Comprehensive Two-Dimensional Gas Chromatography: Instrumental and Methodological Development

Comprehensive two-dimensional gas chromatography (GC×GC) offers enhanced separation efficiency, reliability in qualitative and quantitative analysis, capability to detect low quantities, and information on the whole sample and its components. These features are essential in the analysis of complex samples, in which the number of compounds may be large or the analytes of interest are present at trace level. This study involved the development of instrumentation, data analysis programs and methodologies for GC×GC and their application in studies on qualitative and quantitative aspects of GC×GC analysis. Environmental samples were used as model samples. Instrumental development comprised the construction of three versions of a semi-rotating cryogenic modulator in which modulation was based on two-step cryogenic trapping with continuously flowing carbon dioxide as coolant. Two-step trapping was achieved by rotating the nozzle spraying the carbon dioxide with a motor. The fastest rotation and highest modulation frequency were achieved with a permanent magnetic motor, and modulation was most accurate when the motor was controlled with a microcontroller containing a quartz crystal. Heated wire resistors were unnecessary for the desorption step when liquid carbon dioxide was used as coolant. With use of the modulators developed in this study, the narrowest peaks were 75 ms at base. Three data analysis programs were developed allowing basic, comparison and identification operations. Basic operations enabled the visualisation of two-dimensional plots and the determination of retention times, peak heights and volumes. The overlaying feature in the comparison program allowed easy comparison of 2D plots. An automated identification procedure based on mass spectra and retention parameters allowed the qualitative analysis of data obtained by GC×GC and time-of-flight mass spectrometry. In the methodological development, sample preparation (extraction and clean-up) and GC×GC methods were developed for the analysis of atmospheric aerosol and sediment samples. Dynamic sonication assisted extraction was well suited for atmospheric aerosols collected on a filter. A clean-up procedure utilising normal phase liquid chromatography with ultra violet detection worked well in the removal of aliphatic hydrocarbons from a sediment extract. GC×GC with flame ionisation detection or quadrupole mass spectrometry provided good reliability in the qualitative analysis of target analytes. However, GC×GC with time-of-flight mass spectrometry was needed in the analysis of unknowns. The automated identification procedure that was developed was efficient in the analysis of large data files, but manual search and analyst knowledge are invaluable as well. Quantitative analysis was examined in terms of calibration procedures and the effect of matrix compounds on GC×GC separation. In addition to calibration in GC×GC with summed peak areas or peak volumes, simplified area calibration based on normal GC signal can be used to quantify compounds in samples analysed by GC×GC so long as certain qualitative and quantitative prerequisites are met. In a study of the effect of matrix compounds on GC×GC separation, it was shown that quality of the separation of PAHs is not significantly disturbed by the amount of matrix and quantitativeness suffers only slightly in the presence of matrix and when the amount of target compounds is low. The benefits of GC×GC in the analysis of complex samples easily overcome some minor drawbacks of the technique. The developed instrumentation and methodologies performed well for environmental samples, but they could also be applied for other complex samples.

An Investigation of Environmental Conditions Experienced During the Life of High Value Wood Components and Products

Australian forest industries have a long history of export trade of a wide range of products from woodchips(for paper manufacturing), sandalwood (essential oils, carving and incense) to high value musical instruments, flooring and outdoor furniture. For the high value group, fluctuating environmental conditions brought on by changes in mperature and relative humidity, can lead to performance problems due to consequential swelling, shrinkage and/or distortion of the wood elements. A survey determined the types of value-added products exported, including species and dimensions packaging used and export markets. Data loggers were installed with shipments to monitor temperature and relative humidity conditions. These data were converted to timber equilibrium moisture content values to provide an indication of the environment that the wood elements would be acclimatising to. The results of the initial survey indicated that primary high value wood export products included guitars, flooring, decking and outdoor furniture. The destination markets were mainly located in the northern hemisphere, particularly the United States of America, China, Hong Kong, Europe including the United Kingdom), Japan, Korea and the Middle East. Other regions importing Australian-made wooden articles were south-east Asia, New Zealand and South Africa. Different timber species have differing rates of swelling and shrinkage, so the types of timber were also recorded during the survey. Results from this work determined that the major species were ash-type eucalypts from south-eastern Australia (commonly referred to in the market as Tasmanian oak), jarrah from Western Australia, spotted gum, hoop pine, white cypress, black butt, brush box and Sydney blue gum from Queensland and New South Wales. The environmental conditions data indicated that microclimates in shipping containers can fluctuate extensively during shipping. Conditions at the time of manufacturing were usually between 10 and 12% equilibrium moisture content, however conditions during shipping could range from 5 (very dry) to 20% (very humid). The packaging systems incorporated were reported to be efficient at protecting the wooden articles from damage during transit. The research highlighted the potential risk for wood components to ‘move’ in response to periods of drier or more humid conditions than those at the time of manufacturing, and the importance of engineering a packaging system that can account for the environmental conditions experienced in shipping containers. Examples of potential dimensional changes in wooden components were calculated based on published unit shrinkage data for key species and the climatic data returned from the logging equipment. The information highlighted the importance of good design to account for possible timber movement during shipping. A timber movement calculator was developed to allow designers to input component species, dimensions, site of manufacture and destination, to see validate their product design. This calculator forms part of the free interactive website www.timbers.com.au.

Growth factor-loaded microparticles for tissue engineering: The discrepancies of in vitro characterization assays

Efficient and effective growth factor (GF) delivery is an ongoing challenge for tissue regeneration therapies. The accurate quantification of complex molecules such as GFs, encapsulated in polymeric delivery devices, is equally critical and just as complex as achieving efficient delivery of active GFs. In this study, GFs relevant to bone tissue formation, vascular endothelial growth factor (VEGF) and bone morphogenetic protein 7 (BMP-7), were encapsulated, using the technique of electrospraying, into poly(lactic-co-glycolic acid) microparticles that contained poly(ethylene glycol) and trehalose to assist GF bioactivity. Typical quantification procedures, such as extraction and release assays using saline buffer, generated a significant degree of GF interactions, which impaired accurate assessment by enzyme-linked immunosorbent assay (ELISA). When both dry BMP-7 and VEGF were processed with chloroform, as is the case during the electrospraying process, reduced concentrations of the GFs were detected by ELISA; however, the biological effect on myoblast cells (C2C12) or endothelial cells (HUVECs) was unaffected. When electrosprayed particles containing BMP-7 were cultured with preosteoblasts (MC3T3-E1), significant cell differentiation into osteoblasts was observed up to 3 weeks in culture, as assessed by measuring alkaline phosphatase. In conclusion, this study showed how electrosprayed microparticles ensured efficient delivery of fully active GFs relevant to bone tissue engineering. Critically, it also highlights major discrepancies in quantifying GFs in polymeric microparticle systems when comparing ELISA with cell-based assays.

In vitro antioxidant and in vivo prophylactic effects of two gamma-lactones isolated from Grewia tiliaefolia against hepatotoxicity in carbon tetrachloride intoxicated rats

Grewia tiliaefolia is widely used in traditional Indian medicines to cure jaundice, biliousness, dysentery and the diseases of blood. Bioassay-guided fractionation of methanolic extract of the G. tiliaefolia bark has resulted in the isolation of D-erythro-2-hexenoic acid gamma-lactone (EHGL) and gulonic acid gamma-lactone (GAGL). Hepatoprotective activity of the methanolic extract and the isolated constituents were evaluated against CCl4-induced hepatotoxicity in rats. The treatment with methanolic extract, EHGL and GAGL at oral doses of 100, 150 and 60 mg/kg respectively with concomitant CCl4 intraperitoneal injection (I ml/kg) significantly reduced the elevated plasma levels of aminotransferases, alkaline phosphatase and the incidence of liver necrosis compared with the CCl4-injected group without affecting the concentrations of serum bilirubin and hepatic markers. EHGL and GAGL significantly inhibited the elevated levels of thiobarbituric acid reactive substances and glutathione in liver homogenates. Histology of the liver tissues of the extract and isolated constituents treated groups showed the presence of normal hepatic cords, absence of necrosis and fatty infiltration as similar to the normal control. The results revealed that the hepatoprotective activity of EHGL is significant as similar to the standard drug silymarin. To clarify the influence of the extract and isolated constituents on the protection of oxidative-hepatic damage, we examined in vitro antioxidant properties of the test compounds. The extract and the constituents showed significant free radical scavenging activity. These results suggest that the extract as well as the constituents could protect the hepatocytes from CCl4-induced liver damage perhaps, by their anti-oxidative effect on hepatocytes, hence eliminating the deleterious effects of toxic metabolites from CCl4, (C) 2009 Elsevier B.V. All rights reserved.

Hydrothermal synthesis and characterization of CaSO4 pseudomicrorods

Calcium sulphate (CaSO4) pseudomicrorods have been synthesized by alow-temperature hydrothermal method using CaSO4 powder as a precursor and hexadecylamine as a surfactant at 180 degrees C for at different intervals of time. The powder X-ray diffraction pattern indicates that the as-formed pseudomicrorods are of orthorhombic phase with lattice parameters a = 7.0023(4) angstrom, b = 6.9939(5) angstrom and c = 6.2434(4) angstrom. Scanning electron microscopy images show that the pseudomicrorods have diameters of about 0.2-2.5 mm and lengths of about 2-10 mm. Fourier transform infrared spectroscopy shows a strong doublet near 609 and 681 cm(-1) arising from nu(4) (SO42) bending vibrations. The strongest band observed at 1132 cm(-1) is associated with nu(3) (SO42-) stretching vibrations. The band near 420-450 cm(-1) is attributed to nu(2) (SO42-) bending vibrations. The Raman spectrum exhibits an intense peak at 1008 cm(-1) associated with the SO42- mode. The photoluminescence spectrum exhibits UV bands (330, 350 nm), strong green bands (402, 436 nm) and weak blue bands (503 nm). A widening of the optical band gap was observed as the particle size decreased.

Understanding Connectivity between Groundwater Chemistry Data and Geological Stratigraphy via 3D Sub-surface Visualization and Analysis

This paper describes the 3D Water Chemistry Atlas - an open source, Web-based system that enables the three-dimensional (3D) sub-surface visualization of ground water monitoring data, overlaid on the local geological model. Following a review of existing technologies, the system adopts Cesium (an open source Web-based 3D mapping and visualization interface) together with a PostGreSQL/PostGIS database, for the technical architecture. In addition a range of the search, filtering, browse and analysis tools were developed that enable users to interactively explore the groundwater monitoring data and interpret it spatially and temporally relative to the local geological formations and aquifers via the Cesium interface. The result is an integrated 3D visualization system that enables environmental managers and regulators to assess groundwater conditions, identify inconsistencies in the data, manage impacts and risks and make more informed decisions about activities such as coal seam gas extraction, waste water extraction and re-use.

Towards optimum diffraction efficiency for methylene blue sensitized dichromated gelatin holograms

A systematic investigation has been carried out into the optimization of diffraction efficiency (η) of methylene blue sensitized dichromated gelatin (MBDCG) holograms. The influence of the following parameters on η have been studied: prehardener concentration (CH), concentrations of ammonium dichromate (CA) and methylene blue (CM) as photosensitizers, and exposure (E). This study revealed that with CH similar, equals 0.5, CA similar, equals 30, CM similar, equals 0.3, and E similar, equals 400–600, optimum diffraction efficiency of over 80%, can be easily achieved in MBDCG holograms.

Isolation and characterization of a gonadotropin receptor binding inhibitor from porcine follicular fluid

The presence of a gonadotropin receptor binding inhibitor in pooled porcine follicular fluid has been demonstrated. Porcine follicular fluid fractionation on DE-32 at near neutral pH, followed by a cation exchange chromatography on SPC-50 and Cibacron blue affinity chromatography, yielded a partially purified gonadotropin receptor binding inhibitor (GI-4). The partially purified GI binding inhibitor inhibited the binding of both 125I labelled hFSH and hCG to rat ovarian receptor preparation. SDS electrophoresis of radioiodinated partially purified GI followed by autoradiography made it possible to identify the binding component as a protein of molecular weight of 80000. Subjecting 125I labelled GI-4 to chromatography on Sephadex G-100 helped obtain a homogeneous material, Gl-5. The 125I labelled GI-5 exhibited in its binding to ovarian membrane preparations characteristics typical of a ligand-receptor interaction such as saturability, sensitivity to reaction conditions as time, ligand and receptor concentrations and finally displaceability by unlabelled inhibitor as well as FSH and hCG in a dose dependent manner. This material could bind ovarian receptors for both FSH and LH, its binding being inhibited by added FSH or hCG in a dose dependent manner.

Local systems, global impacts : Using life cycle assessment to analyse the potential and constraints of industrial symbioses

Human activities extract and displace different substances and materials from the earth s crust, thus causing various environmental problems, such as climate change, acidification and eutrophication. As problems have become more complicated, more holistic measures that consider the origins and sources of pollutants have been called for. Industrial ecology is a field of science that forms a comprehensive framework for studying the interactions between the modern technological society and the environment. Industrial ecology considers humans and their technologies to be part of the natural environment, not separate from it. Industrial operations form natural systems that must also function as such within the constraints set by the biosphere. Industrial symbiosis (IS) is a central concept of industrial ecology. Industrial symbiosis studies look at the physical flows of materials and energy in local industrial systems. In an ideal IS, waste material and energy are exchanged by the actors of the system, thereby reducing the consumption of virgin material and energy inputs and the generation of waste and emissions. Companies are seen as part of the chains of suppliers and consumers that resemble those of natural ecosystems. The aim of this study was to analyse the environmental performance of an industrial symbiosis based on pulp and paper production, taking into account life cycle impacts as well. Life Cycle Assessment (LCA) is a tool for quantitatively and systematically evaluating the environmental aspects of a product, technology or service throughout its whole life cycle. Moreover, the Natural Step Sustainability Principles formed a conceptual framework for assessing the environmental performance of the case study symbiosis (Paper I). The environmental performance of the case study symbiosis was compared to four counterfactual reference scenarios in which the actors of the symbiosis operated on their own. The research methods used were process-based life cycle assessment (LCA) (Papers II and III) and hybrid LCA, which combines both process and input-output LCA (Paper IV). The results showed that the environmental impacts caused by the extraction and processing of the materials and the energy used by the symbiosis were considerable. If only the direct emissions and resource use of the symbiosis had been considered, less than half of the total environmental impacts of the system would have been taken into account. When the results were compared with the counterfactual reference scenarios, the net environmental impacts of the symbiosis were smaller than those of the reference scenarios. The reduction in environmental impacts was mainly due to changes in the way energy was produced. However, the results are sensitive to the way the reference scenarios are defined. LCA is a useful tool for assessing the overall environmental performance of industrial symbioses. It is recommended that in addition to the direct effects, the upstream impacts should be taken into account as well when assessing the environmental performance of industrial symbioses. Industrial symbiosis should be seen as part of the process of improving the environmental performance of a system. In some cases, it may be more efficient, from an environmental point of view, to focus on supply chain management instead.  

Direct Growth of Gold Nanorods on Gold and Indium Tin Oxide Surfaces: Spectral, Electrochemical, and Electrocatalytic Studies

The surfactant-assisted seed-mediated growth method was used for the formation of gold nanorods (GNRs) directly on gold (Au) and indium tin oxide (ITO) surfaces. Citrate-stabilized similar to 2.6 nm spherical gold nanoparticles (AuNPs) were first self-assembled on ITO or Au surfaces modified with (3-mercaptopropyl)-trimethoxysilane (MPTS) sol-gel film and then immersed in a cationic surfactant growth solution to form GNRs. The growth of GNRs on the MPTS sol gel film modified ITO surface was monitored by UV-visible spectroscopy. The ITO surface with the attached spherical AuNPs shows a surface plasmon resonance band at 550 nm. The intensity of this absorption band increases while increasing the immersion time of the AuNP-modified ITO surface into the growth solution, and after 5 h, an additional shoulder band around 680 nm was observed. The intensity of this shoulder band increases, and it was shifted to longer wavelength as the immersion time of the AuNP-modified ITO surface into the growth solution increases. After 20 h, a predominant wave at 720 nm was observed along with a band at 550 nm. Further immersion of the modified ITO surface into the growth solution did not change the absorption characteristics. The bands observed at 550 and 720 nm were characteristics of GNRs, corresponding to transverse and longitudinal waves, respectively. The AFM images showed the presence of GNRs on the surface of the MPTS sol gel modified ITO surface with a typical length of similar to 100-120 nm and a width of similar to 20-22 nm in addition to a few spherical AuNPs, indicating that seeded spherical AuNPs were not completely involved in the GNRs' formation. Finally, the electrocatalytic activity of the surface-grown GNRs on the MPTS sol gel film modified Au electrode toward the oxidation of ascorbic acid (AA) was studied. Unlike a polycrystalline Au electrode, the surface-grown GNR-modified electrode shows two well-defined voltammetric peaks for AA at 0.01 and 0.35 V in alkaline, neutral, and acidic pHs. The cause for the observed two oxidation peaks for AA was due to the presence of both nanorods and spherical nanoparticles on the electrode surface. The presence of spherical AuNPs on the MPTS sol gel film oxidized AA at more positive potential, whereas the GNRs oxidized AA at less positive potential. The observed 340 mV less positive potential shift in the oxidation of AA suggested that GNRs are better electrocatalysts for the oxidation of AA than the spherical AuNPs.

Synthesis and properties of rare earth doped lamp phosphors

Red, blue and green emitting lamp phosphors such as EU(3+) doped Y2O3 (red phosphor), EU(2+) doped Ba0.64Al12O18.64, BaMgAl10O17 and BaMg2Al16O27 (blue phosphors) and Ce0.67Tb0.33MgAl11O19 and Eu2+, Mn2+ doped BaMgAl10O17 (green phosphors) have been prepared by the combustion of the corresponding metal nitrates (oxidizer) and oxalyl dihydrazide/urea/carbohydrazide (fuel) mixtures at 400 degrees-500 degrees C within 5 min. The formation of these phosphors has been confirmed by their characteristic powder X-ray diffraction patterns and fluorescence spectra. The phosphors showed characteristic emission bands at 611 nm (red emission), 430-450 nm (blue emission) and 515-540 nm (green emission). The fine-particle nature of the combustion derived phosphors has been investigated using powder density, particle size and BET surface area measurements.

Ba(3)(P(1-x)Mn(x)O(4))(2): Blue/green inorganic materials based on tetrahedral Mn(V)

We describe a blue/green inorganic material, Ba(3)(P(1-x)-Mn(x)O(4))(2) (I) based on tetrahedral MnO(4)(3-):3d(2) chromophore. The solid solutions (I) which are sky-blue and turquoise-blue for x <= 0.25 and dark green for x >= 0-50, are readily synthesized in air from commonly available starting materials, stabilizing the MnO(4)(3-) chromophore in an isostructural phosphate host. We suggest that the covalency/ionicity of P-O/Mn-O bonds in the solid solutions tunes the crystal field strength around Mn(V) such that a blue colour results for materials with small values of x. The material could serve as a nontoxic blue/green inorganic pigment.

Two new atom centered fragment descriptors and scoring function enhance classification of antibacterial activity

Classification of pharmacologic activity of a chemical compound is an essential step in any drug discovery process. We develop two new atom-centered fragment descriptors (vertex indices) - one based solely on topological considerations without discriminating atomor bond types, and another based on topological and electronic features. We also assess their usefulness by devising a method to rank and classify molecules with regard to their antibacterial activity. Classification performances of our method are found to be superior compared to two previous studies on large heterogeneous data sets for hit finding and hit-to-lead studies even though we use much fewer parameters. It is found that for hit finding studies topological features (simple graph) alone provide significant discriminating power, and for hit-to-lead process small but consistent improvement can be made by additionally including electronic features (colored graph). Our approach is simple, interpretable, and suitable for design of molecules as we do not use any physicochemical properties. The singular use of vertex index as descriptor, novel range based feature extraction, and rigorous statistical validation are the key elements of this study.

Zoledronic acid in combination with alfacalcidol has additive effects on trabecular microarchitecture and mechanical properties in osteopenic ovariectomized rats

We conducted the present study to investigate the therapeutic effects of the antiresorptive agent zoledronic acid (ZOL), alone and in combination with alfacalcidol (ALF), in a rat model of postmenopausal osteoporosis. Female Wistar rats were ovariectomized (OVX) or sham-operated at 3 months of age. Twelve weeks post surgery, rats were randomized into six groups: (1) sham + vehicle, (2) OVX + vehicle, (3) OVX + ZOL (100 mu g/kg, i.v. single dose), (4) OVX + ZOL (50 mu g/kg, i.v. single dose), (5) OVX + ALF (0.5 mu g/kg, oral gauge daily) and (6) OVX + ZOL (50 mu g/kg, i.v. single dose) + ALF (0.5 mu g/kg, oral gauge daily) for 12 weeks. After treatment, we evaluated the mechanical properties of the lumbar vertebra and femoral mid-shaft. Femurs were also tested for bone density, porosity and trabecular micro-architecture. Biochemical markers in serum and urine were also determined. With respect to improvement in the mechanical strength of the lumbar spine and the femoral mid-shaft, the combination treatment of ZOL and ALF was more effective than each administered as a monotherapy. Moreover, combination therapy using ZOL and ALF preserved the trabecular micro-architecture and cortical bone porosity. Furthermore, the combination treatment of ZOL and ALF corrected the decrease in serum calcium and increase in serum alkaline phosphatase and the tartarate-resistant acid phosphatase level better than single-drug therapy using ZOL or ALF in OVX rats. In addition, the combination treatment of ZOL and ALF corrected the increase in urine calcium, phosphorous and creatinine levels better than single-drug therapy using ZOL or ALF in OVX rats. These data suggest that the combination treatment of ZOL and ALF has a therapeutic advantage over each monotherapy for the treatment of osteoporosis.

Effect of thermal annealing on dual photoluminescence emission characteristics of chemically synthesized uncapped Mn2+ doped ZnS quantum dots

Dual photoluminescence (PL) emission characteristics of Mn2+ doped ZnS (ZnS:Mn) quantum dots (QDs) have drawn a lot of attention recently. However, here we report the effect of thermal annealing on the PL emission characteristics of uncapped ZnS:Mn QDs of average sizes similar to 2-3 nm, synthesized by simple chemical precipitation method by using de-ionized (DI) water at room temperature. As-synthesized samples show dual PL emissions, having one UV PL band centred at similar to 400 nm and the other in the visible region similar to 610 nm. But when the samples are isochronally annealed for 2 h at 100-600 degrees C temperature range in air, similar to 90% quenching of Mn2+ related visible PL emission intensity takes place at the annealing temperature of 600 degrees C. X-ray diffraction data show that the as-synthesized cubic ZnS has been converted to wurtzite ZnO at 600 degrees C annealing temperature. The nanostructural properties of the samples are also determined by transmission electron micrograph, electron probe micro-analyser and UV-vis spectrophotometry. The photocatalytic property of the annealed ZnS:Mn sample has been demonstrated and photo-degradation efficiency of the as-synthesized and 600 degrees C annealed ZnS:Mn sample has been found out to be similar to 35% and similar to 61%, respectively, for the degradation of methylene blue dye under visible light irradiation. The synthesized QDs may find significant applications in future optoelectronic devices. (C) 2014 Elsevier B.V. All rights reserved.