High-speed Gas Chromatography Research Articles

Fuel property modeling by high-speed gas chromatography coupled with partial least squares data analysis

Partial least squares (PLS) regression is a valuable chemometric tool for property prediction when coupled with gas chromatography (GC). Since the separation run time and stationary phase selection are crucial for effective PLS modeling, we study these GC parameters on the prediction of viscosity, density and hydrogen content for 50 aerospace fuels. Due to the diversity of compounds in the fuels (primarily alkanes, cycloalkanes, and aromatics), we explore both polar and non-polar stationary phase columns. The robustness for the PLS models was evaluated by their normalized root mean square error of cross-validation (NRMSECV). PLS models built for viscosity across 1-min, 3-min, 7-min, and 10-min time window (TW) high-speed GC separations produced nearly the same NRMSECV with the polar column data with an average (standard deviation) of 4.41 % (0.34 %) versus the non-polar column data of 4.69 % (0.15 %). In contrast, while the NRMSECV of density modeling with the polar column data varied more than the viscosity models, averaging 7.54 % (0.67 %), the non-polar column data produced a significantly higher average NRMSECV of 10.06 % (0.35 %). Similarly, for hydrogen content, the NRMSECV with the polar column data averaged 9.50 % (0.87 %), which was significantly lower than the NRMSECV with the non-polar column data averaging 12.10 % (0.88 %). We also investigated the impact of smoothing the GC data on the corresponding PLS models. By applying varying degrees of smoothing, we can effectively obtain similar chromatographic peak patterns in a shorter TW. For example, a 10-min smoothed chromatogram appears like the 1-min separation with no smoothing but resulted in nearly the same NRMSECV. Overall, the fast separation with a 1-min TW produced robust PLS models for viscosity with either stationary phase column, whereas for density and hydrogen content the polar stationary phase column produced superior PLS models, thus with proper stationary phase selection, a fast separation run time could be readily applied with optimal PLS property modeling results.

Mist formation during micro-explosion of emulsion droplets

The micro-explosion of emulsion droplets plays an important role in promoting atomization, improving combustion efficiency, and reducing pollutant emissions. In this experimental study of the micro-explosion of emulsion droplets, we find that mist can be generated during the heating of emulsion droplets, and the mist generation is closely related to the micro-explosion process. Combined analysis from high-speed images, gas chromatography, and droplet temperature variation shows that the mist generation is due to the condensation of vapor into small droplets as the temperature decreases. Two micro-explosion modes are observed, intense micro-explosion with a large amount of mist and weak micro-explosion with a small amount of mist. Different emulsified fuels are tested, and mist can be produced for all the emulsified fuels. The mist is quantitatively analyzed via digital image processing. According to the mist concentration curve in the micro-explosion process, the micro-explosion mode can be distinguished. The effects of the water and surfactant contents in the emulsion droplets are studied, and the mists are used to characterize the micro-explosion. Increasing the water content can promote the vaporization of the water phase, increase the strength of micro-explosion, and result in a large amount of mist. Increasing the surfactant content can improve the stability of the emulsion droplet, reduce the probability of intense micro-explosion, and hence reduce the mist concentration.

Optimizing column-to-column retention time alignment in high-speed gas chromatography by combining retention time locking and correlation optimized warping

We examine and then optimize alignment of chromatograms collected on nominally identical columns using retention time locking (RTL), an instrumental alignment tool, and software-based alignment using correlation optimized warping (COW). For this purpose, three samples are constructed by spiking two sets of analytes into a base test mixture. The three samples are analyzed by high-speed gas chromatography with four nominally identical columns and identical separation conditions. The data is first analyzed without alignment, then using COW alone, then RTL alone, and finally with RTL followed by COW to correct the severe column-to-column misalignment. Principal component analysis (PCA) is used to investigate how well each alignment method clustered the chromatograms into the three sample classes via a scores plot without being compromised by the specific column(s) used. The degree-of-class separation (DCS) is used as a classification metric, measured as the Euclidian distance between the centroids of two clusters in PC space in the scores plot, normalized by their pooled variance. With no alignment, the average DCS between sample classes (DCSsam) was 3.0, while the average DCS between the four nominally identical columns, i.e., column classes (DCScol) was 76.1 (ideally the DCScol should be 0), indicating the chromatograms were initially classified by the columns used. Using either COW or RTL alone also produced unsatisfactory results, with COW alone incorrectly aligning many peaks, leading to a DCSsam of only 1.9 and DCScol of 1.7, while RTL alone provided a DCSsam of 4.7 and DCScol of 4.2. Finally, using RTL followed by COW alignment, DCSsam increased to 32.5, indicating successful classification by chemical differences between sample classes, while the DCScol decreased to 0.4, indicating virtually no classification due to column-to-column differences, as desired. Thus, RTL provided a “first-order” correction of the initial retention mismatch observed for the nominally identical columns, while additional alignment via COW was required to optimize sample classification by PCA.

Development of Ultrafast Separations Using Negative Pulse Partial Modulation To Enable New Directions in Gas Chromatography.

Partial modulation via a pulse flow valve operated in the negative pulse mode is developed for high-speed one-dimensional gas chromatography (1D-GC), comprehensive two-dimensional (2D) gas chromatography (GC × GC), and comprehensive three-dimensional gas chromatography (GC3). The pulse flow valve readily provides very short modulation periods, PM, demonstrated herein at 100, 200, and 300 ms, and holds significant promise to increase the scope and applicability of GC instrumentation. The negative pulse mode creates an extremely narrow, local analyte concentration pulse. The reproducibility of the negative pulse mode is validated in a 1D-GC mode, where a pseudosteady-state analyte stream is modulated, and 8 analytes are baseline resolved (resolution, Rs ≥ 1.5) in a 200 ms window, providing a peak capacity, nc, of 14 at unit resolution ( Rs = 1.0). Additionally, the pulse width, pw, of the pulse flow valve "injection" relationship to peak width-at-base, wb, resolution between peaks and detection sensitivity are studied. To demonstrate the applicability to GC × GC, a high-speed separation of a 20-component test mixture of similar, volatile analytes is shown. Analytes were separated on the second-dimension column, 2D, with 2 wb ranging from 7 to 12 ms, providing an exceptional 2D peak capacity, 2 nc, of ∼12 using a modulation period ( PM) of 100 ms. Next, a 12 min separation of a diesel sample using a PM of 300 ms is presented. The 1 wb is ∼4 s, resulting in a 1 nc of ∼180, and 2 wb is ∼18 ms, resulting in a 2 nc of ∼17, thus achieving a nc,2D of ∼3000 in this rapid GC × GC diesel separation. Finally, GC3 with time-of-flight mass spectrometry (TOFMS) detection using a PM of 100 ms applied between the 2D and 3D columns is reported. Narrow third dimension, 3D, peaks with 3 wb of ∼15 ms were obtained, resulting in a GC3 peak capacity, nc,3D, of ∼35 000 in a 45 min separation.

Determining Erucic Acid Content in Individual Seeds of Rape, Brassica napus, by Gas Chromatography

Abstract A convenient method for determining erucic (cis-13-docosenoic acid) content in individual seeds of rape is presented. Fatty acid methyl esters were prepared from naked cotyledon (including hypocotyl) of single seeds and were analyzed by high-speed gas chromatography. This method consists of two steps: 1) using rapid methanolysis directly on seed tissue and 2) employing high-speed gas chromatography. Hence, a single seed can be tested in less than ten minutes. This method was used to analyze seeds from high-, low-, and zero-erucic-acid varieties of rape. We found that almost all the seeds from low-erucic-acid varieties produced no erucic acid and a few seeds produced erucic acid.

Extension of the two-dimensional mass channel cluster plot method to fast separations utilizing low thermal mass gas chromatography with time-of-flight mass spectrometry

Implementation of a data reduction and visualization method for use with high-speed gas chromatography and time-of-flight mass spectrometry (GC-TOFMS) is reported. The method, called the “2D m/z cluster method” facilitates analyte detection, deconvolution, and identification, by accurately measuring peak widths and retention times using a fast TOFMS sampling frequency (500 Hz). Characteristics and requirements for high speed GC are taken into consideration: fast separations with narrow peak widths and high peak capacity, rapid data collection rate, and effective peak deconvolution. Transitioning from standard GC (10–60+ minute separations) to fast GC (1–10 min separations) required consideration of how to properly analyze the data. This report validates use of the 2D m/z cluster method with newly developed GC technology that produces ultra-fast separations (∼1 min) with narrow analyte peak widths. Low thermal mass gas chromatography (LTM-GC) operated at a heating rate of 250 °C/min coupled to a LECO Pegasus III TOFMS analyzed a 115 component test mixture in 120 s with peak widths-at-base, wb (4σ), of 350 ms (average) to produce a separation with a high peak capacity, nc ∼ 340 (at unit resolution Rs = 1). The 2D m/z cluster method is shown to separate overlapped analytes to a limiting Rs ∼ 0.03, so the effective peak capacity was increased nearly 30-fold to nc ∼10,000 in the 120 s separation. The method, when coupled with LTM-GC-TOFMS, is demonstrated to provide unambiguous peak rank (i.e. the number of analytes per overlapped peak in the total ion current (TIC)), by visualizing locations of pure and chromatographically overlapped m/z. Hence, peak deconvolution and identification using MCR-ALS (multivariate curve resolution – alternating least squares) is demonstrated.

Profiling the fatty acids from a strain of the microalgae Alexandrium tamarense by means of high-speed counter-current chromatography and gas chromatography coupled with mass spectrometry

Fatty acids of microalgae have been studied as potential chemotaxonomic markers, to reveal plausible lipid phycotoxins or in the context of mass production of algal biofuels. The planctonic microalgae Alexandrium tamarense (Dinophyceae) is a common harmful algal bloom species that often proliferates in eutrophic costal waters. Alexandrium blooms are the proximal source of toxins associated with paralytic shellfish poisoning (PSP), a neurological affliction that has caused human illness for centuries via consumption of contaminated shellfish. However, data on the fatty acid composition of A. tamarense is currently limited. For this reason, we cultivated a well-defined strain of A. tamarense (Alex2, group I, North American clade) in order to study both its major and minor fatty acids. The harvested microalgae were transesterified and the fatty acid methyl esters were fractionated by means of high-speed counter-current chromatography (HSCCC). The resulting 31 HSCCC fractions were analyzed by gas chromatography with mass spectrometry (GC/MS). Unknown substances were identified by transferring assorted HSCCC fractions into picolinyl or pyrrolidide derivatives. Twenty fatty acids (range 0.2–22.9% contribution to total fatty acids) were identified in the unfractionated sample with 14:0, 16:0, 18:1n-9, 18:4n-3, 18:5n-3 and 22:6n-3 representing>80% of the total fatty acids. HSCCC fractionation enabled the identification of further 22 trace fatty acids contributing between ∼0.01 and 0.2% to total fatty acids. The fatty acids included several branched-chain fatty acids as well as scarcely reported fatty acids like 11-methyl-18:1n-6tr or 18:2Δ4,9. In order to enable a better comparability and repeatability of HSCCC fractionations, we calculated for each HSCCC fraction the total volume of mobile phase, which had passed the HSCCC. From this volume we subtracted the volume of extruded stationary phase and divided the corrected volume by the total coil volume. These elution values were in good agreement with the partition ratios of randomly chosen fatty acid methyl esters obtained in shake flask tests, which allows the prediction of the elution from the HSCCC system when the partition ratio is known.

Multivariate Characterization of Milk Fat Fractions by Gas Chromatography

A high-speed gas chromatography method has been developed to separate the fatty acids in different milk fat fractions obtained via the dry fractionation deodorization process (TIRTIAUX method). Exploratory data techniques, namely cluster analysis and principal component analysis (PCA), were applied to gas chromatographic data for fatty acids composition in these milk fractions. Cluster analysis allowed the authors to visualize natural groupings corresponding to milk fat cracking achieved via the TIRTIAUX method. Principal component plots showed that six fractions are grouped in different classes, each group being clearly distinguished. Furthermore, a relationship was established between these classes and fatty acids through PCA analysis. A discriminant linear model for predicting milk fat classes from fatty acid composition was computed; 99 % of the criterion variable (milk fat class) variance was explained by the constructed model. Enrichment in unsaturated cis-fatty acids in the olein fractions and in the saturated and unsaturated trans-fatty acids in the stearin fractions was visualized from chemometric analysis. This differentiation of the milk fat fractions on the basis of fatty acids composition will enable food industries to use these fractions in both an efficient and safe way to enrich dairy products, or other foods, for healthy consumption.

On the Chemical Kinetics of n-Butanol: Ignition and Speciation Studies

Direct measurements of intermediates of ignition are challenging experimental objectives, yet such measurements are critical for understanding fuel decomposition and oxidation pathways. This work presents experimental results, obtained using the University of Michigan Rapid Compression Facility, of ignition delay times and intermediates formed during the ignition of n-butanol. Ignition delay times for stoichiometric n-butanol/O(2) mixtures with an inert/O(2) ratio of 5.64 were measured over a temperature range of 920-1040 K and a pressure range of 2.86-3.35 atm and were compared to those predicted by the recent reaction mechanism developed by Black et al. (Combust. Flame 2010, 157, 363-373). There is excellent agreement between the experimental results and model predictions for ignition delay time, within 20% over the entire temperature range tested. Further, high-speed gas sampling and gas chromatography techniques were used to acquire and analyze gas samples of intermediate species during the ignition delay of stoichiometric n-butanol/O(2) (χ(n-but) = 0.025, χ(O(2)) = 0.147, χ(N(2)) = 0.541, χ(Ar) = 0.288) mixtures at P = 3.25 atm and T = 975 K. Quantitative measurements of mole fraction time histories of methane, carbon monoxide, ethene, propene, acetaldehyde, n-butyraldehyde, 1-butene and n-butanol were compared with model predictions using the Black et al. mechanism. In general, the predicted trends for species concentrations are consistent with measurements. Sensitivity analyses and rate of production analyses were used to identify reactions important for predicting ignition delay time and the intermediate species time histories. Modifications to the mechanism by Black et al. were explored based on recent contributions to the literature on the rate constant for the key reaction, n-butanol+OH. The results improve the model agreement with some species; however, the comparison also indicates some reaction pathways, particularly those important to ethene formation and removal, are not well captured.

A monolithically fabricated gas chromatography separation column with an integrated high sensitivity thermal conductivity detector

The monolithic integration of a high sensitivity detector with a gas chromatography (GC) separation column creates many potential advantages over the discrete components of a traditional chromatography system. In miniaturized high-speed GC systems, component interconnections can cause crucial errors and loss of fidelity during detection and analysis. A monolithically integrated device would eliminate the need to create helium-tight interconnections, which are bulky and labor intensive. Additionally, batch fabrication of integrated devices that no longer require expensive and fragile detectors can decrease the cost of micro GC systems through economies of scale. We present the design, fabrication and operation of a monolithic GC separation column and detector. Our device is able to separate nitrogen, methane and carbon dioxide within 30 s. This method of device integration could be applied to the existing wealth of column geometries and chemistries designed for specialized applications.

A novel method for the determination of total 1,3-octanediols in apple juice via 1,3-dioxanes by solid-phase microextraction and high-speed gas chromatography

In this work, a novel, simple and fast method based on solid-phase microextraction (SPME) followed by high-speed gas chromatography (HSGC) was developed for the analysis of total 1,3-octanediols in apple juices by means of derivatization reaction to volatile 1,3-dioxanes. The derivatization reaction, SPME conditions, glycosidically bound fraction and 1,3-nonanediol as a surrogate standard were studied. The formation of 1,3-dioxanes from 1,3-diols was confirmed by GC-MS. The method was validated obtaining a regression coefficient (r(2)) of 0.9996, precisions between 0.3 and 9.8%, extraction recoveries in the range 94.7-112.2% and LOD of 2.9 microg l(-1). Experimental design has been employed in the optimization of extraction factors and robustness assessment. The method was applied to the analysis of 21 Asturian apple varieties finding a double reciprocal relationship between the concentrations of saturated and unsaturated 1,3-octanediol.

Characterisation of Asturian cider apples on the basis of their aromatic profile by high-speed gas chromatography and solid-phase microextraction

Headspace solid-phase microextraction (SPME) coupled to high-speed gas chromatography with FID detector (HSGC-FID) and with quadrupole mass spectrometric detector (GC–MS) was employed to study the volatile compounds in Asturian cider apples. The optimised conditions used for characterisation of cider apple were: sample equilibration at 25 °C for 12 h, followed by PDMS–DVB fibre exposure to the headspace above the sample for 5 min and finally thermal desorption of the adsorbed substances in the injector port for GC analysis. The use of high-speed gas chromatography allowed the separation of 27 compounds in less than 8 min, reducing the analysis time in 80% compared to conventional gas chromatography. A simple, rapid and reliable method to analyze volatile compounds in cider apples has been developed. The aromatic profile of 59 apple samples included in eight apple varieties was analysed. The different apples were obtained from two consecutive harvests (2005 and 2006). The apples volatile compounds together with chemometric techniques such as principal components analysis (PCA), Bayesian analysis and linear discriminant analysis (LDA), allowed us to differentiate apples on the basis of the sweet or sharp category to which the cider apple variety belongs. Volatile compounds such as ethyl heptanoate, E-farnesene, ethyl butyrate and hexyl caprylate are closely related to cider apple cultivars of the sweet category, while propyl butyrate and butyl acetate are related to the sharp class.

Protocol for the development of automated high-throughput SPME–GC methods for the analysis of volatile and semivolatile constituents in wine samples

Ever since the invention of gas chromatography (GC), numerous efforts within the chromatographic community have been directed toward the development of fast GC methods. However, the developments in high-speed GC technologies have simultaneously created demand for the availability of compatible detection and sample preparation methods, so that the speed of the overall analytical process is increased. Solid phase micro extraction (SPME) is a sample preparation technique developed to address the need for rapid sample preparation. Therefore, the objective of this protocol is to outline recent developments in SPME technology that can be applied toward high-throughput automated qualitative and quantitative analyses of volatile and semivolatile compounds in wine samples. The use of this protocol facilitates routine high-throughput determinations of 200-500 analytes of different physicochemical properties with SPME step requiring only 10-15 min per sample.

Columns for gas chromatography: performance and selection

Preface. Acknowledgments. 1 Introduction. 1.1 Evolution of Gas Chromatographic Columns. 1.2 Central Role Played by the Column. 1.3 Justification for Column Selection and Care. 1.4 Literature on Gas Chromatographic Columns. 1.5 Gas Chromatographic Resources on the Internet. References. 2 Packed Column Gas Chromatography. 2.1 Introduction. 2.2 Solid Supports and Adsorbents. Supports for Gas-Liquid Chromatography. Adsorbents for Gas-Solid Chromatography. 2.3 Stationary Phases. Requirements of a Stationary Phase. USP Designation of Stationary Phases. Kovats Retention Index. McReynolds and Rohrschneider Classifications of Stationary Phases. Evaluation of Column Operation. Optimization of Packed Column Separations. 2.4 Column Preparation. Coating Methods. Tubing Materials and Dimensions. Glass Wool Plugs and Column Fittings. Filling the Column. Conditioning the Column and Column Care. 2.5 United States Pharmacopeia and National Formulary Chromatographic Methods. References. 3 Capillary Column Gas Chromatography. 3.1 Introduction. Significance and Impact of Capillary Gas Chromatography. Chronology of Achievements in Capillary Gas Chromatography. Comparison of Packed and Capillary Columns. 3.2 Capillary Column Technology. Capillary Column Materials. Fused Silica and Other Glasses. Extrusion of a Fused-Silica Capillary Column. Aluminum-Clad Fused-Silica Capillary Columns. Fused-Silica-Lined Stainless Steel Capillary Columns. 3.3 Preparation of Fused-Silica Capillary Columns. Silanol Deactivation Procedures. Static Coating of Capillary Columns. Capillary Cages. Test Mixtures for Monitoring Column Performance. Diagnostic Role Played by Components of Test Mixtures. 3.4 Chromatographic Performance of Capillary Columns. Golay Equation Versus the van Deemter Expression. Choice of Carrier Gas. Measurement of Linear Velocity and Flow Rate. Effect of Carrier Gas Viscosity on Linear Velocity. Phase Ratio. Coating Efficiency. 3.5 Stationary-Phase Selection for Capillary Gas Chromatography. Requirements. History. Comparison of Columns from Manufacturers. Polysiloxane Phases. Polyethylene Glycol Phases. Cross-Linked Versus Chemically Bonded Phase. Chemical Bonding. MS-Grade Phases Versus Polysilarylene or Polysilphenylene Phases. Sol-Gel Stationary Phases. Phenylpolycarborane-Siloxane Phases. 3.6 Specialty Columns. EPA Methods. Chiral Stationary Phases. Gas-Solid Adsorption Capillary Columns: PLOT Columns. 3.7 Capillary Column Selection. Practical Considerations of Column Diameter, Film Thickness, and Column Length. Capillary Columns of 0.53mm i.d.: Megabore Columns. Correlation of Column Dimensions and Film Thickness with Parameters in the Fundamental Resolution Equation. Column Selection for Gas Chromatography by Specifications. 3.8 Column Installation and Care. Carrier Gas Purifiers. Ferrule Materials and Fittings. Column Installation. Column Conditioning. Column Bleed. Retention Gap and Guard Columns. Column Fatigue and Regeneration. 3.9 Special Gas Chromatographic Techniques. Simulated Distillation. Multidimensional Gas Chromatography. Computer Modeling of Stationary Phases. References. 4 Column Oven Temperature Control. 4.1 Thermal Performance Variables and Electronic Considerations. 4.2 Advantages of Temperature Programming over Isothermal Operation. 4.3 Oven Temperature Profiles for Programmed-Temperature Gas Chromatography. 4.4 Role of Computer Assistance in Optimizing Separations in Gas Chromatography. DryLab (LC Resources). ProezGC (Restek Corporation). GC-SOS (Chem SW). 4.5 Fast or High-Speed Gas Chromatography. Selectivity Tuning. Resistively Heated Columns and Column Jackets. 4.6 Subambient Oven Temperature Control. References. Selected References. Appendix A: Guide to Selection of Packed Columns. Appendix B: Column Selection. Index.

Investigation of high-speed gas chromatography using synchronized dual-valve injection and resistively heated temperature programming

High-speed temperature programming is implemented via the direct resistive heating of the separation column (2.3 m MXT-5 Silicosteel column with a 180 μm I.D. and a 0.4 μm 5% phenyl/95% dimethyl polysiloxane film). Resistive temperature programming was coupled with synchronized dual-valve injection (with an injection pulse width of 2 ms), producing a complete high-speed gas chromatography (GC) system. A comparison of isothermal and temperature programmed separations of seven n-alkanes (C 6 and C 8–C 13) shows a substantial improvement of peak width and peak capacity with temperature programming. The system was further implemented in separations of a mixture of analytes from various chemical classes. Separations of the n-alkane mixture using three different temperature programming rates are reported. A temperature programming rate as high as 240 °C/s is demonstrated. The method for determination of temperature programming rate, based on isothermal data, is discussed. The high-speed resistive column heating temperature programming resulted in highly reproducible separations. The highest rate of temperature programming (240 °C/s) resulted in retention time and peak width RSD, on average, of 0.5 and 1.4%, respectively, for the n-alkane mixture. This high level of precision was achieved with peak widths-at-half-height ranging from 13 to 36 ms, and retention times ranging from 147 to 444 ms (for n-hexane to n-tridecane).

Rapid analysis of food products by means of high speed gas chromatography

Since the invention of GC, there has been an ever increasing interest within the chromatographic community for faster GC methods. This is obviously related to the fact that the number of samples subjected to GC analysis has risen greatly. Nowadays, in routine analytical applications, sample throughput is often the most important aspect considered when choosing an analytical method. Gas chromatographic instrumentation, especially in the last decade, has been subjected to continuous and considerable improvement. High-speed injection systems, electronic gas pressure control, rapid oven heating/cooling and fast detection are currently available in a variety of commercial gas chromatographs. The main consequence of this favourable aspect is that high-speed GC is being increasingly employed for routine analysis in different fields. Furthermore, the employment of dedicated software makes the passage from a conventional to a fast GC method a rather simple step. The present review provides an overview of the employment of fast GC techniques for the analysis of food constituents and contaminants. A brief historical and theoretical background is also provided for the approaches described.

High-speed gas chromatography in doping control: Fast-GC and fast-GC/MS determination of β-adrenoceptor ligands and diuretics

In official doping controls, about 300 drugs and metabolites have to be screened for each sample. Moreover, the number of determinations to be routinely processed increases continuously as the number of both samples and potential illicit drugs keeps growing. As a consequence, increasingly specific, sensitive, and, above all, fast methods for doping controls are needed. The present study presents an efficient fast-GC/MS approach to the routine screening of two different classes of doping agents, namely beta-adrenoceptor ligands and diuretics (belonging to the S3, P2, and S5 groups of the WADA list of prohibited substances). Narrow bore columns (100 mm id) of different lengths and coated with apolar stationary phases were successfully used to separate the derivatized analytes; preliminary experiments (results not shown) showed better performances with OV-1701 for the separation of beta-adrenoceptor ligands. On the same stationary phase some diuretics required too high a temperature or a long isothermal time for elution, in which case a DB1-MS column was preferred. Two methods of sample preparation, derivatization, and analysis were used on aqueous standard mixtures of, respectively, (i) eight beta-adrenoceptor ligands, including five beta-antagonists (acebutolol, alprenolol, atenolol, metoprolol, pindolol) and three beta2-agonists (salbutamol, clenbuterol, terbutaline) and (ii) seventeen diuretic drugs (acetazolamide, althiazide, bendroflumethiazide, bumethanide, canrenone, chlorothiazide, chlortalidone, clopamide, ethacrinic acid, furosemide, hydrochlorothiazide, hydroflumethiazide, indapamide, indomethacine, spironolactone, triamterene, trichloromethiazide) and one masking agent (probenecid). The mixture of beta-adrenoceptor ligand derivatives was efficiently separated in about 5.6 min, while the one of 18 diuretics and masking agents required less than 5 min for analysis. Limits of detection were from 1 microg/L for pindolol, ethacrinic acid, furosemide, indomethacine, and trichloromethiazide, to 20 microg/L for terbutaline, salbutamol, and metoprolol, and 50 microg/L for clopamide; the instrumental repeatability proved to be excellent (area RSD% <2 for almost all analytes). For this work a quadrupole MS with inert ion source has been used, demonstrating that the quadrupole technology is perfectly adequate to provide precise integration of 400 ms-wide GC peaks.

High-Speed MEMS-Based Gas Chromatography

This paper reports microfabricated silicon-glass separation columns for high-speed micro gas chromatography (muGC) systems. The microfabricated columns are integrated with resistive heaters and temperatures sensors and capacitive pressure sensors to allow temperature and pressure programming and flow control and to achieve reproducible separations in a muGC system. These 25-cm-long, 150-mum-wide, and 250-mum-deep columns are fabricated on a 1.2-cm square die using a silicon-on-glass dissolved wafer process. Programmed with temperature ramps of 10 degC/s, the low-mass columns separate eleven-component gaseous mixtures in less than 10 s, including alkanes from C <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">5</sub> to C <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">16</sub> and simulants for C-4, TNT, sarin, and mustard gas. When used in arrayed architectures, these MEMS columns should allow high-speed analysis without sacrificing separation efficiency

Classification of high-speed gas chromatography–mass spectrometry data by principal component analysis coupled with piecewise alignment and feature selection

A useful methodology is introduced for the analysis of data obtained via gas chromatography with mass spectrometry (GC–MS) utilizing a complete mass spectrum at each retention time interval in which a mass spectrum was collected. Principal component analysis (PCA) with preprocessing by both piecewise retention time alignment and analysis of variance (ANOVA) feature selection is applied to all mass channels collected. The methodology involves concatenating all concurrently measured individual m/ z chromatograms from m/ z 20 to 120 for each GC–MS separation into a row vector. All of the sample row vectors are incorporated into a matrix where each row is a sample vector. This matrix is piecewise aligned and reduced by ANOVA feature selection. Application of the preprocessing steps (retention time alignment and feature selection) to all mass channels collected during the chromatographic separation allows considerably more selective chemical information to be incorporated in the PCA classification, and is the primary novelty of the report. This methodology is objective and requires no knowledge of the specific analytes of interest, as in selective ion monitoring (SIM), and does not restrict the mass spectral data used, as in both SIM and total ion current (TIC) methods. Significantly, the methodology allows for the classification of data with low resolution in the chromatographic dimension because of the added selectivity from the complete mass spectral dimension. This allows for the successful classification of data over significantly decreased chromatographic separation times, since high-speed separations can be employed. The methodology is demonstrated through the analysis of a set of four differing gasoline samples that serve as model complex samples. For comparison, the gasoline samples are analyzed by GC–MS over both 10-min and 10-s separation times. The successfully classified 10-min GC–MS TIC data served as the benchmark analysis to compare to the 10-s data. When only alignment and feature selection was applied to the 10-s gasoline separations using GC–MS TIC data, PCA failed. PCA was successful for 10-s gasoline separations when the methodology was applied with all the m/ z information. With ANOVA feature selection, chromatographic regions with Fisher ratios greater than 1500 were retained in a new matrix and subjected to PCA yielding successful classification for the 10-s separations.

Low Thermal Mass Gas Chromatography: Principles and Applications

In gas chromatography (GC), temperature programming is often considered to be the second most important parameter to control, the first being column selectivity. A radically new GC technology to achieve ultrafast temperature programming with an unprecedented cool down time and low power consumption has recently become available. This technology is referred to as low thermal mass GC (LTMGC). Though the technology has its roots in resistive heating, which forms the basis of principle and design concept, the approach taken to achieve ultrafast heating and cool down time by LTMGC represents a significant break-through in GC. Despite some rectifiable shortcomings, LTMGC has proven to be an ideal methodology to deliver near/real time GC data, high precision, and high throughput applications. It is a new approach for modern high-speed GC. This paper documents the fundamental design principles behind LTMGC, performance data, and examples of applications investigated.