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Modified on-column interface for coupled high-performance liquid chromatography-gas chromatography and its application to the determination of levamisole in milk.

A modified on-column interface is reported for the coupling of high-performance liquid chromatography with gas chromatography, incorporating an adapted, commercially available multidimensional gas chromatography switching system. Novel features include cryogenic analyte focusing, total solvent exclusion from the analytical column and independent carrier gas supplies to the analytical GC column and uncoated pre-column. The instrumentation was used for the determination of the veterinary anthelmintic drug levamisole in milk with analyte detection by both flame ionisation and nitrogen-phosphorus detectors. Detection limits for the assay were 2.2 micrograms l-1 and 0.4 micrograms l-1 by flame ionisation and nitrogen-phosphorus detectors, respectively. The assay was applied to a survey of fourteen milk samples from different dairy outlets.

Animals

On-line coupled liquid chromatography-gas chromatography (LC-GC) and LC-LC-GC for detecting irradiation of fat-containing foods.

On-line coupled liquid chromatography-gas chromatography-flame ionisation detection (LC-GC-FID) enables efficient and unambiguous determination of irradiation for some fat-containing foods (e.g. meat). Other products, however, contain interfering components or are contaminated, e.g., with mineral oil. Since more selective detection by mass spectrometry has limited success, the determination was improved by a more selective isolation of some key components among the fat degradation products, e.g. the dienes or trienes, by LC-LC-GC-FID. Applications are shown for soup mixes, some spices, fish, and shrimps.

Alkanes

Disopyramide determination by gas chromatography, liquid chromatography, and gas chromatography--mass spectrometry.

Disopyramide is determined in serum by gas chromatography with a nitrogen-selective detector, by liquid chromatography, and by gas chromatography--mass spectrometry. Comparable results are obtained with the three techniques, with a within-run and between-run precision of 5 to 10% (coefficient of variation). Least-squares analysis of data on patients' sera, analyzed first by gas chromatography (y) and then liquid chromatography (x), gave a slope of 1.12; y-intercept, -0.31; standard error of estimate, 0.46; and correlation coefficient, 0.94. Comparison of patients' sera by gas chromatography (y) and then by gas chromatography--mass spectrometry (x) gave a slope of 0.94; y-intercept, 0.42; standard error of estimate, 0.38; and correlation coefficient, 0.97. Interferences observed when using one technique--for example, gas chromatography--can be eliminated by analyzing the sample extract with one of the other techniques.

Chromatography, Gas

Use of new silylating agents for identification of hydroxylated steroids by gas chromatography and gas chromatography mass spectrometry.

Differences in methylene unit values were used for the determination of the hydroxyl group number of a steroid by means of gas chromatography. This index is defined as the difference in the methylene unit value between trimethylsilyl and other dimethylalkylsilyl (DMAS) ether derivatives of hydroxylated steroids, namely dimethylethylsilyl (DMES) and dimethyl-n-propylsilyl (DMPS) ethers. The reactivities of DMES and DMPS imidazoles as silylating agents were nearly equal to that of TMS-I. Mass spectra of these derivatives were characterized by the molecular ion cluster, [M]+., [M-15]+ and [M-29]+ (or [M-43]+). The molecular ion cluster of these derivatives is most useful for estimating the molecular weight. Therefore, these DMAS ethers provide valuable information for structural elucidation of hydroxylated steroids by gas chromatography electron impact mass spectrometry.

Chromatography, Gas

Determination of bromocriptine in plasma: comparison of gas chromatography, mass fragmentography and liquid chromatography.

Gas chromatographic, mass fragmentographic and liquid chromatographic techniques for the determinations of bromocriptine (2-bromo-alpha-ergocriptine; Parlodel) in human plasma are described. These methods were found to be suitable for determining concentrations of bromocriptine down to 0.5, 1.0 and 10.0 microgram/l, respectively. Accuracy, specificity and analytical capacity were satisfactory for all three methods. Gas chromatography was compared with liquid chromatography, and the two methods were demonstrated to give identical results in patients treated with bromocriptine for Parkinson's disease. Gas chromatography was also compared with mass fragmentography, and the results from these two assays were also in agreement.

Bromocriptine

Studies on monoterpene glucosides and related natural products. XXXI. Gas chromatography and gas chromatography-mass spectrometry of iridoid and secoiridoid glucosides.

A total of 33 iridoid and secoiridoid glucosides were detected by gas chromatography on several columns such as OV-1 or OV-17. Representative glucosides were then subjected to gas chromatography-mass spectrometry, giving some characteristic peaks that permitted the discrimination of both types of glucosides from other compounds in most instances. The successful detection of both types of glucosides in several plant extracts showed the applicability of this combination of methods to small amounts of plant materials.

Chromatography, Gas

Monoamine metabolites and related compounds in human amniotic fluid: assay by gas chromatography and gas chromatography-mass spectrometry.

Some catecholamine metabolites and related compounds have been identified in amniotic fluid obtained by transabdominal amniocentesis at various stages of pregnancy, including 4-hydroxy-3-methoxymandelic acid, 4-hydroxy-3-methoxyphenylglycol, 4-hydroxy-3-methoxyphenylcetic acid, p-hydroxypheny lacetic acid, p-hydroxphenyllactic acid and N-benzoylglycine (hippuric acid). Analysis was by gas chromatography with electron capture detection and by gas chromatography-mass spectrometry. Two of these compounds were determined quantitatively, free 4-hydroxy-3-methoxphenylglycol and p-hydroxyphenllactic acid: the concentration of the former increased with advancing pregnancy and that of the latter tended to decrease. Conjugated 4-hydoxy-3-methoxyphenylglycol could not be determined with accuracy as appreciable amounts of the unconjugated compound were found in the snail extract used for enzymatic hydrolysis. Assay of 4-hydroxy-3-methoxyphenylglycol in amniotic fluid is likely to be of diagnostic importance in the prenatal diagnosis of congenital neuroblastoma. Although 4-hydroxy-3-methoxyphenylethanol, 3, 4-dihydroxymandelic acid and 3, 4-dihydroxyphenylacetic acid were specifically looked for in amniotic fluid, they could not be detected.

Amniocentesis

Quantitative gas chromatography and gas chromatography-mass spectrometry of Cephalotaxus alkaloids.

Plants of the genus Cephalotaxus contaim many alkaloids, some of which have demonstrated antitumor activity. Analysis of crude alkaloid mixtures by gas chromatography provides quantitation of the active principles and other, non-active, alkaloids. Mass spectrometry is used to identify known alkaloids in extracts and to confirm the presence of previously unknown ones. Such data provide a means for predicting the biological activity of new plant accessions.

Alkaloids

The analysis of organic water pollutants by gas chromatography and gas chromatography-mass spectrometry.

Four methods for the analysis of trace levels or organic compounds in water have been discussed: direct aqueous injection, vapor stripping, solvent extraction, and lipophilic adsorption. Table 6 presents a comparison of these techniques. Direct injection is applicable to compounds having a wide range of polarities and volatilities, but it is not a very sensitive technique. For applications in which low sensitivity is acceptable, direct injection offers a very rapid and potentially accurate means of measuring organics in water. Vapor stripping is a factor of 10(6) more sensitive than direct injection, but this is achieved at the expense of simplicity. This method is applicable to compounds of volatilities less than that of eicosane. A subtle operational problem with most vapor stripping techniques is that the contents of the trap are consumed with one analysis; if anything goes awry, the analysis of that trapped sample cannot be repeated. Solvent extraction has a respectable sensitivity (about 0.5 ppb) and operationally it is very simple. Furthermore, aliquots of the resulting extract can be analyzed many times with different techniques if necessary. Because of the evaporation step, very volatile compounds (greater than that of decane) cannot be measured effectively with solvent extraction. The introduction of a solvent into the water carries with it the potential for contamination. Thus, ultrapure solvents must be used and all glassware should be carefully cleaned [96]. Lipophilic adsorption has the unique property of sampling many hundreds of liters of water. Thus, the method is quite sensitive (potentially in the ppt range) and, in addition, it can provide several milligrams of an isolated component. This latter feature is of considerable advantage if one wants to complement GC-MS analyses with infrared or NMR for difficult structural identifications. As a solvent extraction, the evaporation of the final solvent limits the applicability of adsorption methods to compounds with volatilities greater than that of decane. Finally, the importance of avoiding contamination should be emphasized. Many of the compounds encountered in environmental samples are also common laboratory artifacts, for example plasticizers and antioxidants. When one finds such compounds in a water sample, it is absolutely essential to demonstrate that they are indeed present in the water and are not the result of laboratory contamination. The best such demonstration is procedural blank analyses that are indeed blank.

Chromatography, Gas

Use of silylating agents for the identification of hydroxylated steroids by gas chromatography and gas chromatography-mass spectrometry. Discrimination between phenolic and alcoholic hydroxyl groups.

A phenolic trimethylsilyl (TMS) group was selectively exchanged for a dimethylalkylsilyl (DMAS) group on a gas chromatographic column by use of sandwich injection technique with DMAS-imidazole, and a TMS ether derivative of a phenolic steroid was converted into a DMAS ether or a mixed TMS and DMAS ether derivative with over 95% recovery. The selective exchange reaction seemed to be caused by the difference in lability between the ethereal TMS linkages to phenolic and alcoholic hydroxyl groups. This selectivity was found to be useful for discriminating gas chromatographically between the phenolic and alcoholic hydroxyl groups in steroids.

Alcohols

Determination of organophosphorus pesticides in fruits by on-line size-exclusion chromatography-liquid chromatography-gas chromatography-flame photometric detection.

The determination of organophosphorus pesticides in fruits by size-exclusion chromatography (SEC) on a polystyrene column coupled on-line to a gas chromatography (GC) system was unsatisfactory as a result of interfering peaks in GC. A liquid chromatography step on silica gel was therefore inserted between the SEC and GC steps to filter out polar by-products. Samples of fruit (apples, grapes and kiwi fruits) were extracted, then the extract filtered or centrifuged and injected into an automated on-line SEC-liquid chromatography-GC-flame photometric detection. Recoveries were about 95% and the detection limits about 1 ng/g.

Chromatography, Gas

Concentration of headspace, airborne and aqueous volatiles on Chromosorb 105 for examination by gas chromatography and gas chromatography-mass spectrometry.

Techniques are described for the collection of volatile material from headspace vapours and the atmosphere and for the direct extraction of volatiles from aqueous solution by traps containing the porous polymer Chromosorb 105. The traps are inserted through a valve into a gas chromatograph which facilitates the desorption and transfer of the volatiles to high-resolution capillary columns. Selected applications of the technique are described.

Air Pollutants

Simultaneous microdetermination of capsaicin and its four analogues by using high-performance liquid chromatography and gas chromatography--mass spectrometry.

An improved method is described for the simultaneous determination of capsaicin and its analogues at levels from nanograms to micrograms using high-performance liquid chromatography (HPLC) and gas chromatography--mass spectrometry. This method consists of two steps: firstly, purification and determination of total capsaicinoid by HPLC, and secondly, the simultaneous determination of capsaicin and its analogues by mass chromatography (MC) or mass fragmentography (MF). Crude extracts of capsaicinoid were purified with a Zorbax SIL column. Total capsaicinoid was detected at 235 nm and measured automatically by a microcomputer. It was collected, evaporated, trimethylsilylated and subjected to MC or MF. After monitoring the molecular ions of trimethylsilyl derivatives of capsaicinoid and the internal standard, the absolute contents of each analogue were determined by computer. By using this method, capsaicin and all of its analogues can be determined simultaneously at levels from micrograms to nanograms without any interferences from other components.

Capsaicin

[Determination of mannitol and lactulose in urine by capillary gas chromatography].

Gas capillary chromatography (GCC) determination of mannitol and lactulose in urine after oral intake is a method for assessing the intestinal permeability in various bowel diseases. The method proposed, using gas capillary chromatography with flame ionization detection after silylation of urine residue, gives good results: coefficients of variation varied from 6 to 8.7% for mannitol and 7.5 to 13.7% for lactulose. Detection limit was 5 mg/l for both compounds.

Flame Ionization