Structure-gas chromatographic electron capture sensitivity relationships of some substituted 17alpha-acetoxyprogesterones.
Structure-electron capture sensitivity relationships were established for underivatized 17alpha-acetoxyprogesterones. While progesterone was very insensitive, 17alpha-acetoxyprogesterone had a response of 4.8 X 10(2) C/mole. Methyl groups in the A or B ring of 17alpha-acetoxyprogesterone had no effect. A keto group at C-6 was 25 times more sensitive (1.2 X 10(4) C/mole). A double bond at C-6,7 enhanced the sensitivity sevenfold (3.5 X 10(3) C/mole), but double bonds at C-1,2 or C-9,11 had only slight effect. Substitution at C-16 was important. A methyl group at C-16 had two and three times the sensitivity in the 3-keto delta4 and 3-keto delta4,6 series (1.1 X 10(3) and 1.1 X 10(4) C/mole), respectively. A methylene group at C-16, in contrast showed a six-and twofold greater sensitivity over the C-16 methyl in the two series (7 X 10(3) and 2.2 X 10(4) C/mole), respectively. The most sensitive compound was 6-dehydro-6methyl-16-methylene-17alpha-acetoxyprogesterone (melengestrol acetate). Its sensitivity was 2.2 X 10(4) C/MOL, Comparable to the most sensitive halo esters of steroid alcohols reported in the literature. Its electron capture coefficient was 3-7.6X 10(10) 1/mole. The coef-icient was independent of the detector temperature, indicating low activation energy for electron absorpiton.
Chapter 14 Steroids
Publisher Summary This chapter focuses on high performance liquid chromatography (HPCL) of steroids and on natural products, including steroids available. It presents genuine sterols having one oxygen function. The genuine sterols and, especially, their esters are difficult to separate, because this class of steroids includes homologs (C 26 to C 30 ) and stereoisomers (C-3, C-5, and C-24 isomers). It also includes double-bond isomers, and the 24, 28-double bond may exhibit geometric isomerism, but the 22, 23-double bond usually has the trans-configuration. For the separation of free sterols by gas chromatography (GC), the phenylmethylsilicones, OV-17 and OV-25, are more suitable than the less polar stationary phases, UCCW-982 and SE-30. The relative retention times (RRT) of homologous sterols are in the order C 27 28 29 . The effect of double bonds depends on the location in the molecule. Whereas conversion of sterols to their acetyl derivatives increases the RRT on all four of the stationary phases, conversion to the TMS ethers increases RRT in UCCW-982 and SE-30 but decreases them in OV-17 and OV-25 columns.
Intentional poisoning cases of animals with anticholinesterase pesticide-carbofuran in Sri Lanka.
Carbofuran is a broad spectrum insecticide and nematicide which inhibits acetyl cholinesterase. Several intentional poisoning cases of animals and birds including crows, dogs, cow, and elephant, using carbofuran were reported in Sri Lanka. Qualitative analysis of carbofuran in biological specimens was carried out using T.L.C and GC-MS. The quantitative analysis was carried out by HPLC using Zorbax Eclips XDB-C18 (150 x 4.6 mm I.D x 5 microm particle size) column with acetonitrile: water 25:75 v/v mobile phase and UV detection at 210 nm. The liquid-liquid extraction with chloroform was reproducible and sensitive. The procedure was validated in terms of linearity (0.996<r<0.999) for concentrations ranging from 1 to 200 microg/ml, repeatability (RSD 4.4% at 100 microg/ml, n=10) extraction recovery (91.7% at 100 microg/g, 77.3% at 20 microg/g), limit of detection (S/N ratio=3, 0.7 microg/ml) and limit of quantification (S/N ratio=10, 2.4 microg/ml). The method was found satisfactory and successfully applied in fatal cases of animals and birds due to carbofuran poisoning. The fatal carbofuran levels detected were in the range of 42-910 microg/g in crow's gizzard and contents, 50-800 microg/g in dog's stomach contents, 13-20 microg/g in dog's liver, 0.9 microg/g in cow's stomach and contents, 35 microg/g in elephant's stomach and contents.