Gas-liquid chromatographic determination of T-2 toxin and diacetoxyscirpenol in corn and mixed feeds

A gas-liquid chromatographic method has been developed for the simultaneous determination of the T-2 toxin and diacetoxyscirpenol (DAS) in corn and mixed feeds. The analytes are extracted with aqueous methanol. Ammonium sulfate is used to denature and precipitate proteinaceous compounds and to salt out low polar compounds. The analytes are selectively concentrated into chloroform, which is washed with aqueous potassium hydroxide to remove acidic compounds. Residual interferences are removed by silica gel column chromatography. Heptafluorobutrylimidazole (HFBI) is added to form esters of the analytes. The HFB-esters are separated on an SE-30 glass column and measured witha 63Ni electron capture detector, using methoxychlor as an internal standard. The method has been applied to corn, livestock feeds, and pet food. The limit of detection is 100 ng T-2 toxin and 25 ng DAS/G. Average recoveries of 105 and 97% and coefficients of variation of 17 and 10% were obtained for T-2 toxin and DAS, respectively.     

Gas-liquid chromatographic headspace technique for determination of vinyl chloride in corn oil and three food-simulating solvents

A gas-liquid chromatographic headspace technique for the determination of vinyl chloride (VC) in corn oil, 50% ethanol, 3% acetic acid, and n-heptane is described. These food-simulating solvents and the corn oil are placed in septum-sealed bottles and heated to 90 degrees C, and aliquots of headspace vapor are injected into a gas-liquid chromatograph equipped with a flame ionization detector. VC may be quantitated at concentrations of 1 ppb or less. This technique was used to measure the migration of VC into corn oil and 50% ethanol from 2 unplasticized polyvinyl chloride sheets containing 0.28 and 0.44 ppm residual monomer.     

Thin layer chromatographic determination of sterigmatocystin in cereal grains and soybeans

A method has been developed for determining sterigmatocystin in yellow and white corn, barley, oats, rye, sorghum, brown and wild rice, and soybeans. A partition column packed with activated magnesium silicate was used for cleanup. Averaged recoveries are 104% in white corn, 114% in rye, 100% in oats, 134% in brown rice, 96% in barley, 105% in sorghum and wild rice, and 92% in soybeans. The limit of sensitivity is 50 mug/kg for any of these commodities.     

Gas-liquid chromatographic determination of azinphos ethyl in human plasma and in mouse plasma, tissue, and fat

A new method for the determination of azinphos ethyl (O,O-diethyl-S-(4-oxo-1,2,3-benzotriazin-3(4H)-ylmethyl) phosphorodithioate) in human plasma and in mouse plasma, tissue, and fat has been developed. The method is based on extraction with benzene or hexane and cleanup of fat and tissue samples by a minicolumn containing Florisil and sodium sulfate. Azinphos ethyl is eluted from the column with 10% acetonitrile in benzene and is concentrated to an appropriate volume for gas-liquid chromatographic analysis, using a 63Ni electron capture detector and a glass column containing 3% OV-1 on Gas-Chrom Q. The method is sensitive to 0.005 ppm in human plasma, 0.01 ppm in mouse plasma, 0.08 ppm in mouse liver, 0.05 ppm in mouse brain, and 0.10 ppm in mouse fat. The limit of detection is 2 pg; mean recoveries ranged from 96 to 98%.     

Gas-liquid chromatographic determination of the optical isomers of fenfluramine and norfenfluramine in biological samples

Cysticercosis is a parasitic disease in which man serves as the intermediate host of Taenia solium, the pork tapeworm. The larvae have a predilection for the central nervous system and can cause a variety of neurologic and psychiatric symptoms. Areas of involvement are classified as intraventricular, parenchymal, arachnoidal, and mixed. The diagnosis is made primarily by roentgenographic and spinal fluid examinations. The authors reviewed 232 cases of cysticercosis involving the central nervous system. It was found that computed tomography is a useful tool in assessing this illness.     

Evaluation of amperometric detector for liquid chromatographic determination of 2-phenylphenol residues in orange rind

A modular component liquid chromatograph has been assembled which has on-stream ultraviolet (UV) and amperometric detectors connected to a dual pen recorder. In this method, the commonly used UV detection technique provides a reference for direct comparisons of results from the amperometric detector. The system has been evaluated and applied to the determination of 2-phenylphenol (2PP) fortified in orange rind. The method is not tedious; before liquid chromatographic analysis, the sample is extracted with methylene chloride and cleaned up on a Florisil column. The method is sensitive to less than 1 ppm 2PP fortified in orange rind; there are no electrically oxidizable interference, from control samples, in the chromatographic region of 2PP. Some background interference does appear from the same samples on the UV chromatogram. Thus, amperometric detection is more specific than UV detection for this application.     

Gas-liquid chromatographic determination of clonidine and some analogues in rat brain tissue. Brain concentrations and hypotensive activity

A simple and sensitive gas-liquid chromatographic method has been developed for the quantitative determination of clonidine and some structurally related imidazolidines in rat brain tissue. The aqueous brain homogenates are first purified and then extracted into benzene. Samples are injected directly into the gas chromatograph. The extraction procedure is selective, and the use of a phosphorus-nitrogen detector enables accurate determinations corresponding to brain concentrations down to at least 10ng/g. The rat brain concentrations of clonidine and its derivatives achieved at the moment of maximal decrease in arterial pressure are proportional to the doses administered intravenously, and are not influenced by the effect of the compounds on the blood pressure or by the method of anaesthesia employed. It is concluded that, for the linear part of the dose-response curves for these compounds, the brain concentration is a measure of the hypotensive effect.     

Inactivation of S-adenosyl-L-homocysteine hydrolase and antiviral activity with 5',5',6',6'-tetradehydro-6'-deoxy-6'-halohomoadenosine analogues (4'-haloacetylene analogues derived from adenosine)

Treatment of a protected 9-(5, 6-dideoxy-beta-D-ribo-hex-5-ynofuranosyl)adenine derivative with silver nitrate and N-iodosuccinimide (NIS) and deprotection gave the 6'-iodo acetylenic nucleoside analogue 3c. Halogenation of 3-O-benzoyl-5,6-dideoxy-1, 2-O-isopropylidene-alpha-D-ribo-hex-5-enofuranose gave 6-halo acetylenic sugars that were converted to anomeric 1,2-di-O-acetyl derivatives and coupled with 6-N-benzoyladenine. These intermediates were deprotected to give the 6'-chloro 3a, 6'-bromo 3b, and 6'-iodo 3c acetylenic nucleoside analogues. Iodo compound 3c appears to inactivate S-adenosyl-L-homocysteine hydrolase by a type I ("cofactor depletion") mechanism since complete reduction of enzyme-bound NAD+ to NADH was observed and no release of adenine or iodide ion was detected. In contrast, incubation of the enzyme with the chloro 3a or bromo 3b analogues resulted in release of Cl- or Br- and Ade, as well as partial reduction of E-NAD+ to E-NADH. Compounds 3a, 3b, and 3c were inhibitory to replication of vaccinia virus, vesicular stomatitis virus, parainfluenza-3 virus, and reovirus-1 (3a < 3b < 3c, in order of increasing activity). The antiviral effects appear to correlate with type I mechanism-based inhibition of S-adenosyl-L-homocysteine hydrolase. Mechanistic considerations are discussed.     

Gas chromatographic determination of micro amounts of cyanide residues in wines, distilled liquors, and other alcoholic beverages

A gas chromatographic method for the determination of cyanide residues in alcoholic beverages has been developed from procedures previously reported for application to water samples. Quantitatively isolating HCN from alcoholic beverages presented difficulties not encountered with aqueous solutions, particularly in the presence of S02 in the sample. HCN was liberated from the acidified sample by heating at 70 degrees C, flushed into an NaOH absorber solution, converted to cyanogen bromide (CNBr), extracted into diisopropyl ether, chromatographed on a Porapak Q column, and detected by an electron capture detector. S02 that is present in most wines interfered with the bromination step and caused low recoveries. This interference was eliminated by initially converting any cyanide present in the sample to the stable mercuric cyanide salt and then purging the acidified sample solution of all S02. The Hg(CN)2 present was then dissociated by adding KI and the analysis proceeded as previously described. Mean recoveries of 80-97% were obtained for 2-20 mug cyanide from replicate analyses of spiked samples of distilled liquors free of S02. The relative standard deviations ranged from 6.1 to 11.1%. Mean recoveries of 65 to 91% were obtained in the same range of cyanide from replicate analyses of spiked wine samples known to contain S02, with relative standard deviations ranging from 0.8 to 10.2%. The limit of detection was 0.2 mug HCN.     

4-(5-氯-2-吡啶偶氮)-1,3-二氨基苯分光光度法测定微量锶

在十二烷基磺酸钠(SDS)胶束溶液存在下,研究了锶(与4-(5-氯-2-吡啶偶氮)-1,3-二氨基苯的显色反应。试验表明,在pH 6.0的乙酸-乙酸钠缓冲溶液中,锶(与该试剂形成1∶1的黄色络合物,络合物的最大吸收峰在460 nm波长处,表观摩尔吸光系数ε为1.29×105。25 mL溶液中,锶(含量在0~12μg范围内符合比尔定律。本法用于铝合金和化学试剂中微量锶的测定,结果令人满意。     

Efficacy of 6-chloro-2'',3''-dideoxyguanosine (6-Cl-ddG) on rhesus macaque monkeys chronically infected with simian immunodeficiency virus (SIVmac239)

The object of the present work was to study the relationship between acute pancreatitis (PA) and hyperlipidic diets. PA was induced by Caerulein (CE) by a single intraperitoneal doses (50 mcg/kg), after feeding the rats during 6 weeks with an hyperlipidic diet (45%). Rats with a normolipidic diet (lipids 5%) were used as control. The increase of serum lipase was similar in both groups treated with CE (control and with hyperlipidic diet). There were increase of interstitial edema, cariorrexis and a specially marked increase in the level of vacuolization of acinar cells with respect to the control group. It was concluded that chronic hyperlipidic diet increases histopathologic lesions in PA induced by CE in rats.     

Synthesis and evaluation of analogues of the partial agonist 6-(propyloxy)-4-(methoxymethyl)-beta-carboline-3-carboxylic acid ethyl ester (6-PBC) and the full agonist 6-(benzyloxy)-4-(methoxymethyl)-beta-carboline-3-carboxylic acid ethyl ester (Zk 93423) at wild type and recombinant GABAA receptors

A pharmacophore and an alignment rule have previously been reported for BzR agonist ligands. The design and synthesis of 6-(propyloxy)-4-(methoxymethyl)-beta-carboline-3-carboxylic acid ethyl ester (6-PBC, 24, IC50 = 8.1 nM) was based on this pharmacophore. When evaluated in vivo this ligand exhibited anticonvulsant/anxiolytic activity but was devoid of the muscle relaxant/ataxic effects of "classical" 1,4-benzodiazepines (i.e., diazepam). Significantly, 6-PBC 24 also reversed diazepam-induced muscle relaxation in mice. The 3-substituted analogues 40-46 and 48 of 6-PBC 24 and Zk 93423 27(IC50 = 1 nM) were synthesized and evaluated in vitro to determine what affect these modifications would have on the binding affinity at recombinant BzR subtypes. With the exception of the 3-amino ligands 40 and 41, all the beta-carbolines were found to exhibit high binding affinity at BzR sites. The 3-propyl ether derivative 45 was also evaluated in vivo and found to be devoid of any proconvulsant or anticonvulsant activity at doses up to 40 mg/kg. The 6-(1-naphthylmethyloxy) and 6-octyloxy analogues 25, 26, 28, and 29 of 6-PBC 24 were synthesized to further evaluate the proposed alignment of agonists vs inverse agonists in the pharmacophore of the BzR. In addition, ligands 26 and 29 were designed to probe the dimensions of lipophilic pocket L3 at the agonist site. The activity of 29 was evaluated in vivo; however, this analogue elicited no pharmacological effects at doses up to 80 mg/kg. These and other related beta-carbolines were also examined in five recombinant GABAA receptor subtypes. Ligands 52-61 all exhibited moderate to high affinity at GABAA receptors containing alpha1 subunits. These ligands will be useful in further defining the pharmacophore at alpha1 beta3 gamma2 receptors.     

New derivatization method for determination of 3-chloro-4(dichloromethyl)-5-hydroxy-2(5H)-furanone in water

An extremely potent mutagen, 3-chloro-4(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) is commonly present in chlorinated drinking water. Due to its high mutagenic activity and according to World Health Organization guidelines its concentration should be controlled in drinking waters. Determination of MX is difficult due to ppt levels at which the compound usually exists in drinking waters. Derivatization of MX with 2-propanol is presented as a method which significantly lowers the GC-MS detection level compared to other alcohol derivatization agents.     

Gas-liquid chromatographic properties of positional isomers of methyl thia, selena, and tellura laurate analogs

Gas-liquid chromatographic analyses of three complete series of synthetic positional isomers of methyl thia, selena, and tellura laurate analogs were carried on a nonpolar (SE-30) and a polar (SP-2330) stationary phase. The average ECL (equivalent chain length) values of the thia, selena, and tellura laurate on SE-30 stationary phase were 13.8, 14.8, and 15.7, respectively, while on SP-2330 the average values for the same series were 17.1, 19.0, and 19.1, respectively. Positional isomers with the heteroatom at the 2-position exhibited the lowest ECL values, while those with the heteroatom at the omega-1 position gave the highest ECL values and were readily separated from the other positional isomers of the same series of analogs by this technique.     

Gas chromatographic determination of Ostwald solubility coefficients for cyclopropane, halothane and trichloroethene (trichloroethylene)

Gas chromatographic methods using solvent extraction for the analysis of cyclopropane and and trichloroethene (trichloroethylene) are described and evaluated; cyclopropane was extracted into carbon tetrachloride and trichloroethene into carbon disulphide, using chloroform and toluene respectively as the internal standards. Ostwald solubility coefficients were measured for cyclopropane, halothane and trichloroethene in Krebs solution: at 310 K the respective values +/- SEM of the Ostwald coefficients are 0.181 +/- 0.009, 0.78 +/- 0.02 and 1.54 +/- 0.02; over the temperature range 295-310 K the respective temperature coefficients of solubility are -2.27, -4.18 and -3.81 in units of per cent/K at 310 K.     

Anti-hepatitis B virus activity and metabolism of 2',3'-dideoxy-2',3'-didehydro-beta-L(-)-5-fluorocytidine

2',3'-Dideoxy-2',3'-didehydro-beta-L(-)-5-fluorocytidine [L(-)Fd4C] was found to be at least 10 times more potent than beta-L-2',3'-dideoxy-3'-thiacytidine [L(-)SddC; also called 3TC, or lamivudine]against hepatitis B virus (HBV) in culture. Its cytotoxicity against HepG2 growth in culture was also greater than that of L(-)SddC (3TC). There was no activity of this compound against mitochondrial DNA synthesis in cells at concentrations upto 10 microM. The dynamics of recovery of virus from the medium of cells pretreated with equal drug concentrations were slower with L(-)Fd4C than with L(-)SddC (3TC). L(-)Fd4C could be metabolized to mono-, di-, and triphosphate forms. The degree of L(-)Fd4C phosphorylation to the 5'-triphosphate metabolite was higher than the degree of L(-)SddC (3TC) phosphorylation when equal extracellular concentrations of the two drugs were used. The apparent K(m) of L(-)Fd4C phosphorylated metabolites formed intracellularly was higher than that for L(-)SddC (3TC). This may be due in part to a difference in the behavior of L(-)Fd4C and L(-)SddC (3TC) towards cytosolic deoxycytidine kinase. Furthermore, L(-)Fd4C 5'-triphosphate was retained longer within cells than L(-)SddC (3TC) 5-triphosphate. L(-)Fd4C 5'-triphosphate inhibited HBV DNA polymerase in competition with dCTP with a Ki of 0.069 +/- 0.015 microM. Given the antiviral potency and unique pharmacodynamic properties of L(-)Fd4C, this compound should be considered for development as an expanded-spectrum anti-HBV drug.