4,6,8,10,16-Penta- and 4,6,8,10,16,18-hexamethyldocosanes from the cane beetle Antitrogus parvulus - Cuticular hydrocarbons with unprecedented structure and stereochemistry

The major cuticular hydrocarbons from the cane beetle species Antitrogus parvulus were deduced to be 4,6,8,10,16,18-hexa- and 4,6,8,10,16- pentamethyldocosanes 2 and 3, respectively. Isomers of 2,4,6,8-tetramethylundecanal 27, 36, and 37, derived from 2,4,6-trimethylphenol, were coupled with the phosphoranes 28 and 29 to furnish alkenes and, by reduction, diastereomers of 2 and 3. Chromatographic and spectroscopic comparisons confirmed 2 as either 6a or 6b and 3 as either 34a or 34b.

Essential Oil Composition of Diploid and Tetraploid Clones of Ginger (Zingiber officinale Roscoe) Grown in Australia

Ginger oil, obtained by steam distillation of the rhizome of Zingiber officinale Roscoe, is used in the beverage and fragrance industries. Ginger oil displays considerable compositional diversity, but is typically characterized by a high content of sesquiterpene hydrocarbons, including zingiberene, arcurcumene, â-bisabolene, and â-sesquiphellandrene. Australian ginger oil has a reputation for possessing a particular “lemony” aroma, due to its high content of the isomers neral and geranial, often collectively referred to as citral. Fresh rhizomes of 17 clones of Australian ginger, including commercial cultivars and experimental tetraploid clones, were steam distilled 7 weeks post-harvest, and the resulting oils were analyzed by GC-MS. The essential oils of 16 of the 17 clones, including the tetraploid clones and their parent cultivar, were found to be of substantially similar composition. These oils were characterized by very high citral levels (51-71%) and relatively low levels of the sesquiterpene hydrocarbons typical of ginger oil. The citral levels of most of these oils exceeded those previously reported for ginger oils. The neral-to-geranial ratio was shown to be remarkably constant (0.61 ( 0.01) across all 17 clones. One clone, the cultivar “Jamaican”, yielded oil with a substantially different composition, lower citral content and higher levels of sesquiterpene hydrocarbons. Because this cultivar also contains significantly higher concentrations of pungent gingerols, it possesses unique aroma and flavor characteristics, which should be of commercial interest.

Spiroacetal biosynthesis in insects from diptera to hymenoptera: The Giant Ichneumon wasp Megarhyssa nortoni nortoni Cresson

The volatile components of the mandibular gland secretion generated by the Giant Ichneumon parasitoid wasp Megarhyssa nortoni nortoni Cresson are mainly spiroacetals and methyl ketones, and all have an odd number of carbon atoms. A biosynthetic scheme rationalizing the formation of these diverse components is presented. This scheme is based on the results of incorporation studies using 2H-labeled precursors and [18O]dioxygen. The key steps are postulated to be decarboxylation of β-ketoacid equivalents, β-oxidation (chain shortening), and monooxygenase-mediated hydroxylation leading to a putative ketodiol that cyclizes to spiroacetals. The generality of the role of monooxygenases in spiroacetal formation in insects is considered, and overall, a cohesive, internally consistent theory of spiroacetal generation by insects is presented, against which future hypotheses will have to be compared.

Hardness Methods for Testing Maize Kernels

Maize is a highly important crop to many countries around the world, through the sale of the maize crop to domestic processors and subsequent production of maize products and also provides a staple food to subsistance farms in undeveloped countries. In many countries, there have been long-term research efforts to develop a suitable hardness method that could assist the maize industry in improving efficiency in processing as well as possibly providing a quality specification for maize growers, which could attract a premium. This paper focuses specifically on hardness and reviews a number of methodologies as well as important biochemical aspects of maize that contribute to maize hardness used internationally. Numerous foods are produced from maize, and hardness has been described as having an impact on food quality. However, the basis of hardness and measurement of hardness are very general and would apply to any use of maize from any country. From the published literature, it would appear that one of the simpler methods used to measure hardness is a grinding step followed by a sieving step, using multiple sieve sizes. This would allow the range in hardness within a sample as well as average particle size and/or coarse/fine ratio to be calculated. Any of these parameters could easily be used as reference values for the development of near-infrared (NIR) spectroscopy calibrations. The development of precise NIR calibrations will provide an excellent tool for breeders, handlers, and processors to deliver specific cultivars in the case of growers and bulk loads in the case of handlers, thereby ensuring the most efficient use of maize by domestic and international processors. This paper also considers previous research describing the biochemical aspects of maize that have been related to maize hardness. Both starch and protein affect hardness, with most research focusing on the storage proteins (zeins). Both the content and composition of the zein fractions affect hardness. Genotypes and growing environment influence the final protein and starch content and. to a lesser extent, composition. However, hardness is a highly heritable trait and, hence, when a desirable level of hardness is finally agreed upon, the breeders will quickly be able to produce material with the hardness levels required by the industry.

Analysis of Daphnane Orthoesters in Poisonous Australian Pimelea Species by Liquid Chromatography-Tandem Mass Spectrometry.

Cattle grazing in arid rangelands of Australia suffer periodic extensive and serious poisoning by the plant species Pimelea trichostachya, P. simplex, and P. elongata. Pimelea poisoning (also known as St. George disease and Marree disease) has been attributed to the presence of the diterpenoid orthoester simplexin in these species. However, literature relating to previous studies is complicated by taxonomic revisions, and the presence of simplexin has not previously been verified in all currently recognized taxa capable of inducing pimelea poisoning syndrome, with no previous chemical studies of P. trichostachya (as currently classified) or P. simplex subsp. continua. We report here the isolation of simplexin from P. trichostachya and the development of a liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) method to measure simplexin concentrations in pimelea plant material. Simplexin was quantified by positive-ion atmospheric pressure chemical ionization (APCI) LC-MS/MS with selected reaction monitoring (SRM) of the m/z 533.3 > 253.3 transition. LC-MS/MS analysis of the four poisonous taxa P. trichostachya, P. elongata, P. simplex subsp. continua, and P. simplex subsp. simplex showed similar profiles with simplexin as the major diterpenoid ester component in all four taxa accompanied by varying amounts of related orthoesters. Similar analyses of P. decora, P. haematostachya, and P. microcephala also demonstrated the presence of simplexin in these species but at far lower concentrations, consistent with the limited reports of stock poisoning associated with these species. The less common, shrubby species P. penicillaris contained simplexin at up to 55 mg/kg dry weight and would be expected to cause poisoning if animals consumed sufficient plant material.

Key Role of Fe2+ in Epithiospecifier Protein Activity.

The chemical nature of the hydrolysis products from the glucosinolate-myrosinase system depends on the presence or absence of supplementary proteins such as epithiospecifier proteins (ESPs). ESPs promote the formation of epithionitriles from terminal alkenyl glucosinolates and, as recent evidence suggests, simple nitriles at the expense of isothiocyanates. From a human health perspective isothiocyanates are the most important because they are major inducers of carcinogen-detoxifying enzymes. Fe2+ is an essential factor in ESP activity, although several recent studies have highlighted discrepancies in the understanding of the ESP-iron interaction. To investigate further the role iron species play in regulating ESP activity, four ESP-containing seedpowders were analyzed for ESP and myrosinase activities, endogenous iron content, and glucosinolate degradation products after the addition of iron species, specific chelators, and reducing agents. For the first time this paper shows the effect of these additions on the hydrolysis of individual glucosinolates that constitute the total pool. Aged seeds and 3-day seedlings were also tested to investigate the effects of seed storage and early plant development on iron levels and ESP activity. The four ESP-containing plant systems tested gave two distinctive responses, thus providing strong evidence that ESPs vary markedly in their Fe2+ requirement for activity. The results also indicated that reduction of ferric to ferrous iron drives variations in ESP activity during early plant development. The reverse oxidation reaction provided a convincing explanation for the loss of ESP activity during seed storage. Aged seeds produced seedlings with substantially lower ESP activity, and there was a concomitant loss in germination rate. It was concluded that manipulation of endogenous iron levels of ESP-containing plants could increase the conversion of glucosinolates to isothiocyanates and enhance potential health benefits.

Pyrrolizidine Alkaloids in Crotalaria Taxa from Northern Australia: Risk to Grazing Livestock.

Crotalaria species containing hepatotoxic pyrrolizidine alkaloids grow widely in pastures in northern Australia and have sporadically poisoned grazing livestock. The diverse Crotalaria taxa present in these pastures include varieties, subspecies, and chemotypes not previously chemically examined. This paper reports the pyrrolizidine alkaloid composition and content of 24 Crotalaria taxa from this region and assesses the risk of poisoning in livestock consuming them. Alkaloids present in C. goreensis, C. aridicola subsp. densifolia, and C. medicaginea var. neglecta lack the esterified 1,2-unsaturated functionality required for pyrrole adduct formation, and these taxa are not hepatotoxic. Taxa with high levels of hepatotoxic alkaloids, abundance, and biomass pose the greatest risk to livestock health, particularly C. novae-hollandiae subsp. novae-hollandiae, C. ramosissima, C. retusa var. retusa, and C. crispata. Other species containing moderate alkaloid levels, C. spectabilis and C. mitchellii, also pose significant risk when locally abundant.

Daphnane- and Tigliane-Type Diterpenoid Esters and Orthoesters from Pimelea elongata.

Investigation of Pimelea elongata ("Lakebed Pimelea") afforded 18 tigliane- and daphnane-type diterpenes (1-18). Eight of these were new compounds: four (1-3, 5) tigliane esters and four (7, 8, 10, 11) daphnane orthoesters. The 10 known compounds were 12-O-decanoylphorbol-13-acetate (4), P. simplex subtoxin B (6), wikstroelide E (9), pimelotides A and B (12, 13), gnidiglaucin (14), simplexin (15), huratoxin (16), kirkinine D (17), and 12-beta-acetoxyhuratoxin (18). The structures and relative configurations of the new compounds were determined by ID and 2D NMR spectroscopic studies in combination with MS analyses.

Norsesquiterpene Glycosides in Bracken Ferns (Pteridium esculentum and Pteridium aquilinum subsp wightianum) from Eastern Australia: Reassessed Poisoning Risk to Animals.

Austral bracken Pteridium esculentum contains three unstable norsesquiterpene glycosides: ptaquiloside, ptesculento-side, and caudatoside, in variable proportions. The concentration of each of the glycosides was determined in this study as their respective degradation products, pterosin B, pterosin G and pterosin A, by HPLC-UV analysis. Samples of P. esculentum collected from six sites in eastern Australia contained up to 17 mg of total glycoside/g DW, with both ptaquiloside and ptesculentoside present as major components accompanied by smaller amounts of caudatoside. Ratios of ptaquiloside to ptesculentoside varied from 1:3 to 4:3, but in all Australian samples ptesculentoside was a significant component. This profile differed substantially from that of P. esculentum from New Zealand, which contained only small amounts of both ptesculentoside and caudatoside, with ptaquiloside as the dominant component. A similar profile with ptaquiloside as the dominant glycoside was obtained for Pteridium aquilinum subsp. wightianum (previously P. revolutum) from northern Queensland and also P. aquilinum from European sources. Ptesculentoside has chemical reactivity similar to that of ptaquiloside and presumably biological activity similar to that of this potent carcinogen. The presence of this additional reactive glycoside in Australian P. esculentum implies greater toxicity for consuming animals than previously estimated from ptaquiloside content alone.

Residue Potential of Norsesquiterpene Glycosides in Tissues of Cattle Fed Austral Bracken (Pteridium esculentum).

Austral bracken, Pteridium esculentum, occurs widely in Australian grazing lands and contains both the known carcinogen ptaquiloside and its hydroxy analogue, ptesculentoside, with untested carcinogenic potential. Calves were fed a diet containing 19% P. esculentum that delivered 1.8 mg of ptaquiloside and 4.0 mg of ptesculentoside per kilogram of body weight (bw) per day to explore the carcass residue potential of these compounds. Concentrations of ptaquiloside and ptesculentoside in the liver, kidney, skeletal muscle, heart, and blood of these calves were determined as their respective elimination products, pterosin B and pterosin G, by HPLC-UV analysis. Plasma concentrations of up to 0.97 mu g/mL ptaquiloside and 1.30 mu g/mL ptesculentoside were found, but were shown to deplete to <10% of these values within 24 h of bracken consumption. Both glycosides were also detected in all tissues assayed, with ptesculentoside appearing to be more residual than ptaquiloside. Up to 0.42 and 0.32 mu g/g ptesculentoside was present in skeletal muscle and liver, respectively, 15 days after bracken consumption ended. This detection of residual glycosides in tissues of cattle feeding on Austral bracken raises health concerns for consumers and warrants further investigation.