Interactions of insecticides with biological membranes

Many insecticides (e.g. DDT, lindane, pyrethroids) are hydrophobic molecules which bind extensively to biological membranes. Binding of insecticides to phospholipid bilayers frequently shows saturation, with binding increasing with increasing insecticide concentration up to some limit, beyond which no further insecticide is incorporated into the bilayer. For lindane, this limit has been shown to correspond to the concentration at which the aqueous phase becomes saturated. Simple alkanes show similar saturation phenomena, and binding of halogenated alkanes can be followed by fluorescence quenching methods. It is shown that effects of hydrophobic molecules on bilayer fluidity are small. Effects of alkanes and insecticides on the activity of the (Ca²⁺-Mg²⁺)-ATPase purified from sarcoplasmic reticulum follow from direct binding to the ATPase, at sites which are not at the lipid-protein interface of the ATPase.     

Contaminant and formulation analysis of MSMA using high-pressure liquid chromatography — graphite furnace atomic absorption spectrophotometry

High-pressure liquid chromatography with an ion-exchange column combined with graphite furnace atomic absorption spectrometry was used to analyse commercial formulations of sodium hydrogen methylarsonate (MSMA). No arsenite or arsenate salts or dimethylarsinic acid were detected as contaminants in the formulations, and the MSMA concentrations were found to be in accordance with the concentrations given on the containers.     

The physical and chemical properties of the herbicide cinmethylin (SD 95481)

Cinmethylin (SD 95481), is a novel herbicide developed for the selective pre-emergence control of many annual grass weeds in a wide range of temperate and tropical crops. Representing new herbicide chemistry, cinmethylin is in the cineole family. Cinmethylin is a mobile colourless liquid with a boiling point of 313°C under an inert atmosphere at atmospheric pressure. It has a density of 1015 kg m^?3 and a viscosity of 70–90 mPa s, both at 20°C. It is miscible in all proportions with most organic solvents but has a low solubility, 63 mg litre^?1, in water. It has a vapour pressure of 10.2 mPa (20°C) and the vapour pressure/temperature relationship is given by log_e P(Pa)=28.9–9816/T (K). The n-octanol/water partition coefficient is 6850 and soil organic matter/water sorption coefficient (K_om) ranges between 165 and 235 over the three types of soil used in these studies. Cinmethylin is stable in water over the pH range 3–11. Solutions of cinmethylin in water or solvents are reasonably stable to sunlight, though thin films on a quartz surface photooxidise mainly to an ester within 24 h. This rate can be reduced by the addition of photostabilisers or by sorption onto soil surfaces. In an inert atmosphere cinmethylin is stable to high temperatures, though, in air, oxidation occurs at temperatures above 100°C to give the same product as by photodecay.     

Physiological interactions between the herbicide EPTC and selected analogues of the antidote naphthalic anhydride on two hybrids of maize

The efficacies of nine structural analogues of the herbicide antidote naphthalene-1,8-dicarboxylic acid anhydride (naphthalic anhydride, NA) for the protection of maize (Zea mays L. cv. DeKalb XL72AA and DeKalb XL67) against injury by the herbicide S-ethyl dipropyl(thiocarbamate) (EPTC) were elevated under greenhouse conditions. The chemical analogues of NA tested were: acenaphthenequinone (ACQ); 4-aminonaphthalene-1,8-dicarboxylic acid anhydride (NH₂NA); 1,8:4,5-naphthalenetetracarboxylic acid dianhydride (NDiA); naphthalene- 1,8-carboximide (NHNA); 4-chloronaphthalene-1,8-dicarboxylic acid anhydride (C1NA); biphenyl-2,2′-dicarboxylic acid anhydride (diphenic anhydride; DA); 2-phenylglutaric anhydride (PGA); phthalic anhydride (PHA); phenalen-1-one (PA). Pre-plant incorporated applications of EPTC at 2.2, 4.5, 6.7, and 9.0 kg ha^?1 were highly toxic to XL67 maize. Appreciable injury to XL72AA maize by EPTC was observed only with the high rates of EPTC (6.7 and 9.0 kg ha^?1). Of the analogues tested PGA and PA were very toxic and inhibited germination of both maize hybrids. NA, ACQ, NH₂NA, NDiA, NHNA, C1NA, DA, and PHA applied as seed dressings at 5.0 and 10 g per kg of seed offered satisfactory protection to XL72AA maize against EPTC rates higher than 6.7 kg ha^?1. The same antidotes significantly antagonised the EPTC activity against XL67 maize but the overall protection obtained was partial and not agronomically important. The presence of the dicarboxylic anhydride group and of at least one aromatic ring attached directly to the anhydride appeared to be essential for the exhibition of protective activity by the structural analogues of NA. NA was slightly toxic to both hybrids of maize and chlorination of NA increased the phytotoxicity of this molecule. A genetic component that is present in the thiocarbamate-tolerant XL72AA hybrid but absent from the thiocarbamate-susceptible XL67 hybrid of maize appeared to be important for the phytotoxic activity of EPTC and may be involved in the protective activity of NA and its structural analogues.     

New mite-borne virus isolates from rakkyo,shallot and wild leek species

Flexuous viruses were transmitted from rakkyo (Allium chinense) and wild leek species (especiallyA. commutatum) to plants of crow garlic (A. vineale), by transfer of dry bulb mites. By electron microscope decoration tests using three antisera and by inoculations onto test plants, it was concluded that from each of the two natural host species at least two viruses were isolated. The viruses from wild leeks are both pathogenic onAllium spp. and may be of economic importance. Decoration tests on a virus mixture from shallot obtained earlier, revealed another new mite-borne virus in this species. The mite-borne viruses ofAllium spp. appear to be very common; they are largely diverse and their identification remains difficult.     

Activity of two novel insecticides against permethrin-resistant Pseudoplusia includens

Two experimental insecticides, AC 303,630 and MK 244, were tested against a laboratory colony and three field strains of Pseudoplusia includens (Walker). Topical application bioassays indicated that permethrin resistance in the field strains ranged from 3.9 to 489.0-fold. In leaf dip bioassays, LC₅₀ and LC₉₀ values for AC 303,630 ranged from 6.7 to 15.1 mg litre ?1 and 8.7 to 28.2 mg litre ?1, respectively, for third-instar larvae. The Louisiana 1991 field strain was significantly more susceptible to AC 303,630 than the laboratory and other field strains. The LC₅₀ (but not LC₉₀) for the Louisiana 1992 field strain was significantly higher than that of the laboratory strain. However, there was no difference in toxicity of AC 303,630 between the field strain with the highest level of permethrin resistance and the laboratory strain. LC₅₀ and LC₉₀ values for MK 244 in leaf dip bioassays ranged from 0.014 to 0.023 mg litre ?1 and 0.079 to 0.174 mg litre ?1, respectively. There were no significant differences in LC 50 or LC 90 among any of the strains for MK 244. Field trials in soybean were also conducted in 1991 and 1992 in an area of Louisiana where permethrin efficacy against P. includens has declined. In both years, AC 303,630 at 0.11–0.22 kg ha ?1, and MK 244 at 0.0042–0.0084 kg ha ?1, provided significantly better control than permethrin at 0.11 kg ha ?1, and control equal to the recommended standard, thiodicarb. These studies indicate no cross-resistance exists between the experimental insecticides and permethrin.     

Exploration of glycoprotein structures: Sequences and consequences

The vast expansion in our knowledge of the detailed molecular structure of many glycoproteins has been achieved by purpose-designed methodologies. In this review, principal experimental methods for gaining fundamental evidence are assessed with respect to well-known iV-glycoproteins (e.g. ribonucleases), 0,N-glycoproteins (e.g. glycophorin A) and O-glycoproteins (e.g. submaxiilary gland mucins and some sulfated forms). Relevant properties of N-carbohydrate-peptide links (N-acetylglucosaminyl-asparagine) and O-linkages (N-acetylgalac-tosaminyl-Thr (or -Ser)) are reviewed and the classification and structure of more elaborate glycoproteins is outlined. Key reactions, both chemical and enzymic, effect the cleavage of N- and O-oligosaccharide side-chains from core protein, and subsequent calibrated chromatographic analysis can permit the identification of certain oligosaccharide groupings characteristic of glycoforms (families of glycoproteins different only in the oligosaccharide chain lengths and bond structures). Basic sequencing of individual oligosaccharides is generally achieved by chemical methods (e.g. methylation analysis, degradation with periodate) and by the action of well-characterised specific exo- and endoglycosidases. Degradation of a glycoprotein chemically (e.g. by cyanogen bromide) or enzymically by endopeptidases to glycopeptides provides means for locating oligosaccharide position(s) on the core protein. The presence of O-sulfate ester groups on oligosaccharide side-chains presents further challenging problems for sequencing investigations. Some correlations between oligosaccharide sequences and biological function are considered. While, in the main, the best-known glycoprotein structures are for those of mammalian origin (e.g. Igs), evidence points to other areas of interest in plants (especially yeasts), invertebrates and micro-organisms. Allusion is made to current comparative and fundamental physico-chemical techniques, especially gel permeation chromatography, membrane-transfer, FAB-MS and NMR (NOE, COSY, etc.).     

Supercritical fluid chromatography—finding a place in the chromatographers' arsenal?

In the mid- to late 1980s, supercritical fluid chromatography (SFC) was ‘reborn’ as a technique for the 1990s. Supercritical fluids have physical properties (viscosity, diffusivity and density) intermediate between those of licuids and gases. Analyte solubilities are similar to those in some liquid chromatography solvents and the gas-like properties of supercritical fluids make higher resolution or shorter analysis times possible. Applications and experience with a home-built SFC system, as well as methods developed elsewhere, are described. The successes and limitations of the technique are reviewed together with details of the instrumentation. Areas in which SFC may become the procedure of choice include multi-residue methods, non-polar analyses, micro-preparative uses and for difficult extractions. The advances in GC and HPLC technology, however, lead us to believe that SFC will remain a specialist technique, appealing only to a minority of analysts.     

Experimental reproduction of severe disease in CD/CD pigs concurrently infected with type 2 porcine circovirus and porcine reproductive and respiratory syndrome virus

Three-week-old cesarean-derived colostrum-deprived (CD/CD) pigs were inoculated with porcine circovirus type 2 (PCV2, n = 19), porcine reproductive and respiratory syndrome virus (PRRSV, n = 13), concurrent PCV2 and PRRSV (PCV2/PRRSV, n = 17), or a sham inoculum (n = 12) to compare the independent and combined effects of these agents. Necropsies were performed at 7, 10, 14, 21, 35, and 49 days postinoculation (dpi) or when pigs became moribund. By 10 dpi, PCV2/PRRSV-inoculated pigs had severe dyspnea, lethargy, and occasional icterus; after 10 dpi, mortality in this group was 10/11 (91%), and all PCV2/ PRRSV-inoculated pigs were dead by 20 dpi. PCV2-inoculated pigs developed lethargy and sporadic icterus, and 8/19 (42%) developed exudative epidermitis; mortality was 5/19 (26%). PRRSV-inoculated pigs developed dyspnea and mild lethargy that resolved by 28 dpi. Microscopic lesions consistent with postweaning multisystemic wasting syndrome (PMWS) were present in both PCV2- and PCV2/PRRSV-inoculated pigs and included lymphoid depletion, necrotizing hepatitis, mild necrotizing bronchiolitis, and infiltrates of macrophages that occasionally contained basophilic intracytoplasmic inclusion bodies in lymphoid and other tissues. PCV2/ PRRSV-inoculated pigs also had severe proliferative interstitial pneumonia and more consistent hepatic lesions. The most severe lesions contained the greatest number of PCV2 antigen-containing cells. PRRSV-inoculated pigs had moderate proliferative interstitial pneumonia but did not develop bronchiolar or hepatic lesions or lymphoid depletion. All groups remained seronegative to porcine parvovirus. The results indicate that 1) PCV2 coinfection increases the severity of PRRSV-induced interstitial pneumonia in CD/CD pigs and 2) PCV2 but not PRRSV induces the lymphoid depletion, granulomatous inflammation, and necrotizing hepatitis characteristic of PMWS.     

Canine renal pathology associated with grape or raisin ingestion: 10 cases.

Ten dogs suffered acute renal failure after ingesting > or = 3 g/kg (dry matter) of grapes or raisins. All dogs had degeneration or necrosis (or both) of proximal renal tubules with basement membranes remaining intact, and epithelial regeneration was observed in 5 out of 10 cases. Mineralized tubular debris or granular to proteinaceous casts (or both) were present in all cases. A golden-brown, globular, intracellular pigment of varying amounts and sizes was observed in 6 out of 10 cases with variable reaction with Prussian blue. Multifocal fibrinous arteritis of the large colon was seen in 2 out of 5 cases with globulin insudation of vessel wall demonstrated by immunohistochemical staining for immunoglobulin (Ig)G and IgM. Mineral analysis on frozen renal tissue from 2 out of 2 cases revealed mildly elevated Ca:P ratio in both. Clinically significant observations were preservation of the integrity of basement membranes after grape-induced tubular injury and presence of early epithelial regeneration. Thus, recovery may be possible if anuria is aggressively managed. With respect to potential pathophysiologic mechanisms, further research into the roles of calcium homeostasis, vascular reactivity, and the significance of the golden-brown pigment is indicated.