Comparative assessment of solid-phase extraction clean-up procedures, GC columns and perfluoroacylation reagents for determination of type B trichothecenes in wheat by GC-ECD

Various solid-phase extraction (SPE) procedures for clean-up, two perfluoroacylation reagents (pentafluoropropionic anhydride (PFPA) and heptafluorobutyric anhydride (HFBA)) and two chromatographic columns (HP-1701 and HP-5) have been assessed comparatively to achieve the determination of type B trichothecenes (deoxynivalenol (DON), nivalenol (NIV), 3- and 15-acetyldeoxynivalenol (3- and 15-ADON)) in wheat grain by gas chromatography (GC)-electron-capture detection (ECD). Spiked wheat samples were extracted with acetonitrile-water (84:16, v/v). Tested SPE procedures were MycoSep 225 column, Florisil and different cartridges prepared in the laboratory with mixtures of various sorbents like alumina, Celite 545, C18, silica and charcoal. We propose MycoSep 225 column, and cartridges made with alumina-charcoal-silica and alumina-charcoal-C18 silica mixtures as clean-up procedures on the basis of recovery values (89.6, 87.3 and 86.1% for deoxynivalenol, respectively, at 1.0 mg/kg spiking level). The two last procedures are less expensive. Pentafluoropropionic anhydride was more stable against moisture and less expensive, while recoveries were similar to those obtained with heptafluorobutyric anhydride. HP-1701 column can separate 3- and 15-acetyldeoxynivalenol derivatives while HP-5 cannot, although this last column provided lower bleed and better sensitivity.     

Trace determination of iodide by derivatization and electron-capture gas chromatography

Summary A simple, sensitive and specific method is described for the determination of iodide as pentafluorobenzyl iodide, based on the chemical derivatization of iodide anion with pentafluorobenzyl bromide. The derivative formed in the reaction solution was directly analyzed, without further pretreatment, by gas chromatography with an electroncapture detector. The detection limit was about 1 ng of iodide anion in 0.10 ml of aqueous sample analyzed. Interferences of some common anions with the method were investigated and were proved to be minimal. It was demonstrated that the proposed method is applicable to the determination of iodide in spring water.

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Bestimmung von Iodidspuren durch Derivatisierung und Electron-Capture GC

Zusammenfassung Eine einfache, empfindliche und spezifische Methode wird beschrieben zur Iodidbestimmung als Pentafluorbenzyliodid, die auf der Reaktion von Iodid mit Pentafluorbenzylbromid beruht. Das gebildete Derivat wird direkt ohne weitere Vorbehandlung der GC mit Electron-Capture-Detektion unterworfen. Die Nachweisgrenze liegt bei etwa 1 ng Iodid in 0,1 ml. Störungen durch andere Anionen wurden untersucht und erwiesen sich als unbedeutend. Das Verfahren wurde zur Iodidbestimmung in Quellwasser angewendet.

     

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.     

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.     

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.     

Single-step multi-cartridge clean-up for organophosphate pesticide residue determination in vegetable oil extracts by gas chromatography

A multi-cartridge system has been developed which, in a single step, performs the extraction and clean-up of organophosphate (OP) pesticide residues from oils and fatty extracts. A solution in hexane containing up to 1.8 g of lipidic material is loaded on to an Extrelut-3 column to which a silica-gel cartridge and a C18 silica cartridge have been connected in series. The OP pesticide residues are eluted with 15 ml of acetonitrile. Carry-over of fatty material is in the range 2-5 mg per 1.8 g of different oils, which makes the final solution amenable to capillary gas chromatography. Recoveries of 23 OP pesticides were in the range 82-111%. The whole procedure takes ca. 20 min and compares favourably with current procedures.     

Enzyme activity determination by radio gas chromatography on capillary columns

Androgen 5α-reductase from the foreskin of 48 boys in prepubertal age was analyzed by evaluation of the apparent K_m-and V_max- values after tissue incubation. Reaction rates were calculated after determination of specific radioactivity of distinct metabolites, by comparison to the radioactivity of the precursor. Reaction products were separated by radio gas chromatography on capillary columns. The chromatography system was based on multicolumn equipment with column switching facilities and a variable splitter at the outlet of the separation column. A radioactivity monitor (gas proportional counter) was used for measurement of radioactivity in the column effluents. An electron capture detector was used for mass detection of steroid acyl derivatives.     

Rapid and highly sensitive method for determination of methamphetamine and amphetamine in urine by electron-capture gas chromatography

A rapid and sensitive method for determination of methamphetamine and amphetamine in urine was developed by using electron-capture gas chromatography. The extraction procedure, the experimental conditions for pentafluorobenzoyl derivative formation and the percentage recovery of the drugs from urine are described. The pentafluorobenzoyl derivative of methamphetamine showed a higher electron-capture sensitivity and was detected in at least 23-fold lower concentration than the heptafluorobutyryl derivative which is commonly used as a derivatizing agent for the amine. The detection limit of pentafluorobenzoyl derivatives of methamphetamine and amphetamine was ca. 10 pg. A concentration as low as 10 ng/ml of methamphetamine and amphetamine in urine was easily detected by this method.     

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.     

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.     

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.     

Comparative study of clean-up and fractionation methods for the determination of organochlorine pesticides in lipids by gas chromatography.

Three of the methods most often used for the clean-up and fractionation of organochlorine pesticides in lipid residue analysis by gas chromatography with electron-capture detection were compared. The overall recoveries of twenty pesticides from spiked samples were higher than 88%, the relative standard deviation being in the range 3-11% (n = 6) at the 36-80 ppb (10(9) level. The three methods were compared by analysis of variance, with no differences in precision at the 0.05 significance level. Differences in recoveries appeared in only two instances. None of the three methods seems to be significantly better than the others for the determination of the pesticides studied.     

Use of deactivated fused-silica capillary precolumns in pesticide analysis by gas chromatography with electron-capture detection.

The advantages and disadvantages of coupling a retention gap of fused-silica between the injection port and the chromatographic column are discussed. The influence on the peak width and height of several factors such as the solvent (n-hexane, acetone, ethyl acetate and methanol), the gap (length, inner diameter, deactivation mode), the injection volume and the pesticide concentration has been examined. Those factors have very different incidences so, it is not possible to extract a general recommendation about the use of gaps. For this reason, checking its viability in each particular case is more advisable.     

Sample clean-up by sol-gel immunoaffinity chromatography for determination of chloramphenicol in shrimp

The paper describes the characterisation and application of sol-gel columns prepared by entrapping anti-chloramphenicol (CAP) antibodies. Retention of CAP in the column was caused by specific interactions with the anti-CAP antibodies and not by non-specific adsorption to the sol-gel glass. After optimising important operation conditions, e.g. feeding medium, feeding flow-rate, elution medium, elution flow-rate and elution volume, the sol-gel columns were included in a clean-up procedure developed to determine CAP in shrimp. The selectivity of the columns was high enough to efficiently remove interfering matrix compounds. Due to the chromatographic conditions applied retention of cross-reacting substances in the immunoaffinity column did not pose a problem. CAP recovery of the analytical method was 68% with a relative standard deviation of 4% (n=4). In spite of applying highly complex shrimp extracts the columns could be used for clean-up of at least 12 samples. However, when detection of CAP is carried out with an UV detector the analytical method has a relatively poor sensitivity (LOD=1.8 ng/g, S/N=3). The most obvious way is to replace the UV detector by a detector based on an inherently more sensitive and selective detection principle, like a mass spectrometer.