On-line multidimensional chromatography using packed capillary liquid chromatography and capillary gas chromatography

The introduction of selected fractions from a liquid chromatograph into a gas chromatograph has been described; however, analyses were performed by off-line experiments requiring collection and reinjection of the separate fractions or by on-line procedures where disadvantageously, only a fraction of the separated peak or a well resolved component in a mixture could be introduced into a gas chromatograph. This disadvantage is overcome by the apparatus and method described in this paper, which utilizes a multidimensional chromatography system employing a high efficiency, packed capillary LC column coupled on-line to a capillary gas chromatograph. The liquid chromatograph (so designed) can act as a highly efficient clean-up or chemical class fractionation step prior to introduction into the gas chromatograph, significantly reducing sample preparation times in many applications. Thus minor components in a complex matrix can be determined without prior sample clean-up, an example of which is the determination of polychlorinated biphenyls in a complex hydrocarbon matrix.     

Determination of extracolumn effects in recycle gas chromatography with capillary columns

Extracolumn band broadening in multidimensional systems utilizing flow switching is clearly undesirable. In certain cases, i.e. capillary recycle gas chromatography, the success of an experiment is contingent on the minimization of pre- and post-column dispersion of the peaks. Knowledge of these sources of peak distortion is necessary to optimize the experimental design. A system that extracts statistical parameters from real chromatographic peaks is discussed and used to evaluate band broadening in a capillary recycle experiment.     

Dynamic headspace capillary gas chromatography: A versatile analytical technique

The applicability of dynamic headspace analyses for viscous liquids and solid samples is demonstrated. Some comments on the usefulness of this technique for quantifying volatiles in polymeric matrices are made.     

Applications of a miniaturized fluorimetric photodiode array detector for capillary liquid chromatography

A high sensitivity, multichannel fluorescence detector with small volume has been developed for capillary column liquid chromatography. Using an intensified linear photodiode array to monitor fluorescence emission, several important mixtures exhibiting native fluorescence have been examined following high efficiency separation on a capillary column. By correlating mass spectral, fluorescence spectral, and retention time data, information of potential utility in the structural elucidation of aromatic molecules contained in complex mixtures can be obtained. Examples include the separation and spectral examination of the polyaromatic compounds in samples of both biological and environmental interest.     

Gas chromatography and gas chromatography/mass spectrometry for the characterization of complex mixtures of large oligosaccharides

High temperature gas chromatography and gas chromatography/mass spectrometry are used in the characterization of complex natural mixtures of permethylated oligosaccharides released from proteins or lipids. The high resolution allows separation of isomeric compounds and the mass range extends to oligosac-charides around molecular mass 2000 daltons or 10 sugar residues for isomalto-oligosaccharides. The mass spectra of permethylated oligosaccharide alditols from mucin glycopeptides are very informative and the approach allows a simple and rapid characterization of these complex components.     

Determination of polychlorinated biphenyls in sediment by on-line narrow-bore column liquid chromatography/capillary gas chromatography

Narrow-bore column liquid chromatography coupled on-line with capillary gas chromatography (LC/GC) is used for the determination of polychlorinated biphenyls (PCBs) in sediment via a heart-cutting technique. This method is compared with a method in which two off-line column clean-up steps are used with subsequent analysis by capillary gas chromatography. For the LC/GC analysis the recovery of PCBs was 90–100%. For two sediment samples from the river Meuse the LC/GC and the other, more laborious method showed good agreement.     

Preparation of polysiloxane stationary phases for capillary column chromatography: A New methoxyphenyl phase

Contemporary methods for the synthesis of alkyl- and arylsubstituted polysiloxane stationary phases are reviewed. A new, moderately polar phase containing the 3-(4-methoxyphenyl)-propyl group is reported.     

Analysis of pyrethrins using capillary supercritical fluid chromatography and capillary gas chromatography with fourier transform infrared detection

The six insecticidally active components in a commercial preparation of pyrethrin extract are separated by capillary gas chromatography (GC) and by capillary supercritical fluid chromatography (SFC). Thermal degradation of pyrethrin I and II are observed under the GC conditions required to separate the pyrethrin components. The use of shorter columns and thinner stationary phase coatings reduce the amount of degradation but cannot eliminate degradation of pyrethrin II. The SFC chromatograms, obtained under thermally mild conditions, show that all components including pyrethrin II elute without degradation. Infrared spectra of cinerin I & II, jasmolin I & II, and pyrethrin I & II are obtained using a flow through SFC/IR detection cell. Spectra clearly reveal the structural differences needed to distinguish and identify the components in the extract.     

Some applications of capillary gas chromatography in the chemical industry

About three years ago, fused silica capillary columns were introduced in the Quality Control Laboratory of the Shell refinery/chemical complex at Pernis. In general, long, thick-film, wide-bore capillary columns are used together with low split ratios and hydrogen as carrier gas. These conditions enable the analysis of relatively large sample amounts, resulting in low detection limits for the minor components without overloading by the major components, while still maintaining a satisfactory resolution. A number of applications are shown, such as the analysis of complex mixtures, the determination of trace impurities and the analysis of residual volatiles in polymers.     

Practical limitations of capillary gas chromatography

Glass capillary gas chromatography is a high resolution separation method which allows the qualitative and quantitative analysis of even complex mixtures, which may contain many components–also isomeric–in a wide range of volatilities, polarities and concentrations. The principal limitation of gas chromatographic application is given by an insufficient volatility of the species to be separated. Elevated temperatures have to be applied if the application range is to be extended and to achieve steep peak profiles, i.e. low detection limits at high resolution. The use of elevated temperatures is limited, of course, by the temperature stability of both the solvent (stationary liquid and support) and the solutes. The problems of trace analysis for low volatility compounds at high resolution and its limitational parameters regarding sampling, separation and detection are discussed. The applicability of glass capillary columns in this field is influenced by the following parameters: tailing behaviour; irreversible adsorption of polar and decomposition of unstable solutes; thermal stability of stationary liquid (including the support deactivation); separation efficiency and sample capacity (film thickness). Multidimensional gas chromatography using capillary columns coupled either with a packed or another capilllary column for preseparations may be applied with advantage in the analysis of complex mixtures.     

Study of peak profiles in nonlinear gas chromatography: Application to the peak distortions observed with overloaded capillary columns

The elution profiles observed with overloaded capillary columns are well described by a four-parameter theoretical model derived from the basic mass balance equations which relies on an expansion of the partition isotherm to the second term and takes the sorption effect into account. The reliability of the model is demonstrated by the fact that the peak leaning coefficient obtained from a least squares fit of the model to the experimental peak is in good agreement with that obtained from the variation of peak height with retention time at peak maximum. The coefficeint of apparent axial dispersion is independent of sample size and can be used to characterize the plate height at zero concentration of an overloaded capillary column.     

Synthesis of siloxane stationary phases for capillary gas chromatography and supercritical fluid chromatography

A comparison is made between dichlorosilanes and cyclic siloxanes as starting materials in the synthesis of stationary phases for capillary gas chromatography (CGC) and supercritical fluid chromatography (SFC). Siloxanes containing one or more of the side groups methyl, vinyl, phenyl, and cyanoethyl in various ratios were synthesized and compared. These phases were characterized by chromatographic (gel permeation, GPC), spectroscopic (IR, ¹H NMR, ²⁹Si NMR), and thermal (DSC) methods. Coated fused silica columns were evaluated with respect to polarity, crosslinkability with several free-radical initiators, and thermal stability. A new liquid phase, 7% cyanoethyl, 7% phenyl, 1% vinyl methyl polysiloxane is shown to be more polar than OV-1701, more temperature stable, easily crosslinked and suitable for use in supercritical fluid chromatography.     

On-line sample treatment—capillary gas chromatography

Summary Sample pretreatment is often the bottleneck of a tracelevel analytical procedure. In order to increase performance, increasing attention is therefore being devoted to combining sample pretreatment on-line with the separation technique that has to be used. In the present review, a variety of procedures in use today for sample treatment coupled on-line to capillary gas chromatography (GC) is briefly discussed. Special attention is devoted to coupled-column techniques such as SPE-GC and LC-GC (SPE, solid-phase extraction; LC, column liquid chromatography) which are topics of much current interest, also because of their frequent use in so-called hyphenated systems.     

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.