Simple and sensitive determination of methylglyoxal in biological samples by gas chromatography with electron-capture detection

Methylglyoxal was allowed to react with 4,5-dichloro-1,2-phenylenediamine, and the 6,7-dichloro-2-methylquinoxaline formed was determined by gas chromatography with electron-capture detection. The standard curve of the quinoxaline was linear up to 160 pmol/ml. The recoveries of methylglyoxal from coffee and rat liver homogenate were 84.1 and 77.6%, respectively. This procedure was very selective and so sensitive that as little as 9 fmol of the quinoxaline could be measured in biological and food samples.     

Simple and sensitive determination of diacetyl and acetoin in biological samples and alcoholic drinks by gas chromatography with electron-capture detection.

Acetoin was quantitatively oxidized into diacetyl by Fe3+ in 1 M perchloric acid. The reaction of diacetyl with 4,5-dichloro-1,2-diaminobenzene afforded 6,7-dichloro-2,3-dimethylquinoxaline (DCDMQ), which was extracted by benzene containing aldrin (25 ng/ml) as an internal standard, and determined by gas chromatography with electron-capture detection. The method is very simple and sensitive. The detection limit of DCDMQ (either diacetyl or acetoin) was 10 fmol/microliters of the benzene extract, and the determination limit of DCDMQ (either diacetyl or acetoin) was 50 fmol/microliters of the extract. Both acetoin and diacetyl could be determined in 0.1 ml of normal human urine or blood, and both were found in rat liver, kidney and brain. The method was also applied to the determination of acetoin and diacetyl in alcoholic drinks.     

Determination of toxaphene enantiomers by comprehensive two-dimensional gas chromatography with electron-capture detection

Comprehensive two-dimensional gas chromatography with micro electron-capture detection (GC x GC-microECD) has been evaluated for the enantioseparation of five chiral toxaphenes typically found in real-life samples (Parlar 26, 32, 40, 44 and 50). From the two enantioselective beta-cyclodextrin-based columns evaluated as first dimension column, BGB-176SE and BGB-172, the latter provided the best results and was further combined with three non-enantioselective columns in the second dimension: HT-8, BPX-50 and Supelcowax-10. The combination BGB-172 x BPX-50 was finally selected because it provided a complete separation among all enantiomers. A satisfactory repeatability and reproducibility of the retention times in both the first and the second dimension were observed for all target compounds (RSDs below 0.8%, n = 4). Linear responses in the tested range of 10-200 pg/microl and limits of detection in the range of 2-6 pg/microl were obtained. The repeatability and reproducibility at a concentration of 100 pg/microl, evaluated as the RSDs calculated for the enantiomeric fraction (EF), was better than 11% (n = 4) in all instances. The feasibility of the method developed for real-life analyses was illustrated by the determination of the enantiomeric ratios and concentration levels of the test compounds in four commercial fish oil samples. These results were compared to those obtained by heart-cut multidimensional gas chromatography using the same enantioselective column.     

Simultaneous determination of nitroglycerin and its dinitrate metabolites by capillary gas chromatography with electron-capture detection

A sensitive gas chromatographic-electron-capture detection method for the simultaneous determination of the antianginal drug nitroglycerin (GTN) and its dinitrate metabolites (1,2-GDN and 1,3-GDN) was developed. Human plasma samples (1 ml) spiked with 2,6-dinitrotoluene as the internal standard were extracted once with 10 ml of a methylene chloride-pentane mixture (3:7, v/v). Using this solvent system, less contaminants are extracted into the organic phase from plasma, resulting in cleaner chromatograms and prolonged column life. A break point was observed on the standard curves of GTN and GDNs. The two linear regions for the detectable concentrations of GTN are 0.025-0.3 and 0.3-3 ng/ml and for 1,2-GDN and 1,3-GDN they are 0.1-1 and 1-10 ng/ml. The limits of detection by this method for GTN, 1,2-GDN and 1,3-GDN in plasma are 0.025, 0.1 and 0.1 ng/ml, respectively.     

Simultaneous determination of griseofulvin and 6-desmethylgriseofulvin in plasma by electron-capture gas chromatography

Two methods have been developed for the simultaneous determination of griseofulvin and its major metabolite 6-desmethylgriseofulvin in plasma using electron-capture gas chromatography. The first method was based on the quantitative reversion of the 6-desmethyl metabolite to griseofulvin by diazomethane. Plasma extract was chromatographed both before and after treatment with diazomethane, the former being the measure of griseofulvin and the latter representing the sum of the two compounds. In the second method, plasma extract was treated with diazobutane and griseofulvin and the butylated metabolite were separated by gas chromatography. The sensitivity for griseofulvin was 20 ng/ml by both methods and that for the metabolite was 20 ng/ml and 40 ng/ml by the first and the second method, respectively. The concentrations of the metabolite as well as griseofulvin were determined in dog and human plasma after oral administration of griseofulvin.     

Semiautomatic method for the screening and determination of 23 organochlorine pesticides in horticultural samples by gas chromatography with electron-capture detection.

A rapid, simple, efficient device for the extraction-preconcentration of 23 organochlorine pesticides currently applied to vegetables is proposed. Pesticide residues are extracted from chopped samples by using a mixture of distilled water and light petroleum (1:1, v/v). After phase separation, an aliquot of the organic layer is continuously evaporated to dryness under a N2 stream as it is dropped into a glass tube containing distilled water. The aqueous phase, containing the analytes, is then passed through a miniaturized RP-C18 column for preconcentration, clean-up and subsequent elution with 150 microliters of ethyl acetate. A volume of 1 microliter of the extract containing pesticides is injected into the gas chromatograph, fitted with an electron-capture detector, for their selective determination. Limits of detection vary between 0.04 and 10 ng/ml, with linear ranges from 0.2 to 500 ng/ml; the average relative standard deviation at the low nanogram-per-millilitre level is 5.3%. The potential of the proposed method was realized by applying it to the screening/determination of organochlorine pesticides in horticultural commodities.     

Annular denuder tube preconcentrator for nitrobenzene determination by gas chromatography with electron-capture detection

A platinum/lead alloy-coated annular denuder tube was employed to concentrate nitrobenzene from nitrogen atmospheres of relative humidity < 5% at ambient temperatures. The limit of detection achieved was 1.7 ng of nitrobenzene, which could be obtained from a concentration of 0.15 μg m^?3 of nitrobenzene in nitrogen. Quantification was carried out at concentrations above 0.12 μg m^?3 of nitrobenzene in nitrogen over a 4-month period, although ageing and deterioration of the denuder system were noted, necessitating regular recalibration. The results support claims made elsewhere regarding the suitability of denuder tubes for organic vapour determination, in this instance with an analyte-selective collection surface.     

Quantitative determination of nitroglycerin in human plasma by capillary gas chromatography with electron-capture detection

A sensitive method for the selective determination of nitroglycerin at concentrations down to 50 pg/ml in human plasma is described. After the addition to plasma of a known amount of butane-1,2,4-triol trinitrate as internal standard, both compounds are extracted into hexane. Nitroglycerin is then quantitated by capillary gas chromatography with electron-capture detection.     

Affordable and sensitive determination of artemisinin in Artemisia annua L. by gas chromatography with electron-capture detection

Artemisinin demand has increased sharply since the World Health Organization recommended its use as part of the artemisinin combination therapies in 2001. The area for the crop cultivation has expanded in Africa and Asia and simpler and affordable methods for artemisinin analysis are needed for crop quality control. This work presented a novel chromatographic method of artemisinin analysis using gas chromatography with electron-capture detection. The sample extraction and preparation involved a single-solvent one-step extraction, with samples being analyzed in the extraction solvent directly after extraction. This method was accurate and reproducible with over 97% recoveries. The limit of detection was less than 3 microg/mL and the limit of quantification was less than 9 microg/mL, allowing samples as low as 100mg dry weight to be analyzed for artemisinin. The method can be applied to quality control of commercial plant extracts and to artemisinin-derived pharmaceuticals.     

Solid-phase extraction of fluoxetine and norfluoxetine from serum with gas chromatography-electron-capture detection

A rapid, selective, and sensitive method is described for the purification and analysis of fluoxetine and norfluoxetine using a solid-phase extraction column and gas chromatography-electron-capture detection. Linear quantitative response curves for fluoxetine and norfluoxetine are generated over a concentration range of 20-200 ng/ml. Overall extraction efficiency of the extraction procedure is found to be greater than 90% and greater than 75% with correlation coefficients of 0.997 and 0.993 for fluoxetine and norfluoxetine, respectively.     

Direct acetylation and determination of chlorophenols in aqueous samples by gas chromatography coupled with an electron-capture detector

A method was developed that offers a rapid, simple and accurate technique for the determination of chlorophenols at trace levels in aqueous samples with very limited volumes of organic solvents. These compounds were acetylated, then preliminarily extracted with n-hexane. The enriched chlorophenols were directly analyzed using gas chromatography with an electron-capture detector. The detection limits were in the range of 0.001-0.005 mg/L, except for 2-chlorophenol, which was always above 0.013 mg/L. Relative standard deviation for the spiked water samples ranged from 2.2 to 6.1%, while relative recoveries were in the range of 67.1 to 101.3%.     

Simultaneous determination of "earthy-musty" odorous haloanisoles and their corresponding halophenols in water samples using solid-phase microextraction coupled to gas chromatography with electron-capture detection

Certain haloanisoles present at trace levels cause a large part of earthy-musty off-flavor problems in drinking water. These potent odorous chemicals come mainly through biomethylation of their corresponding halopenols. To enable the investigation of both families of compounds, a method involving solid-phase microextraction (SPME) was developed and the main parameters governing SPME were optimized. This method allows the simultaneous quantification of haloanisoles and halophenols at levels ranging from 1 to 100 or 250 ng/l, with detection limits of about 0.5 ng/l and could be applied to potable as well as raw surface waters.     

Multiresidue determination of pesticides in honey by matrix solid-phase dispersion and gas chromatography with electron-capture detection

A multiresidue method was developed for the determination of 15 pesticides (organochlorines, organophosphorus compounds, pyrethroids, and other acaricides) in various commercial honeys (eucalyptus, lavender, orange, rosemary, and multifloral). The analytical procedure is based on the matrix solid-phase dispersion of honey in a mixture of Florisil and anhydrous sodium sulfate; the mixture is placed in small plastic columns and extracted with hexane-ethyl acetate (90 + 10, v/v). The pesticide residues are determined by capillary gas chromatography with electron-capture detection. Recoveries with the method at concentrations between 0.15 and 1.5 microg/g ranged from 80 to 113%, and relative standard deviations were <10% for all the pesticides studied. The pesticide detection limits were within the range 0.5-5 microg/kg for organochlorines, around 3 microg/kg for the chlorinated organophosphorus pesticides studied, near 15 microg/kg for fluvalinate, and about 3 microg/kg for the other pyrethroids.     

Determination of propafenone in biological fluids by fused-silica capillary gas chromatography using electron-capture detection

A gas-liquid chromatographic method with electron-capture detection using a capillary column with the inlet in the splitless injection mode is reported for the assay of propafenone. A 25 m X 0.31 mm cross-linked, 5% phenylmethylsilicone-coated fused-silica capillary column was employed for all analyses. The present method provides improved selectivity and sensitivity over other existing gas chromatographic and high-performance liquid chromatographic (HPLC) methods. Linearity was observed in the ranges 2.5-50 and 10-100 ng/ml. The coefficient of variation was found to be less than 10% over the concentration ranges studied. Application of the developed method is demonstrated by measuring serum propafenone concentrations over 24 h in a normal healthy volunteer after a single oral dose of propafenone and by measuring trough plasma propafenone concentrations at steady state in patients receiving this new antiarrhythmic drug. Validity of the present method is further demonstrated by comparison of analytical results obtained from measurement of patient samples using a modified published HPLC method.     

Comparison of two digestion methods used in the determination of selenium in marine biological tissues by gas chromatography with electron-capture detection

The performance of two decomposition procedures, with (a) nitric/perchloric/sulphuric acid and (b) nitric acid/magnesium nitrate, in the determination of selenium in marine biological tissues by gas chromatography with electron-capture detection was compared. Both methods were found satisfactory and performed equally well for sample dissolution, but method (b) was judged to be more convenient.