Ladybird defence alkaloids: Structural,chemotaxonomic and biosynthetic aspects (Col.: Coccinellidae)

Summary The defensive mechanisms which protect ladybird beetles (Coccinellidae) against predators are reviewed. Besides behavioural mechanisms, such as thanatosis and reflex bleeding, chemical defence mechanisms are playing a prevalent role. Indeed, ladybirds are protected not only by their smell, but also by repulsive alkaloids, most of which are considered to be of autogenous origin. In a few cases, dietarily-acquired substances are also involved. Particular emphasis is laid on the repellent alkaloids which are contained in the haemolymph of many species. The structures of 34 nitrogen-containing compounds isolated so far are presented, and their distribution within the family is discussed in the light of the most widely accepted classification of these beetles. To conclude, the mode of release of the alkaloids, their variation through the life cycle and their repellent and toxic properties are discussed, as well as the few biosynthetic data yet available.     

Sorption of Isoproturon and Dimetomorph on lignocellulose from wheat

The adsorption of toxic chemicals on solid substates is a potential means to clean polluted waters. Here, the adsorption of two pesticides, isoproturon and dimetomorph, on lignocellulose extracted from wheat straw is investigated at 20 °C using batch adsorption experiments. Here, we show that the sorption of both pesticides is independent of pH. The sorption capacity of lignocellulose is evaluated. We show that the presence of metallic cations has no influence on the retention capacity of lignocellulose towards pesticides.     

Recycling plant wax constituents for chemical defense: hemi-biosynthesis of triterpene saponins from β-amyrin in a leaf beetle

Several species of Doryphorina leaf beetles from Central- and South America produce oleanane triterpene glycosides in their defensive glands. The presence of pentacyclic triterpenes in insects is intriguing since they lack the key enzymes necessary to synthesize these compounds. Since -amyrin is a common constituent of leaf waxes, we hypothesized that these leaf beetles use this compound as a precursor to their oleanane glycosides. To test this hypothesis we first confirmed the presence of -amyrin in Ipomoea batatas, the food plant of Platyphora kollari. Next, adults of P. kollari were fed for 10 days with I. batatas leaf disks painted with a solution of [2,2,3-²H₃]-amyrin ([2,2,3-²H₃]-1). The secretion from their defensive glands was collected and analyzed by HPLC-ESIMS. The results demonstrated that the secretion of beetles fed with an amount of [2,2,3-²H₃]-amyrin corresponding to the quantity of unlabeled (natural) -amyrin present in the leaf disks contained on average 5.1% of [2,2,3-²H₃]-3-O--d-glucopyranosyl-(1-->4)--d-glucuronopyranosyl-hederagenin ([2,2,3-²H₃]-2), whereas the secretions of beetles fed with 10 times this amount of [2,2,3-²H₃]-amyrin contained on average 23.9% of [2,2,3-²H₃]-2. In both series of experiments, the percentage of labeled versus unlabeled triterpene glycoside in the secretion was positively correlated with the amount of deuterated -amyrin ingested. These results demonstrate for the first time that some leaf beetles are able to metabolize a widespread triterpenic constituent of leaf wax into more complex glycosides that are stored in their defensive glands.     

Effects of waterborne exposure to 4-nonylphenol on plasma sex steroid and vitellogenin concentrations in sexually mature male carp (Cyprinus carpio)

4-Nonylphenol (NP) has been shown to elicit estrogenic responses both in vivo and in vitro. The mechanism by which NP exerts estrogenic and other endocrine-modulating effects in vivo remains unclear, however. The goal of this study was to evaluate the ability of NP to elicit estrogenic responses through indirect mechanisms of action involving the modulation of endogenous steroid hormone concentrations. Sexually mature male common carp (Cyprinus carpio) were exposed to aqueous NP concentrations ranging from <0.05 to 5.4 microg NP/l for 28-31 d. Approximately 0.5-3.5 ppm of NP was detected in pooled plasma samples or tissue samples from the carp studied. NP exposure did not significantly increase plasma concentrations of 17beta-estradiol (E2), testosterone (T) or vitellogenin (VTG). Excluding outliers, plasma E2 concentrations ranged from <175 to 700 pg E2/ml. T concentrations ranged from 940 to 24,700 pg T/ml plasma. The greatest VTG concentration detected was 52 microg/ml. One-third of the plasma samples tested contained <1 microg VTG/ml. Overall, the results of this study did not support the hypothesis that exposure to waterborne NP can modulate concentrations of steroid hormones in the plasma of sexually mature male carp. The results did, however, raise a number of questions regarding the utility of estradiol equivalent (EEQ) estimates as a means of predicting in vivo effects of estrogenic substances. Furthermore, they provide information regarding the concentrations and variability of E2, T, and VTG in the plasma of sexually mature male carp, which may aid in design and interpretation of future studies.     

A teratological assessment of four trihalomethanes in the rat

Four trihalomethanes were administered by gavage to Sprague-Dawley rats from day 6 to day 15 of gestation. Chloroform (Ch) was administered at levels of 100, 200 and 400 mg/kg and bromoform (Br), bromodichloromethane (BDCM) and chlorodibromomethane (CDBM) were administered at levels of 50, 100 or 200 mg/kg/day. A separate control was used for each compound. Maternal weight gain was depressed in all groups receiving Ch and at the highest dose levels of BDCM and CDBM. Ch administration caused decreased maternal hemoglobin and hematocrit values at all dose levels and also produced increased serum inorganic phosphorus and cholesterol at the highest dose. Liver enlargement was observed at all dose levels of Ch but in no other treatment groups. Evidence of a fetotoxic response was observed with Ch, CDBM and Br but not BDCM. No dose-related histopathological changes were observed in either mothers or fetuses as a result of treatment. None of the chemicals tested produced any teratogenic effects.     

Photochimie et environnement - V. Photohydrolyse du monochlorobenzene en solution aqueuse diluee

A primary photohydrolysis of monochlorobenzene into phenol in dilute aqueous solution is occuring quantitatively whatever the experimental conditions were: pH (1<pH<12), excitation wavelength (253.7 nm or 300 nm), presence or absence of oxygen, initial concentration (in the range 10^?4M – 4.10^?3 M). The initial quantum yield of appearance of phenol has been found to be 0.10 ± 0.02 at 253.7 nm, and 0.19 ± 0.06 at 300 nm. The excited state leading to phenol cannot be quenched by acetonitrile at concentration up to 1.9 M. An heterolytic scission of the C-Cl bond parallels the concerted scission of water; a photosubstitution mechanism cannot account for the observed phenomena, especially in acidic media.Monofluoro- and bromobenzene irradiated in degased solution undergo a similar photohydrolysis; the initial quantum yields of appearance of phenol are 0.003 ± 0.001 and 0.06 ± 0.01, respectively for fluoro- and bromobenzene.     

Reproduction study of toxaphene in the rat

The purpose of the present study was to investigate in rats the reproductive effects of toxaphene, an insecticidal mixture which has been identified as a pollutant in the Great Lakes ecosystem. Groups of 30 female and 15 male weanling rats were given toxaphene in the diets at 0, 4.0, 20, 100 or 500 ppm in a 1 generation 2 litter reproduction study. Toxaphene treatment at the levels studied had no effects on the litter size, pup weight, fertility, or gestation and survival indices. Toxic effects in the parental rats included depressed weight gain, elevated serum cholesterol, and increased liver and kidney weight and hepatic microsomal enzyme activities. Most of these effects were associated only with 500 ppm toxaphene treatment. Treatment-related histological changes in the liver, thyroid and kidney of adult rats were observed at levels as low as 20 ppm. Based on the data presented, the no observable adverse effect dose of toxaphene was considered to be 4.0 ppm in the diet (0.29-0.38 mg/kg b.w./day depending on the amount of dietary intake).     

The toxicity of pyrene in the fish : Synergism by piperonyl butoxide and by ultraviolet light

A saturated solution of pyrene in water was not toxic to the fish , even in the presence of ultraviolet light. A survival curve possessing one minimum, and therefore defining two LC₅₀ values, was obtained when fish placed in water containing increasing amounts of a pyrene solution in dimethylsulfoxide were exposed to ultraviolet light after a short incubation period. The phototoxicity was linked to the presence of undissolved pyrene. A normal survival curve with only one LC₅₀ value was found when pyrene was solubilized with the surfactant Tween-20. Practically no phototoxicity was produced when the pyrene mixtures were filtered before use, or when a saturated aqueous solution of pyrene was used. Piperonyl butoxide, present at a concentration where it was not toxic, synergized the toxicity of pyrene . The environmental significance of this observation may be considerable.     

Toxicological assessment of chlorinated diphenyl ethers in the rat

Chlorinated diphenyl ethers are environmental contaminants that have been found in Great Lakes fish and birds. Because of their presence in the food chain, and potential for human exposure, the present short-term study was conducted to assess their toxicity. Groups of 10 male and 10 female rats were each given by gavage 2,2',4,4'6-pentachlorodiphenyl ether (CDE1), 2,2',4,4',5,6-hexachlorodiphenyl ether (CDE2) or 2,2',3,3',4,6'-hexachlorodiphenyl ether (CDE3) at dose levels of 0.04, 0.4, 4.0 or 40 mg/kg b.w./day for a period of 28 days. The control group received an equivalent volume of corn oil only (0.5 ml/100 g b.w.). Treatment with the three CDE congeners did not result in suppression of growth rate or food consumption. Increased liver weights were seen in the animals of both sexes fed 40 mg/kg CDE2, in males treated with 40 mg/kg CDE1, and in females with 40 mg/kg CDE3. Hepatic microsomal aminopyrine demethylase activity was significantly higher in the male rats administered 40 mg/kg CDE2, and aniline hydroxylase activity was elevated in the females following the same treatment. Serum glucose, calcium, protein and urea nitrogen of CDE1-treated males were higher than the control. Levels of uric acid, potassium and LDH of CDE3-treated females were also elevated. No hematological changes were observed. Histological examination revealed that the liver and thyroid were the target organs affected by CDE treatment but the morphological changes were mild even at the highest dose level. Changes in the liver consisted of nuclear vesiculation and increased cytoplasmic volume. Alterations in the thyroid were characterized by increased epithelial height and follicular collapse. Based on the data presented above, the 3 CDE congeners can only be considered moderately toxic in the rat.     

Assessing the recovery of lakes in southeastern Canada from the effects of acidic deposition

Reductions in North American sulfur dioxide (SO2) emissions promoted expectations that aquatic ecosystems in southeastern Canada would soon recover from acidification. Only lakes located near smelters that have dramatically reduced emissions approach this expectation. Lakes in the Atlantic provinces, Quebec and Ontario affected only by long-range sources show a general decline in sulfate (SO4(2-)) concentrations, but with a relatively smaller compensating increase in pH or alkalinity. Several factors may contribute to the constrained (or most likely delayed) acidity response: declining base cation concentrations, drought-induced mobilization of SO4(2-), damaged internal alkalinity generation mechanisms, and perhaps increasing nitrate or organic anion levels. Monitoring to detect biological recovery in southeastern Canada is extremely limited, but where it occurs, there is little evidence of recovery outside of the Sudbury/Killarney area. Both the occurrence of Atlantic salmon in Nova Scotia rivers and the breeding success of Common Loons in Ontario lakes are in fact declining although factors beyond acidification also play a role. Chemical and biological models predict that much greater SO2 emission reductions than those presently required by legislation will be needed to promote widespread chemical and latterly, biological recovery. It may be unrealistic to expect that pre-industrial chemical and biological conditions can ever be reestablished in many lakes of southeastern Canada.