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.

A Radical Cyclization Route To +/-Andirolactone, A Spiro-Gamma-Butyrolactone

Synthesis of Andirolactone (Image ), starting from 4-methyl cyclohex-3-en-1-one (Image ), via the radical cyclisation of the bromoacetal (Image ), is described.

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.

Chemical aspects of the hypergolic preignition reactions of some hybrid hypergols

A new class of solid compounds, viz., bisthiocarbonohydrazones and thiosemicarbazones, have been found to be hypergolic with fuming nitric acid. The observed ignition delays of these hypergols have been compared with those of the monothiocarbonohydrazones-nitric acid systems and explained in terms of the chemical reactions-neutralization, oxidation, and nitration-occurring in the preignition stage. p-Nitrobenzoic acid, benzoic acid, benzaldehyde, sulfur trioxide, nitrogen dioxide, and nitrogen have been isolated as preignition reaction intermediates in the mono- and bisbenzaldehydethiocarbonohydrazone-nitric acid systems. A scheme of reactions occurring in the preignition stage is proposed based on the formation of these products.

Species and Hybrids: Chemical and Physical Foliar Attributes and Implications for Herbivory.

Hybridization is an important biological phenomenon that can be used to understand the evolutionary process of speciation of plants and their associated pests and diseases. Interactions between hybrid plants and the herbivores of the parental taxa may be used to elucidate the various cues being used by the pests for host location or other processes. The chemical composition of plants, and their physical foliar attributes, including leaf thickness, trichome density, moisture content and specific leaf weight were compared between allopatric pure and commercial hybrid species of Corymbia, an important subtropical hardwood taxon. The leaf-eating beetle Paropsis atomaria, to which the pure taxa represented host (C. citriodora subsp. variegata) and non-host (C. torelliana) plants, was used to examine patterns of herbivory in relation to these traits. Hybrid physical foliar traits, chemical profiles, and field and laboratory beetle feeding preference, while showing some variability, were generally intermediate to those exhibited by parent taxa, thus suggesting an additive inheritance pattern. The hybrid susceptibility hypothesis was not supported by our field or laboratory studies, and there was no strong relationship between adult preference and larval performance. The most-preferred adult host was the sympatric taxon, although this species supported the lowest larval survival, while the hybrid produced significantly smaller pupae than the pure species. The results are discussed in relation to plant chemistry and physical characteristics. The findings suggest a chemical basis for host selection behavior and indicate that it may be possible to select for resistance to this insect pest in these commercially important hardwood trees.