A micro-volume electron capture detector for use in high resolution capillary column gas chromatography

A new design for an electron capture detector cell is described. The cell is compatible with the requirements of high resolution capillary columns and is shown to be useful in applications that require high analysis speed. A unique method of sample introduction reduces the problems of sample loss by adsorption on the surfaces of the cell. Previously reported problems of sample loss by adsorption on active surfaces within the cell when using hydrogen carrier gas are shown to have been eliminated. Examples are shown demonstrating the increased speed of analysis that can be obtained when using hydrogen carrier gas and 100 micron diameter columns.     

A new configuration for coupling purge-and-trap/cryogenic focusing/capillary column gas chromatography with splitless injection mode

A new configuration for coupling a purge-and-trap unit to a capillary column gas chromatograph via a cryogenic focusing interface has been developed. In this configuration, the precolumn of the cryogenic focusing interface was inserted through the septum of a split/splitless injection port where it served as both sample transfer and carrier gas supply lines. The injection port of the gas chromatograph was modified by plugging the carrier gas and the septum purge lines. This configuration allowed for the desorption of analytes at high flow rates while maintaining low, analytical-column flow rates which are necessary for optimum capillary column operation. The capillary column flow rate is still controlled by the column backpressure regulator. Chromatograms of purgeable aromatics exhibited improved resolution, especially for early eluting components compared to those obtained by direct liquid injection using the normal splitless injection mode. Quantitative sample transfer to the analytical column afforded excellent linearity and reproducibility of compounds studied.     

Evaluation of electron capture cell designs for use in high resolution capillary column gas chromatography

A comparison of the effects on peak shape is made between a 350 and 100 microliter displaced coaxial and a 350 microliter concentric cylinder electron capture cell. Peaks as fast as W_1/2 = 0.5 second were detected using electronics operating in the constant current mode. The measured peak shapes are compared to those obtained by computer simulation assuming either complete mixing or plug-like flow within ECD cell. The advantage of controlling the flow pattern through the cell to obtain plug-like flow is demonstrated. Differences in peak shape between the displaced coaxial and concentric cylinder cells of the same volume are explained in terms of the electrostatic fields within the cells.     

The solvent venting injection technique in capillary supercritical fluid chromatography

A solvent venting technique for injection of volumes up to 1 μl on 50 μm i.d. SFC columns has been compared to direct injection methods. The peak broadening and peak splitting observed with direct injection have been examined and found to be related to the starting pressure, the column temperature, and the sample solvent, in addition to the sample volume. The solvent venting technique removed peak splitting and improved the column efficiency. With a proper selection of experimental conditions, the sample recovery was 100%. The major part of the solvent was eluted in 15–20 s. Several applications have been demonstrated.     

Distorted solvent peaks in capillary GC: A symptom of porous column surfaces

Many uncoated precolumns, and to a lesser extent separation columns, strongly retain some of the solvent. Retarded release of such solvent elevates the baseline after the solvent peak and causes ugly “humps” of eluted solvent as the temperature is increased. The problem is probably a result of retention by a porous surface, e.g. surfaces obtained by leaching or hydrothermal treatment of capillaries prior to silylation. It is assumed that other problems with capillary columns can be explained by the same mechanism, including: a kind of adsorption including apolar compounds, and “ghost” peaks as well as “memory” effects. Fused silica capillaries are superior to glass, but even for these special procedures are required in order to achieve thorough deactivation of the internal surface without introducing porosity.     

Limits in arson debris analysis by capillary column gas chromatography/mass spectrometry

Sample enrichment technology and instrumental sensitivity are no longer limiting factors in arson debris analysis. When pyrolyzed, petroleum based composite materials may produce artifacts. Urban air is another major source of interference since some of the components typically found in air, in particular alkylated aromatic hydrocarbons, are customarily used as indicators for the presence of gasoline. It is suggested to replace qualitative analysis with a quantitative approach, taking the sample matrix into consideration.     

Application of capillary gas chromatography to automated on-line quantitative analysis of solvent vapors

Solvent vapors in air may be measured with capillary gas chromatographic columns. By using large diameter columns and sample loops of approximately the same internal diameter, the column may be connected directly to the gas sampling valve. This approach eliminates the use of a splitter or cryogenic trapping and allows low levels to be measured. By operating the column at high velocity, column efficiency is sacrificed for increase in speed.     

Evaluation of smectic biphenylcarboxylate ester liquid-crystalline polysiloxane stationary phases for capillary column gas chromatography

Mesomorphic biphenylcarboxylate esters were coupled via flexible aliphatic hydrocarbon spacers to a polysiloxane backbone. The influence of spacer length, percent mesomorphic substitution, and crosslinking of the stationary phase on liquid-crystalline transition temperatures and on chromatographic performance was investigated. Unique selectivity and good efficiency over a wide temperature range for gum and cross-linked liquid-crystalline phases were demonstrated by the separation of various isomeric polycyclic aromatic compounds.     

Solute focusing technique for on-column injection in capillary gas chromatography

A novel solute focusing technique for on-column injection of liquid samples onto capillary GC columns is described. The focusing technique allows injection of 8.0 microliters or more of sample without producing the peak distortion or splitting observed under conventional on-column injection conditions. The experimentally determined performance of the technique is given for a wide volatility range sample. Solute focusing is useful in situations where on-column injection of 1.0 microliter or greater is required.     

Multichannel autosampler for Curie-point pyrolysis capillary gas chromatography

A multichannel autosampler which can automatically analyze up to 20 samples in sequence has been developed for on-line Curie-point pyrolysis – capillary GC. The results obtained from the system show that the analysis of thermally labile samples could be performed without either thermal degradation or reaction during the waiting time before the final pyrolysis. The reproducibilities of the relative peak areas and retention times of the characteristic pyrolysates of a tricomponent copolymer were significantly better than those obtained by manual sample manipulation.     

Stationary-phase focusing in capillary gas-liquid chromatography: Enhancement of the maximum permissible sample size

Equations have been derived to predict the extent to which the sample size may be increased, without decreasing the column performance, by stationary-phase focusing at sub-ambient temperatures. Under favorable circumstances the sample size may be enhanced several hundredfold.     

Isoelectric focusing sample injection for capillary electrophoresis of proteins

Carrier ampholyte-free isoelectric focusing (IEF) sample injection (concentration) for capillary electrophoresis (CE) is realized in a single capillary. A short section of porous capillary wall was made near the injection end of a capillary by HF etching. In the etching process, an electric voltage was applied across the etching capillary wall and electric current was monitored. When an electric current through the etching capillary was observed, the capillary wall became porous. The etched part was fixed in a vial, where NaOH solution with a certain concentration was added during the sample injection. The whole capillary was filled with pH 3.0 running buffer. The inlet end vial was filled with protein sample dissolved in the running buffer. An electric voltage was applied across the inlet end vial and etched porous wall. A neutralization reaction occurs at the boundary (interface) of the fronts of H+ and OH-. A pH step or sharp pH gradient exists across the boundary. When positive protein ions electromigrate to the boundary from the sample vial, they are isoelectricelly focused at points corresponding to their pH. After a certain period of concentration, a high voltage is applied across the whole capillary and a conventional CE is followed. An over 100-fold concentration factor has been easily obtained for three model proteins (bovine serum albumin, lysozyme, ribonuclease A). Furthermore, the IEF sample concentration and its dynamics have been visually observed with the whole-column imaging technique. Its merits and remaining problem have been discussed, too.     

Computer-assisted optimization of temperature programming and flow rate in capillary gas chromatography

A computer-assisted method is presented for simultaneous optimization of three-factor of temperature programming (initial temperature, temperature rising rate and carrier gas flow rate) for the separation of eleven compounds in capillary gas chromatography. The optimization of the separation over the experimental region is based on a special polynomial from fifteen preliminary experiments using the resolution as the selection criterion. Computer scanning technique was used for optimum selection on three dimensions. Excellent agreement was found between the predicted data and the experimental results.     

Computer comparisons of variables in capillary gas chromatography

A series of computer-constructed van Deemter curves that permits evaluation of a number of variables in capillary gas chromatography is presented. The graphs permit the comparison of inter-related parameters, including the choice of carrier gas (hydrogen vs helium vs nitrogen), column length (10-100 m), column diameter (0.20, 0.25, 0.32, 0.4 mm), solute partition ratios (0-10), and liquid phase film thickness (0.1, 0.25, 0.5, 1.0 μm). The curves are evaluated, both in terms of the relative magnitude of the optimum average linear carrier gas velocity, and in terms of the significance of the sharpness of the curve.