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PDPS: a pulmonary data processing system for assessment of gas exchange properties by multiple gas wash-out.

A data acquisition and processing system for the analysis of inert gas wash-out tests is described. The described system is in clinical use on spontaneously breathing patients as well as on mechanically ventilated Intensive Care patients. It combines several analysis techniques with an aim to provide a deeper insight into the nature of existing ventilation inhomogeneity than the individual techniques alone can provide. The signals measured are the respiratory flow, the fractions of one or two indicator gases washing out and the fractions of the metabolic gases oxygen and carbon dioxide. Analysis of these signals provides information concerning the end-expiratory lung-volume, distribution of ventilation and perfusion in the lung, the role of diffusion in the ventilation process and the metabolic oxygen uptake and CO2 release. This article describes the algorithms used and the results that are presented.

Algorithms↗

Gas chromatography-mass spectrometry and gas chromatography-tandem mass spectrometry of cyclic fatty acid monomers isolated from heated fats.

The analysis of hydrogenated cyclic fatty acid monomers isolated from heated linseed and sunflower oils is achieved by gas chromatography-tandem mass spectrometry of their pentafluorobenzyl esters. Collisionally activated dissociation of the carboxylate anions produced by electron-capture ionization shows remote charge-site fragmentation that allows location of cyclopentane and cyclohexane rings by examining the resulting mass-analysed ion kinetic energy spectra. Oxidative ozonolysis of the methyl esters of the unsaturated cyclic fatty acid monomers allows location of some double bonds. However, preliminary results obtained with remote charge fragmentation of synthetic unsaturated models make this approach an alternative for double bond location in the cyclic fatty acid monomers isolated from heated fats.

Cyclopentanes↗

Investigation of meperidine and its metabolites in urine of an addict by gas chromatography-flame ionization detection and gas chromatography-mass spectrometry.

A gas chromatographic method with flame ionization detection (FID) for the quantitative analysis of meperidine and mass spectrometry (MS) for the qualitative analyses of meperidine and its metabolites in urine was established. Meperidine, normeperidine and acetyl normeperidine in urine were extracted with ether. Free and conjugated meperidinic and normeperidinic acids in urine, which are hydrophillic, were hydrolyzed by acid, esterified with methanol and derivatized with acetic anhydride. Meperidine and its four metabolites were identified by GC-MS. Meperidine was measured by GC-FID during 72 h after intramuscular administration of meperidine to an addict.

Biotransformation↗

Chemical synthesis of dioxygen-18 labelled omega-/beta-oxidized cysteinyl leukotrienes: analysis by gas chromatography-mass spectrometry and gas chromatography-tandem mass spectrometry.

Cysteinyl leukotrienes (LT) C4, LTD4 and LTE4 are potent mediators of anaphylaxis and inflammation. LTE4 is extensively metabolized in man mainly by omega-oxidation followed by subsequent beta-oxidation to more polar and biologically inactive metabolites. This paper describes a method for the synthesis of [1,20-18O2]-carboxy-LTE4, [1,18-18O2]-carboxy-dinor-LTE4, and [1,16-18O2]-carboxy-14,15-dihydro-tetranor-LTE4 starting from the unlabelled dimethyl esters of 20-carboxy-LTA4, 18-carboxy-dinor-LTA4 and 16-carboxy-14,15-dihydro-tetranor-LTA4, respectively, by separate chemical conjugation with cysteine hydrochloride in H2-18O-methanol followed by alkaline hydrolysis with Li18OH. The isotopic purity of the isolated reaction products was 94% at 18O for all three preparations while only 0.3% remained unlabelled as confirmed by negative-ion chemical-ionization gas chromatography-mass spectrometry (GC-NICI-MS) after their catalytical reduction/desulphurization and derivatization. The 18O2-labelled compounds are demonstrated to be suitable internal standards for quantification by GC-NICI-MS and GC-NICI-tandem MS. We found by GC-NICI-tandem MS that the excretion rate of 20-carboxy-LTE4 is comparable to that of LTE4 (both in nmol/mol creatinine, mean +/- S.E.) in healthy children (26.7 +/- 4.7 vs. 32.0 +/- 6.0, n = 9) and adults (13.9 +/- 1.1 vs. 27.2 +/- 5.4, n = 3).

Adult↗

Multidimensional gas chromatography for the detailed PIONA analysis of heavy naphtha: hyphenation of an olefin trap to comprehensive two-dimensional gas chromatography.

A multidimensional method providing the composition of a heavy naphtha in paraffins, isoparaffins, olefins, naphthenes, and aromatics (PIONA) in the C8-C14 range is presented. The analytical set-up consists in a silver modified silica olefin trap on-line coupled to comprehensive two-dimensional gas chromatography (GC x GC). In this configuration, hydrocarbons are separated, in gaseous state, in two fractions, saturate and unsaturate, each fraction being subsequently analysed by GC or by GC x GC. The resolution between saturates and olefins was found to be improved compared to a single GC x GC run. The characterisation of the olefin trap highlights the benefits and the limits related to the use of that stationary phase as a double bond selective fractionation medium.

Alkanes↗

Validated semiquantitative/quantitative screening of 51 drugs in whole blood as silylated derivatives by gas chromatography-selected ion monitoring mass spectrometry and gas chromatography electron capture detection.

A comprehensively validated procedure is presented for simultaneous semiquantitative/quantitative screening of 51 drugs of abuse or drugs potentially hazardous for traffic safety in serum, plasma or whole blood. Benzodiazepines (12), cannabinoids (3), opioids (8), cocaine, antidepressants (13), antipsychotics (5) and antiepileptics (2) as well as zolpidem, zaleplon, zopiclone, meprobamate, carisoprodol, tizanidine and orphenadrine and internal standard flurazepam, were isolated by high-yield liquid-liquid extraction (LLE). The dried extracts were derivatized by two-step silylation and analyzed by the combination of two different gas chromatographic (GC) separations with both electron capture detection (ECD) and mass spectrometry (MS) operating in a selected ion-monitoring (SIM) mode. Quantitative or semiquantitative results were obtained for each substance based on four-point calibration. In the validation tests, accuracy, reproducibility, linearity, limit of detection (LOD) and limit of quantitation (LOQ), selectivity, as well as extraction efficiency and stability of standard stock solutions were tested, and derivatization was optimized in detail. Intra- and inter-day precisions were within 2.5-21.8 and 6.0-22.5%, and square of correlation coefficients of linearity ranged from 0.9896 to 0.9999. The limit of quantitation (LOQ) varied from 2 to 2000 ng/ml due to a variety of the relevant concentrations of the analyzed substances in blood. The method is feasible for highly sensitive, reliable and possibly routinely performed clinical and forensic toxicological analyses.

Gas Chromatography-Mass Spectrometry↗

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↗

Gas chromatographic and gas chromatographic-mass spectrometric analysis of ampicillin.

A method was developed for the quantitative gas chromatographic (GC) determination of ampicillin. The procedure requires silylation iwth hexamethyldisilazane, trimethylchlorosilane, trimethylsilylimidazole and N,O-bis(trimethylsilyl)acetamide in pyridine and subsequent GC on an OV-17 column, using 5 alpha-cholestane as an internal standard. The method was applied to the determination of ampicillin in some pharmaceutical products. The characteristics of the mass spectra and the derivatization GC of ampicillin are also discussed.

Ampicillin↗

Gas chromatographic determination and gas chromatographic-mass sepectrometric analysis of chloramphenicol, thiamphenicol and their metabolites.

A rapid and accurate gas chromatographic (GC) method is described for the determination of chloramphenicol, thiamphenicol and their metabolites excreted in human urine. These excretions were pre-treated with diazomethane and N,O-bis(trimethylsilyl)acetamide, so that they could be easily subjected to GC with satisfactory separation from each other and also from other urinary excretions, and could be determined simultaneously. The structures of the metabolites were confirmed by GC combined with mass spectrometric measurements of the GC peaks. The application of the method to urine specimens enabled more precise results for the amounts of metabolites present to be obtained; the excretion of thiamphenicol glucuronide was not observed.

Administration, Oral↗

Ammonia as carrier gas in capillary gas-liquid chromatography.

Influence of helium and ammonia as carrier gases on retention of neutral solutes on polyethylene glycol has been studied theoretically and experimentally. It was shown that the influence of ammonia on the retention varied significantly depending on the solute's nature. For example, the influence is great for C22 n-alkane and it is small for phenol. Taking into account the results obtained by various researchers it makes sense to express an opinion on the expediency of development of gas chromatography operated under the conditions of acidic-basic chromatography.

Ammonia↗

Gas-liquid chromatography and gas-liquid chromatography combined with mass spectrometry of a butyl ester formulation of (2,4-dichlorophenoxy) acetic acid.

A method is presented for the analysis of (2,4-dichlorophenoxy)acetic acid (2,4-D) in commercial formulations, together with concurrent detection and quantitation of related compounds. The method is based on direct gas-liquid chromatographic (GLC) analysis of the formulation to estimate the various esters present, and on an analysis of the total 2,4-D present involving a prior cleanup, alkaline hydrolysis, acidification and n-butylation steps. This procedure also quantitates any other related acids or phenols present. A step which would extract dioxin impurities is also included. The method was checked by the accepted acid-base estimation of 2,4-D content, GLC, and by subjecting radioactive-labelled herbicide to the above procedures.

2,4-Dichlorophenoxyacetic Acid↗

Ester and related derivatives of ring N-pentafluorobenzylated 5-hydroxymethyluracil. Hydrolytic stability, mass spectral properties, and trace detection by gas chromatography-electron-capture detection, gas chromatography-electron-capture negative ion mass spectrometry, and moving-belt liquid chromatography-electron-capture negative ion mass spectrometry.

One consequence of radiation damage to DNA is the conversion of thymine to 5-hydroxymethyluracil (HMU). In order to sensitively detect this DNA adduct by gas chromatography (GC) or high-performance liquid chromatography (HPLC) with electron-capture detection techniques, it is necessary to derivatize it. This study was designed to select an optimum ester derivative of the aliphatic hydroxyl group on HMU. N1, N3-Bis(pentafluorobenzyl)-HMU was formed as a parent derivative, and from this a series of esters. Also O-pentafluorobenzyl and O-tetrafluorobenzyl ether derivatives were prepared. Of the esters the pivalyl derivative was the best choice because it formed easily, was relatively stable to aqueous hydrolysis (t 1/2 = 9.8 days at pH 11.5, 24 degrees C) and gave a response at fmol levels by GC and LC comparable to that of the ethers. Unanticipated was a good response as well for the parent derivative, a free hydroxyl compound, by GC and LC at this level. The work also demonstrates a high performance by LC-electron-capture negative ion mass spectrometry with a belt interface for the trace detection of derivatives of this type.

Chemical Phenomena↗

Quantitative gas chromatography-olfactometry. Analytical characteristics of a panel of judges using a simple quantitative scale as gas chromatography detector.

Some questions related to the ability of gas chromatography-olfactometry (GC-O) to provide quantitative measurements of the concentration of a given odorant in an extract are explored and discussed. A panel of eight individuals has been used to evaluate the intensity of 15 odorants present at different concentrations. The use of very simple scales, such as a 0-3 scale, makes it possible to build calibration graphs based on the different stimulus-response models (Fechner, Stevens, Hill) and, with a proper calibration, up to nine different concentration levels can be discriminated by an eight-judge panel. The signal shows a good long-term stability, and its precision varies between 3.7 and 8% of the whole scale, with 5.7% as average. Sensitivity is extremely dependent on the compound: in the best case a concentration change of 20% can be detected, while in the worst, concentrations must differ more than one order of magnitude. In average, concentrations must differ between 2 and 4.7 times (including calibration error) or between 1.2 and 2.3 (excluding calibration error). The performance of the different judges, the effect of the close elution of two odors and the benefits derived from the use of more complex scales (7-points) are briefly discussed from the perspective of the analytical performance of GC-O methods.

Calibration↗

Novel preconcentration technique for on-line coupling to high-speed narrow-bore capillary gas chromatography: sample enrichment by equilibrium (ab)sorption. II. Coupling to a portable micro gas chromatograph.

The technique of equilibrium (ab)sorption has been proven to be a powerful method for preconcentration of gaseous samples for high-speed narrow-bore capillary gas chromatography (GC) in general and field-portable GC instruments, often referred as micro GCs, in particular. Using a simple experimental set-up equipped with an open-tubular enrichment column it is possible to produce a homogeneously enriched sample plug, allowing reproducible injections of an enriched sample into the micro GC. Using a non-polar trapping column enrichment factors found for n-alkanes in the range of C7 to C10 ranged from 15 to 150 and agree well with calculated values. Using a highly retentive Thermocap column, the enrichment factor observed for heptane was above 500. As the use of this new preconcentration method requires only minimum modification of the micro GC, the chromatographic performance of the instrument was not compromised by direct coupling to the preconcentration device. Examples of on-line enrichment with portable micro GC analysis of VOCs from air are shown. These examples clearly demonstrate the potentials of the new method in field analysis.

Absorption↗

Gas chromatographic determination of primary alcohols as their formylbenzoic esters by gas-phase luminescence detection.

A new and convenient method is described for the derivatization of primary alcohols with p-formylbenzoyl chloride, and the sensitive photometric detection of the resulting formylbenzoic ester derivatives based on their gas-phase luminescence in excited nitrogen. The coupling reaction proceeds rapidly and quantitatively, and the formylbenzoic esters show good GC properties. The minimum detectable amounts of the derivatized alcohols, at a signal three-times the peak-to-peak noise, lie between 10 and 100 pg per injection, and their linear ranges cover approximately three-orders of magnitude.

Alcohols↗

Use of equations for the description of experimental dependence of the height equivalent to a theoretical plate on carrier gas velocity in capillary gas-liquid chromatography.

Optimal equation for fitting the experimental data on the height equivalent to a theoretical plate (HETP) versus carrier gas velocity in GLC was determined. The data obtained by authors and the literary data by other investigators were used for the comparative study of Van Deemter, Golay and the little known Golay-Guiochon equations. The Golay-Guiochon equation takes into account instrumental contribution and other sources of additional band broadening. Correlation coefficient R and Pirson's criterion chi2 were used as a criterion of the data correspondence to the equations. The Golay-Guiochon equation is the best for fitting of the experimental data in 71% considered examples, 19% experimental data may be fitted very precisely by the Van Deemter equation, the Golay equation is preferable for 7% experimental data only. Three percent experimental data may be fitted with the same precision by the Golay and the Van Deemter equations. The results obtained are of theoretical and practical interest. The Golay-Guiochon equation must be used more widely in analytical practice and physicochemical measurements.

Chromatography, Gas↗

The assay of fentanyl and its metabolites in plasma of patients using gas chromatography with alkali flame ionisation detection and gas chromatography-mass spectrometry.

Fentanyl was determined using gas chromatography (GC) and alkali flame ionisation detection (AFID), in the plasma of patients who had received a high single dose (up to 60 microgram/kg body weight). The relative standard deviation is 6% for 11 ng/ml while the calculated detection limit is 3.3 ng of fentanyl per 1 ml of plasma. The concentration of fentanyl in patients ranged from 40 to 3 ng/ml of plasma. The concentration of fentanyl in patients ranged from 40 to 3 ng/ml of plasma in the first hour after administration. In the plasma of patients treated with fentanyl two metabolites could be detected and identified using GC-AFID and GC-MS.

Fentanyl↗

Comparison of sensitivity between gas chromatography-low-resolution mass spectrometry and gas chromatography-high-resolution mass spectrometry for determining metandienone metabolites in urine.

In doping control laboratories the misuse of anabolic androgenic steroids is commonly investigated in urine by gas chromatography-low-resolution mass spectrometry with selected ion monitoring (GC-LRMS-SIM). By using high-resolution mass spectrometry (HRMS) detection sensitivity is improved due to reduction of biological background. In our study HRMS and LRMS methods were compared to each other. Two different sets were measured both with HRMS and LRMS. In the first set metandienone (I) metabolites 17alpha-methyl-5beta-androstan-3alpha,17beta-dio l (II), 17-epimetandienone (III), 17beta-methyl-5beta-androst-1-ene-3alpha,17alpha-diol (IV) and 6beta-hydroxymetandienone (V) were spiked in urine extract prepared by solid-phase extraction, hydrolysis with beta-glucuronidase from Escherichia coli and liquid-liquid extraction. In the second set the metabolites were first spiked in blank urine samples of four male persons before pretreatment. Concentration range of the spiked metabolites was 0.1-10 ng/ml in both sets. With HRMS (resolution of 5000) detection limits were 2-10 times lower than with LRMS. However, also with the HRMS method the biological background hampered detection and compounds from matrix were coeluted with some metabolites. For this reason the S/N values of the metabolites spiked had to be first compared to S/N values of coeluted matrix compounds to get any idea of detection limits. At trace concentrations selective isolation procedures should be implemented in order to confirm a positive result. The results suggest that metandienone misuse can be detected by HRMS for a prolonged period after stopping the intake of metandienone.

Adult↗