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An improved strategy for compound identification incorporating gas chromatography hyphenated with Fourier transform infrared spectroscopy and mass spectroscopy (GC-FTIR/MS) is reported. (Over)reliance on MS may lead either to ambiguous identity or to incorrect identification of a compound. However, the MS result is useful to provide a cohort of possible compounds. The IR result for each tentative compound match was then simulated using molecular modeling, to provide functional group and isomer differentiation information, and then compared with the experimental FTIR result, offering identification based on both MS and IR. Several basis sets were evaluated for IR simulations; Def2-TZVPP was a suitable basis set and correlated well with experimental data. The approach was applied to industrial applications, confirming the isomers of 2,3-bis(thiosulfanyl)-but-2-enedinitrile, bromination products of 1-bromo-2,3-dimethylbenzene, and autoxidative degradation of phenyl-di-tert-butylphosphine.

This study develops analytical approaches using comprehensive heart-cut multidimensional gas chromatography (H/C MDGC) to experimentally investigate effects of concentration and temperature on peak shapes and on kinetic analysis of E/Z isomerisation of oximes which undergo various extents of interconversion on 1D and 2D separation columns. Different stationary phase combinations were investigated. An SLB-IL76 1D column results in good separation of the isomers but with negligible interconversion (1Dsep). Precise targeted heart-cuts (H/C; 3–15 s windows) and cryogenic trapping of selected sections eluting from this 1D column allows well controlled E/Z isomer ratios to be delivered to a 2D poly(ethyleneglycol) (PEG) phase column. This phase catalyses oxime interconversion, with separation; this is termed 2Dinter. This column set describes a 1Dsep × 2Dinter arrangement. The interconversion forward rate constant ( k 1 UE , calculated by using DCXplorer) was found to be independent of the %E isomer (i.e. first order kinetics); k 1 UE increased at higher temperature (increased Gibbs activation energies, ΔGapp). In addition, a long 1D SLB-IL111 column gave oxime separation with interconversion (1Dinter). Comprehensive multiple H/C of the zone performed on the 2D PEG (2Dinter) at 40, 60 and 80 °C resulted in a 2D presentation (1Dinter × 2Dinter) with a unique rectangular display of interconversion from each H/C pulse with varied isomer concentration ratios. Data for k 1 UE from 1DGC analysis suggests underestimation of k 1 UE on 1Dinter SLB-IL111 from the 2D result. The k 1 UE value on 2Dinter PEG column is more reliably evaluated by summation of all the 2Dinter profiles rather than that obtained from the average value for the individual H/C pulses.

The solid-phase extraction of several polyphenolic compounds with different silica hydride-based stationary phases, as well as an unmodified type-B silica, has been investigated. In particular, the propensities of these stationary phases to extract the selected polyphenolic compounds in the batch-binding mode in the presence of 100% methanol or 50% (v/v) aqueous/methanol solvents have been examined. In addition, the zeta-potential values of these different sorbents have been determined in the same solvent compositions. The results indicated that the batch-extraction behaviour of these polyphenolic compounds with the type-B silica, unmodified silica hydride, the Diamond Hydride™ particles, silica hydride particles modified with immobilized phenyl groups or with other non-polar ligands of larger steric size, such as bidentate octyl, bidentate octadecyl, or cholesteryl groups, did not overall correlate with the particle’s zeta-potential values. However, these results indicated that the selectivity attributes in solid-phase extraction procedures of different types of silica hydride materials with polyphenolic compounds can be differentiated from experimental data acquired with small quantities of structurally related test analytes under aqueous normal-phase conditions solely from physical measurement methods, such as static batch-extraction measurements and associated GS–qMS methods of analysis.

Sapucainha oil, which may be used to treat leprosy, comprises straight chain and cyclic fatty acids (FA), and triacylglycerols (TAG). The FA and TAG content of the oil sample was analysed using gas chromatography–electron ionisation mass spectrometry (GC–EIMS). FA analysis was performed after derivatisation to fatty acid methyl esters (FAME). For free FA and TAG analysis, the oil sample was dissolved in hexane and injected into a short, high-temperature column, for GC with MS analysis. Free FA and FAME were tentatively identified based on mass spectrum information of their molecular and fragment ions, as well as library matching. Overlapping TAG peaks were deconvoluted based on mass fingerprint data. The FA composition was utilised to predict possible TAG identities. FA residues of TAG were identified based on characteristic fragment ions, such as [M–RCO2]+, [RCO+128]+, [RCO+74]+ and RCO+ where R is the aliphatic hydrocarbon chain. FAME analysis showed that the cyclic FA hydnocarpic (36.1%), chaulmoogric (26.5%) and gorlic (23.6%) acids were the major components. In addition, straight chain FA such as palmitic, palmitoleic, stearic, oleic and linoleic acids were detected. Palmitic, oleic, hydnocarpic, chaulmoogric and gorlic acids were also detected as free FA in the oil sample. Six groups of TAG peaks were eluted from GC at temperatures ≥330 °C. After deconvolution and mass spectrum analysis, each TAG peak group was revealed to comprise 2 to 5 co-eluted TAG molecules; >18 TAG were identified. These TAG consisted of a mix of both cyclic and straight chain FA, but were mostly derived from cyclic FA.

In contrast to the well-known comprehensive two-dimensional gas chromatography (GC×GC) method, it is possible to define comprehensive multidimensional gas chromatography. ‘Comprehensiveness’ relates to analysis of the whole sample. Two-dimensional and multidimensional here refer to the use of at least two separation stages for analysis, however comprehensive 2DGC now appears to be reserved for the GC×GC method. This may be differentiated from comprehensive MDGC (CMDGC) simply by the analysis time assigned to the second (2D) column, although there does not appear to be a specific definition that relates to this analysis time parameter. A number of different implementation protocols for comprehensive MDGC are described here, that may involve either a single, or multiple, injection(s). In all cases, independent retention must be achieved on each dimension to ensure the probability of enhanced separation. An original application of a crude oil sample is presented to illustrate development of the MDGC approach that incorporates two Deans switches (DS) and a cryogenic trapping approach, performed using a sequential heart-cut (H/C) event method incremented by 0.5 min for each injection; a total of 40 injections is used to analyse the total sample. The higher peak capacity and consequently greater resolution on the long 2D column is illustrated, compared with that expected for conventional GC×GC, with tentative identification in order to classify chemical classes. Incorporating an approach to acquiring retention indices may be implemented, although its utility for petroleum hydrocarbons is limited. Structured groupings of different chemical classes, as exemplified by mono and diaromatics for the crude oil sample, were noted.

A data interpretation and processing approach for improved compound identification and data presentation in comprehensive two-dimensional gas chromatography (GC×GC) is described. A footprint peak of a compound in 2D space can be represented by a centroid or peak apex, similar to the data-reduced histogram spectra used in mass spectrometry. The workflow was demonstrated on data from GC×GC-TOFMS. Peaks in a modulated chromatogram were initially detected by conventional chromatographic integration, followed by a curve-fitting approach, which interpolated high-precision, absolute retention times for all modulated peaks. First dimension retention time (1tR) was obtained by using an exponentially modified Gaussian (EMG) fitting model for near-Gaussian distributed subpeaks, polynomial fitting for highly asymmetrical peaks, and parabolic fitting for under-sampled peaks, which allows determination of a precise 1tR, considering the dwell-time arising from modulation and 2tR. Area summation of the modulated peaks belonging to the same compound was then performed to yield the total peak area. Each compound in the GC×GC-MS result was then represented by its position at the intersecting coordinates, (1tR, 2tR), in the 2D separation plane, having a height of the same magnitude as the total component summed area. This results in a novel and uncluttered GC×GC output convention based on the scripted total ion chromatogram (TIC) data with precise 1tR, 2tR, and area. Comparison between the contour plots from the scripted and conventional TIC revealed improved data presentation, accompanied by an apparent enhanced resolution. The described approach was applied to the identification of 177 aroma compounds from peaches as indicators of fruit quality.

Comprehensive two-dimensional gas chromatography (GC×GC) and multidimensional GC (MDGC) offer high performance separation capability towards multi-component samples, and improved sample characterisation. Recent advances, particularly with new GC×GC methodologies, which apply additional columns to GC×GC, along with hyphenation with mass spectrometry, potentially have a tremendous impact on the analysis of various applications such as food, petrochemicals, fragrances, drugs and environmental samples. The present review highlights the new experimental designs in GC×GC coupled with MDGC to offer significant changes in operational performance, and applications of these technologies which have been developed since 2000.

Apart from the pure methodological process of implementing a comprehensive two-dimensional gas chromatography (GC×GC) method, surely it is the excitement engendered by a well-designed separation that has captured the attention, fascinated and sustained proponents and users throughout the decades since Liu and Phillips1 were equally enthralled by what they produced, the first time they witnessed their result. This technology update largely addresses developments over the last 2 years (late 2017 – 2019) since the Synovec group presented their review.2 Progressive advances in instrumentation, software and data analysis tools, fundamental relationships and capabilities, and the numerous repertoire of applications to which GC×GC methods have been applied will be included. We attempt to offer an insight into the dynamic nature of the field, and hopefully many newer converts to the field will be recognized for their emerging interest and contributions.

Heart-cut multidimensional gas chromatographic (H/C MDGC) methods under suitable flow and high temperature (T) program conditions were developed to separate olive oil triacylglycerols (TAGs). Different column sets were selected for further evaluation, each with relatively short non-polar first dimension (1D) and mid-polar second dimension (2D) columns of high T limits (350 °C). The 1D separation displayed three major groups of peaks in an area ratio of approximately 5:33:62 (of increasing retention), using flame ionisation detection (FID). Four groups of minor peaks, with 2 of them located between the major peaks, were also detected. The H/C fractions of the minor peaks, and sub-sampled regions across the major peaks eluting from the 1D outlet, were cryotrapped at the 2D inlet. The trapped TAGs then underwent temperature programmed 2D separation. Each of the ‘H/C’ zones generally gave 2–5 – and in some cases more – separated peaks of TAGs on the 2D column, under suitable flow condition and phase polarity that resulted in improved separation. Six sub-sampled H/Cs from various regions of the individual peaks from the 1D column were simultaneously trapped and released to 2D, resulting in apparently more than 22 individual TAG peaks. According to their different retention times, different TAGs were revealed within each of the 3 major groups, using H/C sub-sampling. A comprehensive sampling strategy that covers most of the 1D peaks further revealed the presence of more TAGs in the olive oil sample. This tandem column strategy was able to resolve more components than that usually observed on a single column.

Real-time interconversion processes produce unconventional peak broadening in gas chromatography (GC), and can be used to generate kinetic and thermodynamic data. In this study, an unusual separation situation in comprehensive two dimensional GC where two dimensional interconversion (i.e. a raised plateau in both first and second dimension, 1D and 2D) was observed in analysis of oxime isomers. This resulted in a characteristic and unusual rectangular peak shape in the two dimensional result. A related theoretical approach was introduced to explain the peak shape supported by simulation results which can be varied depending on concentration profiles and kinetics of the process. The simulated results were supported by experimental results obtained by a comprehensive heart-cut multidimensional GC (H/C MDGC) approach which was developed to clearly investigate isomerisation of E/Z oxime molecules in both 1D and 2D separations under different isothermal conditions. The carrier gas flow and oven temperature were selected according to initial results for 1D interconversion on a poly(ethyleneglycol) stationary phase, which was further used in both 1D and 2D separations to result in broad zones of oxime interconversion in both dimensions. The method involved repetitive injections of oxime sample, then sampling contiguous fractions of sample into a long 2D column which is intended to promote considerable interconversion. Comprehensiveness arises from the fact that the whole sample is sampled from the 1D to the 2D column, with the long 2D column replacing the short 2D column used in classical comprehensive two-dimensional gas chromatography, where the latter will not promote sufficient interconversion. Data processing and presentation permits a 'rectangular' distribution corresponding to the separated compounds, characteristic of this experiment.

Molecular spectroscopic detection plays a crucial role in gas chromatography (GC). Some detectors constitute element-selective spectroscopy, where an element-containing species generates the detected signal, e.g. flame photometric detection (S, P, Cu); chemiluminescence detection (S, N). These respond with selective response, usually with excellent analyte detectability and reduced matrix interferences. Classical molecular spectroscopic detectors – Fourier transform infrared, nuclear magnetic resonance, ultraviolet – respond by giving a spectrum characteristic of the (intact) molecule. Molecular structure response plays multi-faceted roles: it produces a unique spectrum of a molecule, provided it is resolved by the column and presented to the detector as a single compound; or the chromatogram can be generated by responding to the total signal, or selectively to a given component of the signal. This review summarises the response, sensitivities, applicability, and recent literature reports of molecular spectroscopic detection. Hyphenation with dual detection and brief comments on multidimensional GC is included.

Multidimensional gas chromatography (MDGC) offers excellent separation efficiency that serves advanced characterisation of volatiles and semi-volatiles in food samples. An overview of recent data analysis, capabilities, and technologies in MDGC commencing from conventional heart-cut (MDGC), to its more recent comprehensive two-dimensional gas chromatography (GC×GC) variant is included. Selected applications are emphasised that include improved untargeted and target compound identification, fingerprinting and group type analysis, applied to food. Benefits to improved compound identification in MDGC by employing different hyphenation approaches are also emphasised. We conclude by highlighting recent advances and future trends, including three- and higher-dimensional GC with MS separation, on-line hyphenation with LC, and hybrid and multifunctional MDGC systems.

This study reports gas chromatography (GC) combined with Fourier transform infrared (FTIR) spectroscopy to investigate the elution profiles of individual oxime isomers undergoing characteristic interconversion (dynamic chromatography) in GC. The use of a light-pipe FTIR interface enables on-line acquisition of FTIR spectra, which in turn render unambiguous identification of the individual molecules. Here, acetaldehyde oxime and propionaldehyde oxime were chosen for comparison of elution behaviour under varying temperature and carrier flow velocities. The choice of selective responses (wavenumber selectivity), which were relatively stronger for each isomer, enabled display and retracing of the individual isomer over the chromatographic time scale and thus provided characteristic single isomer profiles. Chemometric data analysis using the multivariate curve resolution technique further confirmed this isomer elution profile. Simulation of the spectrum for each isomer allowed comparison with instrument-generated FTIR spectra to confirm the elution order of E and Z isomers. The effect of changing chromatographic parameters (temperature, flow) on interconversion rates and/or extents were studied and the corresponding change in FTIR spectrum intensity was noted. The GC–FID data acquired concurrently with GC–FTIR analyses ratified isomerisation chromatographic profiles.

Perfluorinated C8-(PerfluoroC8) and bidentate anchored C8-(BDC8)-modified silica hydride stationary phases have been employed for the isocratic separation of homologous phenylalkanols and phenylalkylamines differing in their n-alkyl chain length, using aqueous-acetonitrile (ACN) mobile phases of different ACN contents from 10 to 90% (v/v) in 10% increments. These analytes showed reversed-phase (RP) retention behaviour with mobile phases of 80% (v/v) ACN content), with the analytes exhibiting overall U-shape retention dependencies on the ACN content of the mobile phase. Further, these stationary phases showed differences in their selectivity behaviour with regard to the n-alkyl chain lengths of the different analytes. These observations could not be explained in terms of pKa, log P, molecular mass or linear solvation energy concepts. However, density functional theory (DFT) simulations provided a possible explanation for the observed selectivity trends, namely differences in the molecular geometries and structural organisation of the immobilised ligands of these two stationary phases under different solvational conditions. For mobile phase conditions favouring the RP mode, these DFT simulations revealed that interactions between adjacent BDC8 ligands occur, leading to a stationary phase with a more hydrophobic surface. Moreover, under mobile phase conditions favouring retention of the analytes in an ANP mode, these interactions of the bidentate-anchored C8 ligands resulted in hindered analyte access to potential ANP binding sites on the BDC8 stationary phase surface. With the PerfluoroC8 stationary phase, the DFT simulations revealed strong repulsion of individual perfluoroC8 ligand chains, with the perfluoroC8 ligands of this stationary phase existing in a more open brush-like state (and with a less hydrophobic surface) compared to the BDC8 ligands. These DFT simulation results anticipated the chromatographic findings that the phenylalkanols and phenylalkylamines had reduced retention in the RP mode with the PerfluoroC8 stationary phase. Moreover, the more open ligand structure of the PerfluoroC8 stationary phase enabled greater accessibility of the analytes to water solvated binding sites on the stationary phase surface under mobile phase conditions favouring an ANP retention mode, leading to retention of the analytes, particularly the smaller phenylalkylamines, via hydrogen bonding and electrostatic effects., Graphical abstract Image 1, Highlights • Separation of phenylalkanols and phenylalkylamines of different alkyl chain length studied. • U-shape retention dependency on organic modifier content with the perfluorinated C8 silica hydride phase observed. • Analyte separation in both RP and ANP modes with perfluorinated C8 phase documented. • Retention behavior of perfluorinated C8 and C8 modified silica hydride phases compared. • Results rationalised with density functional theory simulations of the two stationary phases ligand structures.

Seed and vegetable oils are complex mixtures of components, with the major classes including mono-, di- and triacylglycerols, fatty acids, phytosterols, tocopherols and tocotrienols. An overview of recent advances in the analysis of seed and vegetable oils by both one-dimensional (1D) and multidimensional gas chromatography (MDGC) methodologies is presented. Authenticity of food oils continues to be important, and use of various classes of compounds as markers for adulteration are highlighted. Selected applications of contaminants analysis, including pesticides, hydrocarbons and plasticisers, are emphasised. A brief comparison of the separation technologies gas chromatography (GC) and liquid chromatography (LC) is also included. The review concludes by highlighting recent advances and future trends.

Recent advances in multidimensional gas chromatography (MDGC) comprise methods such as multiple heart-cut (H/C) analysis and comprehensive two-dimensional gas chromatography (GC × GC); however, clear approaches to evaluate the MDGC results, choice of the most appropriate method, and optimized separation remain of concern. In order to track the capability of these analytical techniques and select an effective experimental approach, a fundamental approach was developed utilizing a time summation model incorporating temperature-dependent linear solvation energy relationship (LSER). The approach allows prediction of optimized analyte distribution in the 2D space for various MDGC approaches employing different experimental variables such as column lengths, temperature programs, and stationary phase combinations in order to evaluate separation performance (apparent (1)D, (2)D, total number of separated peaks, and orthogonality) for simulated MDGC results. The methodology applied LSER to generate results for nonpolar-polar and polar-nonpolar 2D column configurations for separation of 678 compounds in an oxidized kerosene-based jet fuel sample. Three-dimensional plots were generated in order to illustrate the dependency of separation performance on (2)D column length and number of injections for different stationary phase combinations. With a given limit of analysis time, a MDGC approach to obtain an optimized total separated peak number for a particular column set was proposed depending on (1)D and (2)D analyte peak distribution. This study introduces fundamental concepts and establishes approaches to design effective GC × GC or multiple H/C systems for different column combinations, to provide the best overall separation outcomes with the highest separated peak number and/or orthogonality.

A 'heart-cut' multidimensional gas chromatography‒mass spectrometry (H/C MDGC‒MS) method for separation and identification of triacylglycerols (TAGs) in extra virgin olive oil was developed. A GC configuration, comprising a non-polar first dimension (1D) column (15 m length) and a mid-polarity second dimension (2D) column (9 m length), was employed. Standard TAGs were used to test and demonstrate the H/C MDGC method, for identification of TAG components and to validate the method. Various chromatographic conditions such as column flow and temperature program were evaluated. The 1D separation resulted in overlap of some standard TAG peaks. These overlapped 1D regions of the standard TAGs were H/C to 2D for further separation and resulted in clearly distinguished individual TAG component peaks. The 1D separation of olive oil TAGs displayed three major peaks and four minor peaks. The application of the H/C MDGC method to olive oil TAGs resulted in the separation of each sampled 1D region into two or more TAG peaks. TAG components in olive oil resolved on the 2D column were identified based on characteristic mass fragment ions such as [M-RCO2]+, [RCO+128]+, [RCO+74]+ and RCO+ and comparison of their mass spectra with that of the standard TAGs. Sixteen olive oil TAGs were identified by MS after 2D separation. The repeatability of the H/C method was evaluated in terms of retention time shift and area response in the 2D and found to be

Comprehensive two-dimensional gas chromatography (C2DGC) offers excellent separation efficiency that serves advanced analysis of volatiles and semi-volatiles in multicomponent and multiple chemical class samples. This review presents an overview of concepts and experimental approaches to continuous flow C2DGC starting from classical single injection C2DGC (conventional GC×GC) to using repeat injections with a longer second column. A strategy of multiple heart-cut multidimensional GC (CH/C MDGC) to construct a variant that is also comprehensive in concept is reviewed, along with various methods – a continuum – between these extremes. Recent selectivity-optimised systems in GC×GC, including new stationary phases or other multiple column arrangements and their applications are also highlighted. The review presents a fundamental background to guide column selection for specific applications in conjunction with experimental design, and future trends.

Molecular spectroscopic detection techniques, such as Fourier transform infrared spectroscopy (FTIR), provides additional specificity for isomers where often mass spectrometry (MS) fails, due to similar fragmentation patterns. A hyphenated system of gas chromatography (GC) with FTIR via a light-pipe interface is reported in this study to explore a number of GC&ndash, FTIR analytical capabilities. Various compound classes were analyzed&mdash, aromatics, essential oils and oximes. Variation in chromatographic peak parameters due to the light-pipe was observed via sequentially-located flame ionization detection data. Unique FTIR spectra were observed for separated mixtures of essential oil isomers having similar mass spectra. Presentation of GC&times, FTIR allows a &lsquo, comprehensive&rsquo, style experiment to be developed. This was used to obtain spectroscopic/separation profiles for interconverting oxime species with their individual spectra in the overlap region being displayed on a color contour plot. Partial least square regression provides multivariate quantitative analysis of co-eluting cresol isomers derived from GC&ndash, FTIR data. The model resulted in an R2 of 0.99. Prediction was obtained with R2 prediction value of 0.88 and RMSEP of 0.57, confirming the method&rsquo, s suitability. This study explores the potential of GC&ndash, FTIR hyphenation and re-iterates its value to derive unambiguous and detailed molecular information which is complementary to MS.

Approaches to simulate peak time and intensity profiles of compounds in comprehensive two dimensional gas chromatography (GC × GC) were developed, and which are demonstrated for separation of a mixture of saturated and unsaturated fatty acid methyl esters (FAME) using a range of column sets. The simulation of first and second dimension time (1tR and 2tR) of FAME relies on use of a Gibbs energy additivity approach to correlate with the structures of FAME. First and second dimension peak standard deviations (1σ and 2σ) of the compounds were further calculated from the 1tR and 2tR data according to the plate height concept which provided good agreement between the predicted and experimental peak widths at half height in one dimension GC (1DGC) with an overall R2 of 0.9628. The effect of 1σ distortion caused by the modulation process was also taken into account in the peak width simulation where the simulated 1σ data were rounded up to multiples of the scale of modulation period (PM). Two dimension Gaussian equations were then used to generate GC × GC results (2D contour plots) from simulated 1tR, 2tR, 1σ and 2σ data for FAME separation on different column sets employing ionic liquid and conventional columns. Good overall correlations between experimental and simulated 1tR and 2tR were obtained with R2 of 0.9951 and 0.9802, respectively, and the simulated 2D contour plots were an acceptable match with the experimental results.

The extraction capabilities of a Diamond Hydride™ phase, as well as silica hydride phases modified with bidentate octadecyl (BDC(18)), phenyl or cholesteryl groups, were evaluated for the analysis of fatty acids, amino acids, sugars and sterols in a dark chocolate extract. These batch adsorption performances were investigated using either methanol or aqueous methanol as the solvent. The compositions of the extracted fractions were assessed by gas chromatography interfaced with quadrupole mass spectrometry (GC-qMS). The batch binding propensities of the various compound classes with silica hydride particles modified with immobilised phenyl groups or larger ligands followed trends predicted from linear solvation energy relationships. Both prediction and experiment revealed that better extraction results could be obtained with the phenyl, BDC(18) and cholesteryl hydride particles for the major chocolate components. Based on these results, separations in micro-pipette tip format with these three types of stationary phase particles have been undertaken.

A precursor solution to the metal-organic framework (MOF), Cd(1,4,7,10-tetrakis(4-carboxybenzyl)-1,4,7,10-tetraazacyclododecane), was aged in a surface-functionalised 250μm-diameter capillary, to generate a film containing the constituents of the bulk phase crystalline material. EDX analysis revealed a higher ratio of ligand elements (C, N and O) to Cd in the capillary coated phase compared to that achieved from bulk synthesis in a vial. Separation performance of the coated capillary for gas chromatography (GC) was compared to the performance of the original MOF crystals packed in tips for liquid elution chromatography (LEC) towards the separation of polycyclic aromatic hydrocarbons (PAHs) and small probe analytes with different properties. This study showed that different retention mechanisms were observed for the same set of analytes in gas and liquid phases. Independently of the trend of vapour pressure difference, the GC result showed less specific size selective retention, but with stronger retention towards larger PAHs. A linear solvation energy relationship correlation further revealed enhanced retention contributions (positive stationary phase descriptor values) by cavity formation/dispersion interactions and H-bonding with acid functionality of the probe analytes in both GC and LEC (though stronger in LEC), whilst H-bonding with basic functional groups slightly increased retention in GC; retention was strengthened by dipole-dipole/dipole-induced dipole interactions only in LEC.

Chiral comprehensive two-dimensional gas chromatography (eGC×GC) coupled to quadrupole–accurate mass time-of-flight mass spectrometry (QTOFMS) was evaluated for its capability to report the chiral composition of several monoterpenes, namely, α-pinene, β-pinene, and limonene in cardamom oil. Enantiomers in a standard mixture were fully resolved by direct enantiomeric-GC analysis with a 2,3-di-O-methyl-6-t-butylsilyl derivatized β-cyclodextrin phase; however, the (+)-(R)-limonene enantiomer in cardamom oil was overlapped with other background components including cymene and cineole. Verification of (+)-(R)-limonene components based on characteristic ions at m/z 136, 121, and 107 acquired by chiral single-dimension GC−QTOFMS in the alternate MS/MSMS mode of operation was unsuccessful due to similar parent/daughter ions generated by interfering or co-eluting cymene and cineole. Column phases SUPELCOWAX, SLB-IL111, HP-88, and SLB-IL59, were incorporated as the second dimension column (2D) in chiral GC×GC analysis; the SLB-IL59 offered the best resolution for the tested monoterpene enantiomers from the matrix background. Enantiomeric ratios for α-pinene, β-pinene, and limonene were determined to be 1.325, 2.703, and 1.040, respectively, in the cardamom oil sample based on relative peak area data. Chirality 26:747–753, 2014. © 2014 Wiley Periodicals, Inc.

Flavonoids represent one of the more abundant classes of phytochemicals. They are renowned for their health benefits against age-related ailments and diseases. Several chromatography techniques have underpinned many chemical analysis methods, developed for superior flavonoid separation and identification. Among these, GC is one of the most powerful tools in separation science, providing precise measurement of a wide range of flavonoids. Combined with various detectors – most commonly MS–GC offers a sensitive and accurate tool for quantitative and qualitative flavonoids analysis. This review features developments in the application of GC and MS for flavonoids determination during past decades, progressing to recent developments and considering future trends. The review will highlight the state-of-the-art of GC, with opportunities for multidimensional GC analysis also briefly discussed.

The selection of the best column sets is one of the most tedious processes in comprehensive two-dimensional gas chromatography (GC × GC) where a multitude of choices of column sets could be employed for an individual sample analysis. We demonstrate analyte/stationary phase dependent selection approaches based on the linear solvation energy relationship (LSER), which is a reliable concept for the study of interaction mechanisms and retention prediction with a large database pool of columns and compounds. Good correlations between our predicted results, with experimental results reported in the literature, were obtained. The developed approaches were applied to the simulation of 157 920 individual experiments in GC × GC, focusing on the application of 30 nonionic liquid and 111 ionic liquid (IL) stationary phases for separation of some example sets of model compounds present in practical samples. The best column sets for each sample separation could then be extracted according to maximizing orthogonality, which estimates the quality of separation.

Comprehensive two-dimensional gas chromatography hyphenated with accurate mass time-of-flight mass spectrometry (GC × GC-accTOFMS) was applied for improved analytical accuracy of saffron analysis, by using retention indices in the two-dimensional separation. This constitutes 3 dimensions of identification. In addition to accTOFMS specificity, and first dimension retention indices ((1)I), a simple method involving direct multiple injections with stepwise isothermal temperature programming is described for construction of isovolatility curves for reference alkane series in GC × GC. This gives access to calculated second dimension retention indices ((2)I). Reliability of the calculated (2)I was evaluated by using a Grob test mixture, and saturated alkanes, revealing good correlation between previously reported I values from the literature, with R(2) correlation being 0.9997. This essentially recognizes the retention property of peaks in the GC × GC 2D space as being reducible to a retention index in each dimension, which should be a valuable tool supporting identification. The benefit of (2)I data, in supplementing (1)I and MS library matching, was clearly demonstrated by the progressive reduction of the number of possible compound matches for peaks observed in saffron. 114 analytes were assessed according to (1)I and (2)I values within ±20 index unit of reference values, and by MS spectrum matching above a match statistic of 750 (including mass accuracy of the molecular ion20 ppm) and their possible identities derived. The described method provides a new avenue to utilize the full capability of the two-dimensional separation (GC × GC), in combination with MS library matching in complex sample analysis, to provide improved component identification.

In this study, a theoretical concept and method to achieve a degree of orthogonality in comprehensive two-dimensional gas chromatography (GC × GC) for separation of fatty acid methyl esters (FAME) by using a single ionic liquid (IL) stationary phase (1-phase-GC × GC) were established. The 1-phase system comprises a long IL column and shorter IL column of the same phase before and after the modulation region, operated under temperature-programmed conditions. Initial isothermal experiments employing six commercial IL columns were conducted at different temperatures. On the basis of the temperature-dependent linear solvation energy relationship (LSER) concept, SLB-IL111 exhibited the greatest thermal sensitivity and degree of difference over the tested temperature (T) range, so it was selected for investigation of the 1-phase-GC × GC mode. With the same temperature program, a significantly high degree of orthogonality was observed for the experiment, varied with column lengths. The switchable separation result, which inverts the retention of saturated and unsaturated FAME on the downstream column ((2)D), was achieved by varying column diameters and surface thicknesses of the IL-coated layers. These results were explained according to the corresponding LSER principles. Also, the time summation model was applied for the simulation of the observed 1-phase-GC × GC results.

Due to their distinct chemical properties, the application of ionic liquid (IL) compounds as gas chromatography (GC) stationary phases offer unique GC separation especially in the analysis of geometric and positional fatty acid methyl ester (FAME) isomers. Elution behaviour of FAME on several commercialised IL capillary columns including phosphonium based SLB-IL59, SLB-IL60, SLB-IL61 and SLB-IL76 and imidazolium based SLB-IL82, SLB-IL100, and SLB-IL111 as well as a general purpose column SLB-5ms, were evaluated in gas chromatography-mass spectrometry (GC-MS) analysis. The phases were further characterised by using a linear solvation energy relationship (LSER) approach according to the equivalent chain length (ECL) index of FAME. Among all tested IL columns, elution temperatures of saturated FAME increased as their McReynolds' polarity value decreased, except for IL60. ECL values increased markedly as the stationary phase polarity increased, particularly for the polyunsaturated FAME. The LSER study indicated a lowest l/e value at 0.864 for IL111, displaying phase selectivity towards unsaturated FAME, with higher peak capacity within a carbon number isomer group. s and e descriptors calculated from LSER were validated by excellent correlation with dipole moments and lowest unoccupied molecular orbital (LUMO) energies, with R(2) values of 0.99 and 0.92 respectively, calculated using GAUSSIAN.

Polymorphic metal-organic framework (MOF) materials offer a platform for small-scale separation of complex mixtures of polycyclic aromatic hydrocarbons (PAHs) and polar compounds. Retention factors show dependence on both analyte dimensions and polarity, suggesting mixed-mode separation, allowing complete resolution of some analytes from multi-component mixtures.