The effect of phosphine on the absorption and circular dichroic spectra of cytochrome c and cytochrome oxidase

The interaction of phosphine with purified cytochrome c and cytochrome oxidase was studied by absorption and circular dichroic spectrometry. Treatment of cytochrome oxidase with phosphine yielded absorption spectra in both the visible and Soret region that were similar to that produced by dithionite. Striking changes in the circular dichroic spectra were also recorded, sugesting that a valence change of the heme iron was accompanied by a conformation change of the prosthetic group.Phosphine treatment of cytochrome c also yielded spectra similar to those produced by reduction with dithionite suggesting a valence change of the heme iron. However, both the time necessary for complete reduction and the concentration of phosphine necessary for this effect suggest that, in comparison with cytochrome oxidase, cytochrome c was relatively insensitive. Reduction of cytochrome oxidase by phosphine had only a very minor effect on the intrinsic dichroic spectrum suggesting little effect on the polypeptide chains.The persistence of a component after reduction by phosphine and the subsequent reduction of this component by dithionite suggests that phosphine primarily reduced only one comonent of the cytochrome aa₃ complex. The failure of EDTA and fluoride, which are known ligands of cytochrome a₃ to affect the reduction of cytochrome aa₃ by phosphine, as well as the occurrence of a 436-nm isosbestic point of the ferric-ferrous absorption spectra suggests that phosphine reduced primarily cytochrome a. However, it is argued that a slow reduction of cytochrome a₃ cannot be ruled out.     

Isomerization and Beckmann rearrangement reactions in the metabolism of methomyl in rats

Methomyl {S-methyl-N-[(methylcarbamoyl)oxy]thioacetimidate}, also known as Lannate, may exist in two geometric configurations but the more stable syn isomer is the form applied as an insecticide. In the rat, syn[¹⁴CN]methomyl [CH₃S(CH₃)CNOC(O)NHCH₃] was metabolized to respiratory ¹⁴CO₂ and $\text{CH}{}_3{}^{14}\text{CN}$ in a ratio of about 2 to 1. Studies with the anti isomer showed that it was metabolized predominately to $\text{CH}{}_3{}^{14}\text{CN}$. These and other data are presented supporting the contention that syn methomyl is partially isomerized to the anti isomer in the animal prior to the hydrolysis of the ester linkage. After hydrolysis, the syn oxime [CH₃S(CH₃)¹⁴CNOH] is further metabolized to ¹⁴CO₂ while the anti oxime is metabolized to $\text{CH}{}_3{}^{14}\text{CN}$. Proposed immediate precursors to the carbon dioxide and acetonitrile, formed by Beckmann rearrangement of the syn and anti oximes, are CH₃S¹⁴C(O)NHCH₃ and $\text{[}\text{CH}{}_3{}^{\mathrm{14\oplus }}\text{CNSCH}{}_3\text{]x}{}^{\mathrm{?}}$, respectively.     

First record of bacillary rickettsia-like organisms in European tick Dermacentor marginatus (Sulzer).

Bacillary rickettsia-like organisms (BRLO) were found in the tick Dermacentor marginatus. They are gram-negative and differ from common bacteria and reckettsiae both in the cultivation conditions and morphology. BRLO are non-pathogenic for ticks and guinea pigs. In our studies they were isolated on half-engorged females of D. marginatus, on which they are still maintained.     

Cestodes of ruminants in Afghanistan.

Five cestode species parasitizing ruminants were found for the first time in Afghanistan: Moniezia benedeni, M. expansa, Avitellina centripunctata, Stilesia globipunctata, and Thysaniezia giardi.     

Seasonal activity of EPTC for Cyperus rotundus L. control in a tropical climate*

Four experiments were conducted at six week intervals to determine the seasonal activity and persistence of soil-incorporated EPTC (5-ethyl N,N-dipropyl(thiocarbamate)) for Cyperus rotundus L. control and tolerance of okra (Hibiscus esculentus L.), cucumber (Cucumis sativus L.), lettuce (Lactuca sativa L.), red beet (Beta vulgaris L.) and carrot (Daucus carota L.) during the dry and wet seasons in Viçosa, Brazil. Satisfactory control of C. rotundus was obtained at 2 kg/ha EPTC during the dry season and 4 kg/ha or more during the wet season. Only red beet and carrot tolerated these doses of EPTC when the crops were planted five days after application. However, selective control of C. rotundus was obtained when the planting date of lettuce was delayed for three or six weeks after EPTC application. EPTC controlled C. rotundus at half the dose that was required to control three species of annual grass that germinated near the soil surface. EPTC persisted longer when applied to air dry soil and incorporated with a rototiller than when incorporated into moist or wet soil.     

Distinguishing between carbamate and organophosphate insecticide poisoning in house flies by symptomology

Three criteria, latency to convulsions, still period, and recovery are used to distinguish between carbamate and phosphate insecticide poisoning in house flies, Musca domestica. Because of shorter latencies with carbamate-treated flies, the central nervous system was considered more sensitive to the presence of carbamates than phosphates. Recovery from carbamate-induced tetany was considered correlated with reactivation of carbamylated cholinesterase. There appeared to be a fundamental difference between the insecticidal actions of carbamates and phosphates not wholly explainable by cholinesterase inhibition. Tethered or held house flies were less susceptible to poisoning than unrestrained flies.     

Spectral interactions of insecticide synergists with microsomal cytochrome P-450 from insecticide-resistant and susceptible house flies

The spectral interactions of 45 insecticide synergists and related compounds with oxidized and reduced cytochrome P-450 from microsomes of insecticide-resistant and -susceptible house flies were investigated. The type III interaction typical of piperonyl butoxide was the most common spectral interaction for the compounds studied. In addition to this, several other varients of the type III interaction were noted. In general these responses with house fly microsomes were similar to those reported for mammals, although some minor species and strain differences were observed. The cytochrome P-450 from susceptible house flies, although reported previously not to exhibit type I difference spectra with many xenobiotics, was found to elicit this spectral response with several methylenedioxyphenyl compounds.     

Biochemical genetics of oxidative resistance to diazinon in the house fly

The genetics and biochemistry of oxidative resistance to diazinon were investigated in a diazinon-resistant strain of the house fly, Musca domestica L. The resistant strain was crossed with a multimarker susceptible strain and substrains containing portions of the resistant strain genome were prepared. Resistance, microsomal oxidase, and cytochrome P-450 spectral characteristics were then compared in the different strains. The major gene for resistance to diazinon is semidominant and is located on chromosome II, 13 crossing over units from the recessive mutant stubby wing. Additional resistance genes occur on chromosome II and on other chromosomes as well. Resistance to diazinon was introduced into a susceptible mutant-marked strain via genetic crossing over. Increases in parathion oxidase, total and P-450-specific N- and O-demethylase activity, and resistant strain type I binding spectrum were introduced along with resistance, indicating genes controlling these parameters and resistance are either identical or closely linked. No increase in activity of cytochrome P-450 itself was introduced into the mutant strain. Additional genes controlling the amount of cytochrome P-450 and several spectral changes characteristic of the resistant strains are apparently controlled by genes located at different loci on chromosome II. Resistance factors on other chromosomes are also present, but were not characterized.     

Comparative enzyme activities and cytochrome P-450 levels of some rat tissues with respect to their metabolism of several pesticides

Cytochrome P-450, A- and B-esterase, amidase, and glutathione S-aryl transferase were assayed in the postmitochondrial centrifugal fraction, microsomes, and supernatant of rat liver, lungs, kidneys, and testes. Liver microsomes contained the highest P-450 levels and A-esterase activity. B-esterase activity was more generally distributed and higher in the microsomal tissue fractions. Microsomal amidase activity was highest in rat lung and lowest in the liver (per mg protein). Glutathione S-aryl transferase activity was highest in the liver. The in vitro metabolism of carbaryl, phosphamidon, and chlorotoluron by the various centrifugal fractions revealed many differences. Carbaryl metabolism was greater in the liver microsomal fractions than in any other preparation. 1-Naphthol was the major metabolite in all tissue fractions. Although very little metabolism of phosphamidon occurred in the rat, metabolism in the rat liver postmitochondrial fraction was slightly higher with respect to the production of metabolites than in the supernatant and microsomes combined. Chlorotoluron was not metabolized by any of the tissue fractions of the rat. At least a low level of activity toward some compounds was observed in all tissues, but this study confirmed that the liver was the most active metabolizing tissue as well as having the highest levels of enzymatic activity usually associated with pesticide metabolism.