Theoretical evidence and chemical origin of the magnetism-dependent electrostructural coupling in La2NiMnO6

Using first-principles density-functional calculations, we determine and analyze the Born effective charges Z(*) that describe the coupling between electric field and atomic displacements for ferromagnetic double-perovskite compound, La2NiMnO6. We find that th Born effective charge matrix of Ni in La2NiMnO6, has an anomalously large antisymmetric component, whose magnitude reduces substantially upon change in the magnetic ordering between Ni and Mn, showing it to be a magnetism-dependent electrostructural coupling. We use a local picture of the electronic structure obtained with Wannier functions, along with its band-by-band decomposition to determine its electronic origin.

Reducing Browning of Fresh-cut ‘Maha’ Carambola with Chemical Additives and Low-oxygen Atmospheres

The greatest attraction to using carambola (Averrhoa carambola L.) in the fresh-cut market is the star shape that the fruit presents after a transverse cut. Carambola is well-suited for minimal processing, but cut surface browning is a main cause of deterioration. This problem is exacerbated as a result of mechanical injuries occurring during processing and is mainly induced by the leakage of phenolic compounds from the vacuole and subsequent oxidation by polyphenol oxidase (PPO) (Augustin et al., 1985). The use of browning inhibitors in processed fruits is restricted to compounds that are non-toxic, ‘wholesome’, and that do not adversely affect taste and flavour (Gil et al., 1998). In the past, browning was mainly controlled by the action of sulphites, but the use of this compound has declined due to allergic reactions in asthmatics (Weller et al., 1995). The shelf life of fresh-cut products may be extended by a combination of oxygen exclusion and the use of enzymatic browning inhibitors. The objectives of this work were to determine the effects of: (1) post-cutting chemical treatments of ascorbic, citric, oxalic acids, and EDTA-Ca; (2) atmospheric modification; and (3) combinations of the above, on the shelf life of carambola slices based on appearance, colour and polyphenol oxidase activity

Flood related loss and recovery of intertidal seagrass meadows in southern Queensland, Australia

The loss and recovery of intertidal seagrass meadows were assessed following the flood related catastrophic loss of seagrass meadows in February 1999 in the Sandy Strait, Queensland. Region wide recovery rates of intertidal meadows following the catastrophic disturbance were assessed by mapping seagrass abundance in the northern Great Sandy Strait region prior to and on 3 occasions after widespread loss of seagrass. Meadow-scale assessments of seagrass loss and recovery focussed on two existing Zostera capricorni monitoring meadows in the region. Mapping surveys showed that approximately 90% of intertidal seagrasses in the northern Great Sandy Strait disappeared after the February 1999 flooding of the Mary River. Full recovery of all seagrass meadows took 3 years. At the two study sites (Urangan and Wanggoolba Creek) the onset of Z. capricorni germination following the loss of seagrass occurred 14 months post-flood at Wanggoolba Creek, and at Urangan it took 20 months for germination to occur. By February 2001 (24 months post-flood) seagrass abundance at Wanggoolba Creek sites was comparable to pre-flood abundance levels and full recovery at Urangan sites was complete in August 2001 (31 months post-flood). Reduced water quality characterised by 2–3 fold increases in turbidity and nutrient concentrations during the 6 months following the flood was followed by a 95% loss of seagrass meadows in the region. Reductions in available light due to increased flood associated turbidity in February 1999 were the likely cause of seagrass loss in the Great Sandy Strait region, southern Queensland. Although seasonal cues influence the germination of Z. capricorni, the temporal variation in the onset of seed germination between sites suggests that germination following seagrass loss may be dependent on other factors (eg. physical and chemical characteristics of sediments and water). Elevated dissolved nitrogen concentrations during 1999 at Wanggoolba Creek suggest that this site received higher loads of sediments and nutrients from flood waters than Urangan. The germination of seeds at Wanggoolba Creek one year prior to Urangan coincides with relatively low suspended sediment concentrations in Wanggoolba Creek waters. The absence of organic rich sediments at Urangan for many months following their removal during the 1999 flood may also have inhibited seed germination. Data from population cohort analyses and population growth rates showed that rhizome weight and rhizome elongation rates increased over time, consistent with rapid growth during increases in temperature and light availability from May to October

Determination of chemical shift anisotropy without a reference and of direct and indirect spin-spin couplings between heteronuclei

A method employing two liquid crystals of opposite diamagnetic anisotropies to determine chemical shift anisotropy without using any reference compound is described. It also provides individual values of the direct and the indirect spin-spin coupling constants between heteronuclei. The parameters for acetonitrile are reported.

Chemical bond approach to determining conductivity band gaps in amorphous chalcogenides and pnictides

The minimum energy required for the formation of conjugate pair of charged defects is found to be approximately equal to the experimental activation energy for d.c. conductivity in a number of amorphous chalcoganides and pnictides. This observation implies that the defect pair formation energy represents an intrinsic gap for transport in amorphous chalcogenides.

Chemical Characterization of Urinary Pheromones in Brown Antechinus, Antechinus stuartii

In the small dasyurid marsupial, Antechinus stuartii, males exhibit scent-marking in the form of cloacal marking of nesting areas during the breeding season. Females of this species show no such behavior. To characterize the potential male pheromonal scent signal, urine-derived volatiles from sexually active males were analyzed by GC-MS and compared to that of females and a castrated male. More than 10 urinary compounds were identified. A series of homologous methylketones was observed in both males and females, whereas aldehydes were present only in female urine. Urine from the castrate was virtually compound-free except for minute concentrations of a compound tentatively identified as 2,4-dithiapentane. This compound was also found in one of the sexually active males. The GC profiles of the sexually active males contained high concentrations of two pyrazine derivatives and four methylketones that were not detected in the profiles of either females or the castrate. These compounds may influence social communication in the brown antechinus, Antechinus stuartii.

Chemical approach to aspirin hypersensitivity

Rabbits and guinea pigs were immunized with functionalized aspirin-protein conjugates prepared by coupling 5-N-Succinylamino aspirin to BSA and BGG using a water soluble carbodiimide (EDC). Two populations of antibodies, one specific to functionalized aspirin and the other exclusively specific to salicylic acid were detected. These antibodies were fractionated and separated on affinity polymers suitably prepared with 5-N-succinylamino salicylic acid and 5-N-succinylamino-2-ethoxy benzoic acid as the ligands. The isolated and purified antibodies were electrophoretically homogeneous. The physico chemical interactions between the antibodies and the respective haptens were studied by radio-immunoassay, equilibrium dialysis and fluorescence quenching techniques.

Chemical synthesis and structure elucidation of bovine K-casein (1-44)

The caseins (αs1, αs2, β, and κ) are phosphoproteins present in bovine milk that have been studied for over a century and whose structures remain obscure. Here we describe the chemical synthesis and structure elucidation of the N-terminal segment (1–44) of bovine κ-casein, the protein which maintains the micellar structure of the caseins. κ-Casein (1–44) was synthesised by highly optimised Boc solid-phase peptide chemistry and characterised by mass spectrometry. Structure elucidation was carried out by circular dichroism and nuclear magnetic resonance spectroscopy. CD analysis demonstrated that the segment was ill defined in aqueous medium but in 30% trifluoroethanol it exhibited considerable helical structure. Further, NMR analysis showed the presence of a helical segment containing 26 residues which extends from Pro8 to Arg34. This is the first report which demonstrates extensive secondary structure within the casein class of proteins.

Beyond chemical dependency for managing plant-parasitic nematodes: Examples from the banana, pineapple and vegetable industries of tropical and subtropical Australia

Plant-parasitic nematodes are important pests of horticultural crops grown in tropical and subtropical regions of Australia. Burrowing nematode (Radopholus similis) is a major impediment to banana production and root-knot nematodes (predominantly Meloidogyne javanica and M. incognita) cause problems on pineapple and a range of annual vegetables, including tomato, capsicum, zucchini, watermelon, rockmelon, potato and sweet potato. In the early 1990s, nematode control in these industries was largely achieved with chemicals, with methyl bromide widely used on some subtropical vegetable crops, ethylene dibromide applied routinely to pineapples and non-volatile nematicides such as fenamiphos applied up to four times a year in banana plantations. This paper discusses the research and extension work done over the last 15 years to introduce an integrated pest management approach to nematode control in tropical and subtropical horticulture. It then discusses various components of current integrated pest management programs, including crop rotation, nematode monitoring, clean planting material, organic amendments, farming systems to enhance biological suppression of nematodes and judicious use of nematicides. Finally, options for improving current management practices are considered.

Response of minimally processed carambola to chemical treatments and low-oxygen atmospheres

Fresh-cut carambola (Averrhoa carambola L.) has limited marketability due to cut-surface browning. The effect of chemical treatments (ascorbic acid, citric acid and Ca-EDTA), controlled atmosphere (0.4-20.3% O2) and the association of these processes was investigated. Post-cutting dip and low-oxygen atmospheres did not prevent discoloration or improve sensory and physicochemical parameters. However, ascorbic acid (0.5% and 1%) dips reduced polyphenol oxidase (PPO) activity during storage at 4.5 °C, with 1% ascorbic acid inducing the lowest activity. Although cut-surface browning of 'Maha' slices was not relevant, carambola slices treated with 1% ascorbic acid in association with 0.4% oxygen did not present significant browning or loss of visual quality for up to 12 days, 3 days longer than low oxygen alone (0.4% O2), thus, their quality can be significantly improved by combining both treatments.

WISENOM. A formal organic chemical nomenclature system

A formal chemical nomenclature system WISENOM based on a context-free grammar and graph coding is described. The system is unique, unambiguous, easily pronounceable, encodable, and decodable for organic compounds. Being a formal system, every name is provable as a theorem or derivable as a terminal sentence by using the basic axioms and rewrite rules. The syntax in Backus-Naur form, examples of name derivations, and the corresponding derivation trees are provided. Encoding procedures to convert connectivity tables to WISENOM, parsing, and decoding are described.

Mode of Coordination and Chemical Reactivity of Alpha-Imine Hydrasone Ligands

Interaction of nickel(I1) and copper(I1) complexes of 4,9-dimethy1-5,8-diazadodeca-4,8diene-2,1 ldione, Ni(baen) and 4,6,9-trimethyl-5, 8diazadodeca-4,8-diene-2,ll-dione, Ni(bapn), with arene diazonium chlorides in buffered solutions of methanol yielded metal derivatives of glyoxaliminearylhydrazones. This typical electrophilic addition at the 3-carbon of the complex occurs owing to the pseudo aromatic behaviour of the chelate ring. A mechanism which predicts the attack of the diazonium cation through the coordination shell of the metal is well documented from the available experimental evidences. The chemical reactivity of a few complexes with a single residual non-substituted y-carbon is reasonably manifested by their reaction with phenyl isocyanate.

The chemical control of the environmental weed basket asparagus (Asparagus aethiopicus L. cv. Sprengeri) in Queensland

A replicated trial to determine effective chemical control methods for the invasive species, basket asparagus (Asparagus aethiopicus L. cv. Sprengeri) was conducted at Currumbin Hill, Queensland, from June 1999 to August 2000. Four herbicides (metsulfuron-methyl, dicamba, glyphosate and diesel) were applied at different times of the year (winter, spring, summer and autumn). Neat diesel applied to adult crowns effectively killed basket asparagus. However, germination of basket asparagus and other weeds was not prevented. An overall spray of 0.06 g metsulfuron-methyl (0.1 g Brush-Off®) + 1 mL BS 1000® L-1 water gave slower but more selective long-term control of basket asparagus when compared to diesel, especially when applied in winter and spring. High rates of foliar applied dicamba were most effective in spring and glyphosate splatter gunned on base of stems in autumn. The combination of increased selectivity, ease of application and likelihood of reduced environmental impacts on native plants, other than coast she-oak (Casuarina equisetifolia L. var. incana Benth.), of metsulfuron-methyl makes it more suitable for controlling large infestations of basket asparagus.

Kinetics of Chemical Vapor Deposition

A generalized mass transport model is developed for predicting the rate ofdeposition in chemical vapor deposition (CVD) systems. This combines thegeneralized method of obtaining equilibrium composition, with elemental fluxbalance expressions. This procedure avoids the usual problems encountered incalculating the rates in multicomponent systems, like writing overall reactionschemes. The dependence of multicomponent diffusivities on the fluxes is accountedin this model using an iterative procedure. The model developed isapplied to the deposition of titanium carbide on cemented carbide tool bitsfrom a gas mixture of titanium tetrachloride, toluene, and hydrogen. Experimentaldeposition rates were obtained using a thermogravimetric assembly.Mass transport controlled rates give an order of magnitude estimates of theobserved rates.