consumption, which minimises the economic and environmental costs.

Minimally constrained model of self-organized helical states in reversed-field pinches.

We show that the self-organized single-helical-axis (SHAx) and double-axis (DAx) states in reversed field pinches can be reproduced in a minimally constrained equilibrium model using only five parameters. This is a significant reduction on previous representations of the SHAx which have required an infinite number of constraints. The DAx state, which has a nontrivial topology, has not previously been reproduced using an equilibrium model that preserves this topological structure. We show that both states are a consequence of transport barrier formation in the plasma core, in agreement with experimental results. We take the limit of zero pressure in this work, although the model is also valid for finite pressure.

Reaction flow chromatography for rapid post column derivatisations: the analysis of antioxidants in natural products.

The analysis of antioxidants from complex samples is conveniently achieved using liquid chromatography, which provides sample fraction, coupled with an on-line antioxidant assay, which provides detection. One particularly useful on-line antioxidant assay that has routinely been coupled with HPLC involves the diphenylpicrylhydrazyl radical (DPPH), which provides a positive test for phenolic antioxidants through a decolorisation of the DPPH reagent. A limitation of this assay, however, is the need to employ a reaction coil, which is often large with respect to the peak volume, consequently adding substantial band broadening to the separation. In this study we introduce a new concept that can be employed for systems requiring post column derivatisations, such as the DPPH assay. We have termed this 'reaction flow' chromatography, whereby, the derivatisation reagent can be added directly into one of the outlet ports of a parallel segmented flow column. Subsequently, the mixing between the derivatising reagent and the solute is very efficient removing the need to employ reaction coils. The concept is tested here using the DPPH assay for the analysis of antioxidants in samples derived from natural origin.

Implications to stormwater management as a result of lot scale rainwater tank systems: a case study in Western Sydney, Australia.

Rainwater tanks are increasingly adopted in Australia to reduce potable water demand and are perceived to reduce the volume of stormwater discharge from developments. This paper investigates the water balance of rainwater tanks, in particular the possible impacts these tanks could have in controlling the stormwater discharge volume. The study collected water quantity data from two sites in the Hawkesbury City Council area, New South Wales, Australia and utilised the collected data in a simple water balance model to assess the effectiveness of rainwater tanks in reducing the stormwater discharge volume. The results indicate that a significant reduction in discharge volume from a lot scale development can be achieved if the rainwater tank is connected to multiple end-uses, but is minimal when using irrigation alone. In addition, the commonly used volumetric runoff coefficient of 0.9 was found to over-estimate the runoff from the roof areas and to thereby under-estimate the available volume within the rainwater tanks for retention or detention. Also, sole reliance on the water in the rainwater tanks can make the users aware of their water use pattern and water availability, resulting in significant reductions in water use as the supply dwindles, through self-imposed water restrictions.

Anomalies in evaporative light scattering detection.

A two-dimensional (2-D) "heart-cutting" HPLC system was used to fractionate oligostyrenes into the respective diastereoisomers. For samples of known composition, the response of an ultraviolet (UV) absorbance detector followed the anticipated pattern. The response of an evaporative light-scattering (ELSD) detector on the other hand indicated quite different concentrations for the two diastereoisomers, relative to what was anticipated and what was indicated by the UV detector. Whereas approximately the same concentration was indicated by UV, ELSD in some cases indicated no detection of the later eluting isomer. The magnitude of the errors depended on both the molecular weight and the tacticity of the diastereomers. These anomalies appear to be an artifact of power transform functions imbedded within the firmware processor of the ELSD, invisible to the user.

Observation of transverse interference fringes on an atom laser beam.

Using the unique detection properties offered by metastable helium atoms we have produced high resolution images of the transverse spatial profiles of an atom laser beam. We observe fringes on the beam, resulting from quantum mechanical interference between atoms that start from rest at different transverse locations within the outcoupling surface and end up at a later time with different velocities at the same transverse position. Numerical simulations in the low output-coupling limit give good quantitative agreement with our experimental data.

Structural-chemical evolution within exfoliated clays.

The exfoliated (delaminated) structures of lamellar clays offer potential as precursors for the formation of various nanostructured materials. In this article, Lucentite and Laponite phyllosilicate clays, which both have empirical formulas of Na(0.33)[Mg(2.67)Li(0.33)Si4O10(OH)2] but differ in nanodimensions, have been exfoliated. Experiments were carried out for mixtures containing approximately 1 wt % phyllosilicate in a 5% aqueous solution of poly(acrylic acid) at different temperatures. X-ray diffraction and photoemission spectroscopy measurements for the solid products recovered after stirring the mixtures at 20 degrees C showed that the fully extended chains of poly(acrylic acid) were intercalated within the interlayer spaces between the silicate plates of the clays. At 85 degrees C, however, the clays were exfoliated and/or partially exfoliated. Photoemission spectroscopy also indicated that the exfoliated structures primarily consisted of silica nanoplates. 29Si nuclear magnetic resonance and oxygen K-edge near-edge X-ray absorption fine structure indicated that the surfaces of the plates were terminated by high concentrations of the silanol (-SiOH) groups, which created structural branches during intercalation. A model was developed in which intercalation and the removal of ions from the clays after the poly(acrylic acid) interactions reduced the electrostatic van der Waals forces between the plates. It was also shown that the formation of branches created a steric effect that inhibited the stacking of the plates. Together these resulted in exfoliation.

Dispersion of organically modified clays within n-alcohols.

A method for formation of polymer-clay nanocomposites involves dispersion of the nanometer silicate layers of clays into a solvent, followed by dispersion into polymers. The dispersion of layered silicates within solvents affects the structure and properties of the nanocomposites. We report the dispersion of organically modified clays, used for formation of nanocomposites with organic polymers, within a range of alcohol solvents. Experiments involved stirring a mixture containing approximately 1 wt% of alkylammonium-modified clays in n-alcohols with general molecular structure RnOH, where n represents the number of carbons of alkyl chains, varying from 2 to 8. The clays precipitated from the dispersion when RnOH solvents with n<5 were used, however, they formed gels for solvents with n5. The increased dispersion was related to the decrease of polarity and hydrogen bonding force within solvents. X-ray diffraction for the dispersed clays indicated that the interlayer spaces (1.8 nm), formed by regular stacking of the silicate layers, expanded to a maximum of 3.0 nm after treatment with RnOH with n5. The interlayer expansion was due to the intercalation of n-alcohol molecules within the interlayer spaces. It is suggested that the alkyl chains of n-alcohols remain parallel to the silicate surface in the intercalate. Preliminary experiments on the influence of these alcohol solvents on the intercalation of polyol (polyether) are also reported.