Nitrile Reversible ketenimine tautomerism in substituted alkylidene malononitriles and alkylidene cyanoacetates: A characteristic UV absorption band

Several alkylidene malononitriles (1b,1d,1e,2b and4b) and alkylidene cyanoacetates (1a,2a and4a) studied exhibit a long wavelength UV absorption band around 355 nm which shows a hyperchromic effect in the presence of ethanolic alkali. This band has been assigned to the ketenimine tautomer (5). Addition of water to1b,1e and2b gives the corresponding pyridine diols (7a,7b and8a) respectively. Similarly, addition of ethanol to1e and2b gave the corresponding ethoxypyridine derivatives (7c and8b). Mechanism of formation of these compounds is discussed. Structures, as well as mechanism of formation of1c,7c and10 obtained from1b,1e and2b respectively on standing at room temperature are also discussed.

Nitrileketenimine tautomerism in substituted alkylidene malononitriles and alkylidene cyanoacetates: A characteristic UV absorption band

Several alkylidene malononitriles (1b,1d,1e,2b and4b) and alkylidene cyanoacetates (1a,2a and4a) studied exhibit a long wavelength UV absorption band around 355 nm which shows a hyperchromic effect in the presence of ethanolic alkali. This band has been assigned to the ketenimine tautomer (5). Addition of water to1b,1e and2b gives the corresponding pyridine diols (7a,7b and8a) respectively. Similarly, addition of ethanol to1e and2b gave the corresponding ethoxypyridine derivatives (7c and8b). Mechanism of formation of these compounds is discussed. Structures, as well as mechanism of formation of1c,7c and10 obtained from1b,1e and2b respectively on standing at room temperature are also discussed.

Dual Drug Delivery Microcapsules via Layer-by-Layer Self-Assembly

The integration of hydrophobic and hydrophilic drugs in the polymer microcapsule offers the possibility of developing a new drug delivery system that combines the best features of these two distinct classes of material. Recently, we have reported the encapsulation of an uncharged water-insoluble drug in the polymer membrane. The hydrophobic drug is deposited using a layer-by-layer (LbL) technique, which is based on the sequential adsorption of oppositely charged polyelectrolytes onto a charged substrate. In this paper, we report the encapsulation of two different drugs, which are invariably different in structure and in their solubility in water. We have characterized these dual drug vehicular capsules by confocal laser scanning microscopy, atomic force microscopy, visible microscopy, and transmission electron microscopy. The growth of a thin film on a flat substrate by LbL was monitored by UV−vis spectra. The desorption kinetics of two drugs from the thin film was modeled by a second-order rate model.

‘How to’ guide for measuring fan performance and efficiency in meat chicken sheds

This ‘how to’ guide provides readers with method to measure fan performance and energy efficiency of fans installed in meat chicken sheds. These methods are also useful for identifying fans that are under-performing or require maintenance. For more information about fan energy efficiency, a complementary report is available on the RIRDC website ‘Review of fan efficiency in meat chicken sheds’ (RIRDC Publication No. 15/018). A spreadsheet was also developed under this project for comparing and ranking fans against others in terms of energy efficiency, air flow and costs (‘Tunnel Ventilation Fan Comparison Spreadsheet’), and is available on the RIRDC website.

Molecular Breeding for Complex Adaptive Traits: How Integrating Crop Ecophysiology and Modelling Can Enhance Efficiency

Progress in crop improvement is limited by the ability to identify favourable combinations of genotypes (G) and management practices (M) in relevant target environments (E) given the resources available to search among the myriad of possible combinations. To underpin yield advance we require prediction of phenotype based on genotype. In plant breeding, traditional phenotypic selection methods have involved measuring phenotypic performance of large segregating populations in multi-environment trials and applying rigorous statistical procedures based on quantitative genetic theory to identify superior individuals. Recent developments in the ability to inexpensively and densely map/sequence genomes have facilitated a shift from the level of the individual (genotype) to the level of the genomic region. Molecular breeding strategies using genome wide prediction and genomic selection approaches have developed rapidly. However, their applicability to complex traits remains constrained by gene-gene and gene-environment interactions, which restrict the predictive power of associations of genomic regions with phenotypic responses. Here it is argued that crop ecophysiology and functional whole plant modelling can provide an effective link between molecular and organism scales and enhance molecular breeding by adding value to genetic prediction approaches. A physiological framework that facilitates dissection and modelling of complex traits can inform phenotyping methods for marker/gene detection and underpin prediction of likely phenotypic consequences of trait and genetic variation in target environments. This approach holds considerable promise for more effectively linking genotype to phenotype for complex adaptive traits. Specific examples focused on drought adaptation are presented to highlight the concepts.

Changes in energy efficiency in Australia: A decomposition of aggregate energy intensity using logarithmic mean Divisia approach

This paper provides an empirical estimation of energy efficiency and other proximate factors that explain energy intensity in Australia for the period 1978-2009. The analysis is performed by decomposing the changes in energy intensity by means of energy efficiency, fuel mix and structural changes using sectoral and sub-sectoral levels of data. The results show that the driving forces behind the decrease in energy intensity in Australia are efficiency effect and sectoral composition effect, where the former is found to be more prominent than the latter. Moreover, the favourable impact of the composition effect has slowed consistently in recent years. A perfect positive association characterizes the relationship between energy intensity and carbon intensity in Australia. The decomposition results indicate that Australia needs to improve energy efficiency further to reduce energy intensity and carbon emissions. © 2012 Elsevier Ltd.

Measuring free ellagic acid: influence of extraction conditions on recovery by studying solubility and UV-Visible spectra

Recent investigations into plant tissues have indicated that the free form of the natural polyphenolic antioxidant, ellagic acid (EA), is much more plentiful than first envisaged; consequently a re-assessment of solvent systems for the extraction of this water-insoluble form is needed. As EA solubility and its UV-Vis spectrum, commonly used for detection and quantification, are both governed by pH, an understanding of this dependence is vital if accurate EA measurements are to be achieved. After evaluating the pH effects on the solubility and UV-Vis spectra of commercial EA, an extraction protocol was devised that promoted similar pH conditions for both standard solutions and plant tissue extracts. The extraction so devised followed by HPLC with photodiode-array detection (DAD) provided a simple, sensitive and validated methodology that determined free EA in a variety of plant extracts. The use of 100 % methanol or a triethanolamine-based mixture as the standard dissolving solvents were the best choices, while these higher pH-generating solvents were more efficient in extracting EA from the plants tested with the final choice allied to the plants’ natural acidity. Two of the native Australian plants anise myrtle (Syzygium anisatum) and Kakadu plum (Terminalia ferdinandiana) exhibited high concentrations of free EA. Furthermore, the dual approach to measuring EA UV-Vis spectra made possible an assessment of the effect of acidified eluent on EA spectra when the DAD was employed.

Superhydrophobic fabrics for oil-water separation based on the metal organic charge transfer complex CuTCNAQ

This work reports on the fabrication of a superhydrophobic nylon textile based on the organic charge transfer complex CuTCNAQ (TCNAQ = 11,11,12,12-tetracyanoanthraquinodimethane). The nylon fabric that is metallized with copper undergoes a spontaneous chemical reaction with TCNAQ dissolved in acetonitrile to form nanorods of CuTCNAQ that are intertwined over the entire surface of the fabric. This creates the necessary micro and nanoscale roughness that is required for the Cassie-Baxter state thereby achieving a superhydrophobic/superoleophilic surface without the need for a fluorinated surface. The material is characterised with SEM, FT-IR and XPS spectroscopy and investigated for its ability to separate oil and water in two modes, namely under gravity and as an absorbent. It is found that the fabric can separate dichloromethane, olive oil and crude oil from water and in fact reduce the water content of the oil during the separation process. The fabric is reusable and tolerant to conditions such as seawater, hydrochloric acid and extensive time periods on the shelf. Given that CuTCNAQ is a copper based semiconductor may also open up the possibility of other applications in areas such as photocatalysis and antibacterial applications.

Crystal structure and semiconductor-metal transition of the quasi-two-dimensional transition metal oxide, La2NiO4

Abstract is not available.

Integration and optimization of pressure retarded osmosis with reverse osmosis for power generation and high efficiency desalination

Salinity gradient power is proposed as a source of renewable energy when two solutions of different salinity are mixed. In particular, Pressure Retarded Osmosis (PRO) coupled with a Reverse Osmosis process (RO) has been previously suggested for power generation, using RO brine as the draw solution. However, integration of PRO with RO may have further value for increasing the extent of water recovery in a desalination process. Consequently, this study was designed to model the impact of various system parameters to better understand how to design and operate practical PRO-RO units. The impact of feed salinity and recovery rate for the RO process on the concentration of draw solution, feed pressure, and membrane area of the PRO process was evaluated. The PRO system was designed to operate at maximum power density of . Model results showed that the PRO power density generated intensified with increasing seawater salinity and RO recovery rate. For an RO process operating at 52% recovery rate and 35 g/L feed salinity, a maximum power density of 24 W/m2 was achieved using 4.5 M NaCl draw solution. When seawater salinity increased to 45 g/L and the RO recovery rate was 46%, the PRO power density increased to 28 W/m2 using 5 M NaCl draw solution. The PRO system was able to increase the recovery rate of the RO by up to 18% depending on seawater salinity and RO recovery rate. This result suggested a potential advantage of coupling PRO process with RO system to increase the recovery rate of the desalination process and reduce brine discharge.

A novel method of current efficiency determination

A simple and rapid method, based on the open-circuit decay of potential, is described for the determination of the current efficiency with which metals are electrodeposited. The advantages and disadvantages of the method are discussed.

Microwave modulation by amorphous-semiconductor switches

Microwave modulation has been achieved by using thin-film amorphous-semiconductor switches made of ternary chalcogenides. X-band microwaves were modulated by a threshold switch at frequencies varying from 100 Hz to 1 MHz, with modulation efficiencies comparable to siliconp¿i¿n diodes. The insertion loss was 0.5 to 0.6 dB and the isolation was 18 dB at 100 mA operating current. Possible applications this method are discussed.

Effect of long-wave UV radiation on mouse melanoma: an in vitro and in vivo study

The skin cancer incidence has increased substantially over the past decades and the role of ultraviolet (UV) radiation in the etiology of skin cancer is well established. Ultraviolet B radiation (280-320 nm) is commonly considered as the more harmful part of the UV-spectrum due to its DNA-damaging potential and well-known carcinogenic effects. Ultraviolet A radiation (320-400 nm) is still regarded as a relatively low health hazard. However, UVA radiation is the predominant component in sunlight, constituting more than 90% of the environmentally relevant solar ultraviolet radiation. In the light of the recent scientific evidence, UVA has been shown to have genotoxic and immunologic effects, and it has been proposed that UVA plays a significant role in the development of skin cancer. Due to the popularity of skin tanning lamps, which emit high intensity UVA radiation and because of the prolonged sun tanning periods with the help of effective UVB blockers, the potential deleterious effects of UVA has emerged as a source of concern for public health. The possibility that UV radiation may affect melanoma metastasis has not been addressed before. UVA radiation can modulate various cellular processes, some of which might affect the metastatic potential of melanoma cells. The aim of the present study was to investigate the possible role of UVA irradiation on the metastatic capacity of mouse melanoma both in vitro and in vivo. The in vitro part of the study dealt with the enhancement of the intercellular interactions occurring either between tumor cells or between tumor cells and endothelial cells after UVA irradiation. The use of the mouse melanoma/endothelium in vitro model showed that a single-dose of UVA to melanoma cells causes an increase in melanoma cell adhesiveness to non-irradiated endothelium after 24-h irradiation. Multiple-dose irradiation of melanoma cells already increased adhesion at a 1-h time-point, which suggests the possible cumulative effect of multiple doses of UVA irradiation. This enhancement of adhesiveness might lead to an increase in binding tumor cells to the endothelial lining of vasculature in various internal organs if occurring also in vivo. A further novel observation is that UVA induced both decline in the expression of E-cadherin adhesion molecule and increase in the expression of the N-cadherin adhesion molecule. In addition, a significant decline in homotypic melanoma-melanoma adhesion (clustering) was observed, which might result in the reduction of E-cadherin expression. The aim of the in vivo animal study was to confirm the physiological significance of previously obtained in vitro results and to determine whether UVA radiation might increase melanoma metastasis in vivo. The use of C57BL/6 mice and syngeneic melanoma cell lines B16-F1 and B16-F10 showed that mice, which were i.v. injected with B16-F1 melanoma cells and thereafter exposed to UVA developed significantly more lung metastases when compared with the non-UVA-exposed group. To study the mechanism behind this phenomenon, the direct effect of UVA-induced lung colonization capacity was examined by the in vitro exposure of B16-F1 cells. Alternatively, the UVA-induced immunosuppression, which might be involved in increased melanoma metastasis, was measured by standard contact hypersensitivity assay (CHS). It appears that the UVA-induced increase of metastasis in vivo might be caused by a combination of UVA-induced systemic immunosuppression, and to the lesser extent, it might be caused by the increased adhesiveness of UVA irradiated melanoma cells. Finally, the UVA effect on gene expression in mouse melanoma was determined by a cDNA array, which revealed UVA-induced changes in the 9 differentially expressed genes that are involved in angiogenesis, cell cycle, stress-response, and cell motility. These results suggest that observed genes might be involved in cellular response to UVA and a physiologically relevant UVA dose have previously unknown cellular implications. The novel results presented in this thesis offer evidence that UVA exposure might increase the metastatic potential of the melanoma cells present in blood circulation. Considering the wellknown UVA-induced deleterious effects on cellular level, this study further supports the notion that UVA radiation might have more potential impact on health than previously suggested. The possibility of the pro-metastatic effects of UVA exposure might not be of very high significance for daily exposures. However, UVA effects might gain physiological significance following extensive sunbathing or solaria tanning periods. Whether similar UVA-induced pro-metastatic effects occur in people sunbathing or using solaria remains to be determined. In the light of the results presented in this thesis, the avoidance of solaria use could be well justified.

Alloying gold with copper makes for a highly selective visible-light photocatalyst for the reduction of nitroaromatics to anilines

Finely control of product selectivity is an essential issue in organic chemical production. In the synthesis of functionalized anilines via reduction of the corresponding nitroarenes, the challenge is to selectively reduce only the nitro group in the presence of other reducible functional groups in nitroarene molecules at a high reaction rate. Normally, the nitroarene is reduced stepwise through a series of intermediates that remain as byproducts, increasing the aniline synthesis cost. Here we report that alloying small amounts of copper into gold nanoparticles can alter the reaction pathway of the catalytic reduction under visible-light irradiation at ambient temperature, allowing nitroaromatics to be transformed directly to anilines in a highly selective manner. The reasons for the high efficiency of the photocatalytic reduction under these comparatively benign conditions as well as the light-excited reaction mechanisms are discussed. This photocatalytic process avoids byproducts, exhibits a high reaction rate and excellent substituent tolerance, and can be used for the synthesis of many useful functionalized anilines under environmentally benign conditions. Switching of the reaction pathway simply by tailoring the bimetallic alloy NPs of the photocatalysts is effective for engineering of product chemoselectivity.

Incorporating the interrelationship between primary and support processes in monitoring and optimising longwall coal mining efficiency

This thesis increased the researchers understanding of the relationship between operations and maintenance in underground longwall coal mines, using data from a Queensland underground coal mine. The thesis explores various relationships between recorded variables. Issues with human recorded data was uncovered, and results emphasised the significance of variables associated with conveyor operation to explain production.