Reduction of surface treatment time by combination of citric acid and ascorbic acid while restoring shear bond strength of metal brackets bonded to bleached enamel: a pilot study.

BACKGROUND: To investigate the effect of a 50% ascorbic acid with 50% citric acid solution on the immediate shear bond strength (SBS) of metallic brackets after tooth bleaching. The enamel etching pattern and the required quantity of these combined acids as antioxidants following 35% hydrogen peroxide (HP) bleaching were also determined. METHODS: The stability of the solution at room temperature was assessed at various time intervals. Fifty teeth were randomly divided into five groups: non-bleached (G1), bleached then acid etched (G2), bleached followed by a 10-minute treatment with 10% sodium ascorbate and acid etched (G3), 5-minute treatment with 50% ascorbic acid (G4), and 5-minute treatment with a combination of 50% ascorbic acid and 50% citric acid (G5). Groups G2, G3, G4 and G5 were bleached by 35% HP gel for a total of 32 min. Acid etching in groups G1, G2, and G3 was performed using 37% phosphoric acid (Ormco®, Orange, CA, USA) for 15 s. In all groups, metal brackets were immediately bonded using Transbond™ XT primer and Transbond™ PLUS adhesive, with light curing for 40 s. The SBS was tested with a universal testing machine, and statistical analysis was conducted using one-way ANOVA followed by Tukey's HSD test. The level of significance was set at p < 0.05 for all statistical tests. RESULTS: Stability tests demonstrated that the combined acids remained effective for up to 21 days. Group G5 significantly increased the SBS of bleached teeth to the level of G1 (p < 0.05), while G3 did not achieve the same increase in SBS (p > 0.05). SEM analysis revealed enamel etching patterns similar to those of both control groups (G1 and G2). Kinetic studies at 6 min indicated that the antioxidation in G5 reacted 0.2 mmole lower than in G3 and G4. CONCLUSION: 5-minute application of the combined acids enhanced the SBS of bleached teeth comparable to unbleached teeth. The combined acids remain stable over two weeks, presenting a time-efficient, single-step solution for antioxidant application and enamel etching in orthodontic bracket bonding.

Development and Application of a Novel Multiloop Splitter-Based Non-cryogenic Artificial Trapping Modulation System in Comprehensive Two-Dimensional Gas Chromatography.

A multiloop splitter-based non-cryogenic artificial trapping (M-SNAT) modulation technique was established, which applied the first (1D) nonpolar and the second (2D) polar columns, deactivated fused silica (DFS) columns, a microfluidic Deans switch (DS), and splitters located between the 1D column outlet and the DS. The splitters were connected into multiple loops with a progressively doubled perimeter of the next loop. This enabled a duplex splitting mechanism within each loop consisting of splitting of analyte pulses, the pulse delay, and their combination which led to equally split peaks of the same analytes with the number of split peaks (nsplit) equal to 2m (m = number of loops). This system resulted in local profiles of artificially split-and-trapped analytes prior to their selective transfers onto the 2D column by means of periodic multiple heart-cuts (H/C). The developed SNAT approach can be successful, providing that the ratio of modulation period to sampling time (PM/tsamp) is equal to nsplit. The approach with nsplit = 16 was further developed into a single device platform and applied for the modulation of a wide range of compounds in waste tire pyrolysis samples with the RSD of ≤0.01 and <10% for the one-dimensional modulated peak times and peak areas, respectively (n = 50). The method enabled an artificial modulation mechanism without cryogen consumption and enhanced the 2D peak capacity (2nc) and 2D separation by use of a longer 2D column.

A fluorescence-based sweat test sensor in a proof-of-concept clinical study for COVID-19 screening diagnosis.

During the corona virus disease 2019 (COVID-19) pandemic period, rapid screening of covid-19 patients has been of great interest by developing a fluorescent sensor for complexation with nonanal, which is a marker for Covid-19 detection in sweat. Solid phase micro-extraction gas chromatography-mass spectrometry (SPME GC-MS) was initially used to quantify nonanal in armpit sweat samples based on an external calibration curve. A sample containing a nonanal content above the threshold of 1.04 µL is expected to be COVID-19 positive with a sensitivity and specificity of 87% and 89%, respectively, validated by comparison with RT-PCR results. For more practical applications, helicene dye-encapsulated ethyl cellulose, namely EC@dyeNH, was applied to screen 140 sweat samples collected from the foreheads of volunteers. The mixed sensor and sweat solution droplets were then visualized and imaged under blacklight. The COVID-19 positive droplets exhibited yellow fluorescence emission, the brightness of which could be measured by using ImageJ in the grey scale. With the optimum color intensity of >73 for positive results, the screening performance was observed with a sensitivity and specificity of 96% and 93%, respectively. The overall test time of this method is approximately less than 15 min. This alternative method offers a promising practical screening approach for the diagnosis of COVID-19 in sweat.

Structure Elucidation Using Gas Chromatography-Infrared Spectroscopy/Mass Spectrometry Supported by Quantum Chemical IR Spectrum Simulations.

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.

Thin layer chromatography based extraction approaches for improved analysis of volatile compounds with gas chromatography-mass spectrometry and direct analysis with gas analyzer.

In this study, thin-layer chromatography was applied for selective extraction of volatile compounds in perfume prior to analysis with solid phase microextraction and gas chromatography-mass spectrometry. The standard compounds were desorbed from the thin-layer chromatography plate and extracted at 80°C for 15 min showing good linearity of the calibration curves (R2  > 0.98) and acceptable recovery range (65-81%). The plate after the separation was cut into four smaller parts followed by solid phase microextraction/gas chromatography-mass spectrometry analysis, which revealed different compound profile in each part with the correlation between log P of the standard compounds and their positions along the thin-layer chromatography plate (R2  = 0.65). This approach was applied to analyze perfume compounds in the sample with strong matrix interference from the synthetic agarwood. Terpene hydrocarbons (woody-based odors), ketones/esters, aldehydes, ethers, and alcohols were mostly observed at 8 ± 1, 6 ± 1, 5 ± 2, 4 ± 2, and 3 ± 2 cm, respectively, from the bottom of the thin-layer chromatography plate. While, the conventional solid phase microextraction/gas chromatography-mass spectrometry analysis of this sample solution revealed only 62 compounds (including 35 perfume compounds), the four-piece approach resulted in 109 compounds (62 perfume compounds). Furthermore, the capability of thin-layer chromatography-Gas Analyzer approach to analyze the isomers in this complex sample was demonstrated.

Application of cup-shaped trilactams for selective extraction of volatile compounds by gas chromatography-mass spectrometry.

Chiral cyclic trilactams ((+)-1 and (-)-1) with C3 symmetry were investigated as liquid phase extraction materials of volatile compounds. Perfume samples, involving a range of chiral odor active terpenoids, were applied and each sample before and after the liquid phase extraction was analyzed by solid phase microextraction (SPME)-gas chromatography hyphenated with mass spectrometry. It was found that (+)-1 exhibited significantly higher enrichment factors for several terpenoids, while (-)-1 did not. The mode of interactions between each enantiomer and l-menthol and Kharismal (methyl dihydrojasmonate) was further investigated by molecular dynamics (MD) simulations and theoretical density functional theory (DFT) calculations, showing the favorable interactions of enriched substrates with (+)-1 through noncovalent interactions, either hydrogen bonds or electrostatic interactions.

Bioassay-Guided Fractionation, Chemical Compositions and Antibacterial Activity of Extracts from Rhizomes of Globba schomburgkii Hook.f.

Bioassay-guided fractionation was conducted on dichloromethane extract from the rhizomes of Globba schomburgkii Hook.f., which have previously been reported as the part with the highest antibacterial activity. 10 fractions and 20 sub-fractions were obtained and evaluated for their potency against various strains of bacteria. The most active sub-fractions were 8 times more effective against Staphylococcus aureus and Micrococcus luteus than the original crude extract. Moreover, two pure compounds, namely petasol and (E)-15,16-dinorlabda-8(17),11-dien-13-one, were successfully isolated and characterized for the first time from this plant species. Untargeted compound analysis of all fractions and sub-fractions was performed by gas chromatography hyphenated with mass spectrometry, leading to positive identification of 167 compounds according to comparison with the mass spectrum and retention index database, 137 of which have never been reported for G. schomburgkii. The correlation between antibacterial activity and composition of each fraction suggests that the bioactive compounds could be 4,8-ß-epoxycaryophyllene, methyl isocostate, (E)-labda-8(17),12-diene-15,16-dial, α-kessyl acetate, zederone, clovanediol, ledene oxide-(I), alantolactone, or 8α,11-elemadiol.

Gas chromatography-mass spectrometry of sapucainha oil (Carpotroche brasiliensis) triacylglycerols comprising straight chain and cyclic fatty acids.

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.

Volatile Chemical Composition, Antibacterial and Antifungal Activities of Extracts from Different Parts of Globba schomburgkii Hook.f.

Globba schomburgkii Hook.f. is an ornamental plant that has recently found increasing demand as cut flowers, hence generating a significant number of by-products from different parts of the plant. To investigate the further applications of these by-products, twelve crude extracts from rhizomes, stalks, leaves, and flowers were prepared by serial exhaustive extraction. The volatile composition of these extracts was analyzed by GC/MS; a total of 89 compounds were identified, most of which were sesquiterpenes as well as some labdane-type diterpenes. The antimicrobial activities of these extracts were evaluated, revealing a correlation between the terpenoid content and antibacterial activities. Notably, the dichloromethane extracts of rhizomes and flowers, which contained the highest amount of terpenoids (e. g., α-gurjunene, guaia-9,11-diene, γ-bicyclohomofarnesal, ß-caryophyllene, and caryophyllene oxide), displayed the most prominent antibacterial activities. This work demonstrates the potential use of the crude extracts from G. schomburgkii as natural antibacterial ingredients for pharmaceutical and other applications.

Comprehensive 2D gas chromatography-time-of-flight mass spectrometry with 2D retention indices for analysis of volatile compounds in frankincense (Boswellia papyrifera).

Frankincense gum resin secreted from Boswellia papyrifera was analysed by comprehensive 2D gas chromatography hyphenated with accurate mass time-of-flight mass spectrometry (GC×GC-accTOFMS). Direct multiple injection experiments with stepwise isothermal temperature programming were then performed to construct isovolatility curves for reference alkane series in GC×GC. This provides access to calculation of second dimensional retention indices (2I). More than 500 peaks were detected and 220 compounds mainly comprising monoterpenes, sesquiterpenes, diterpenes and oxygenated forms of these compounds were identified according to their 1I, 2I and accurate mass data. The study demonstrates the capability of GC×GC-accTOFMS with retention data on two separate column phases, as an approach for improved component identification. A greater number of identified and/or tentatively identified terpenoids in this traditional Chinese medicine allow for a more comprehensive coverage of the volatile composition of frankincense.

Ionic liquid phases with comprehensive two-dimensional gas chromatography of fatty acid methyl esters.

New generation inert ionic liquid (iIL) GC columns IL60i, IL76i and IL111i, comprising phosphonium or imidazolium cationic species, were investigated for separation of fatty acid methyl esters (FAME). In general, the iIL phases provide comparable retention times to their corresponding conventional columns, with only minor selectivity differences. The average tailing factors and peak widths were noticeably improved (reduced) for IL60i and IL76i, while they were slightly improved for IL111i. Inert IL phase columns were coupled with conventional IL columns in comprehensive two-dimensional GC (GC × GC) with a solid-state modulator which offers variable modulation temperature (TM), programmable TM during analysis and trapping stationary phase material during the trap/release (modulation) process, independent of oven T and column sets. Although IL phases are classified as polar, relative polarity of the two phases comprising individual GC × GC column sets permits combination of less-polar IL/polar IL and polar IL/less-polar IL column sets; it was observed that a polar/less-polar column set provided better separation of FAME. A higher first dimension (1D) phase polarity combined with a lower 2D phase polarity, for instance 1D IL111i with 2D IL59 gave the best result; the greater difference in 1D/2D phase polarity results in increasing occupancy of peak area in the 2D space. The IL111i/IL59 column set was selected for analysis of fatty acids in fat and oil products (butter, margarine, fish oil and canola oil). Compared with the conventional IL111, IL111i showed reduced column bleed which makes this more suited to GC × GC analysis of FAME. The proposed method offers a fast profiling approach with good repeatability of analysis of FAME.

Determination of selected emerging contaminants in freshwater invertebrates using a universal extraction technique and liquid chromatography accurate mass spectrometry.

A simple sample preparation method based on a modified liquid-phase extraction approach to extract selected pharmaceuticals and personal care products from freshwater organisms is described. Extracted samples were analysed using liquid chromatography with Q-Exactive plus hybrid quadrupole Orbitrap mass spectrometry, using 2.6 µm C18 media. A 0.1% v/v acetic acid/acetonitrile mobile phase was applied over a 20 min gradient. Method detection limits in full scan mode were ca. 0.04-2.38 ng of analyte per g of sample. Linearity ranged from 0.9750 to 0.9996 over the calibration range of 0.01-100 µg/L; MS mass accuracy was <2 ppm for most analytes. This method was applied to quantify six pharmaceuticals and personal care products in seven invertebrate samples. For tandem mass spectrometry analysis, selection of precursor ions was performed for each pharmaceutical, with Mass Frontier software illustrating the fragmentation mechanism. Effects of collision energy on intensities of ions was further investigated. The tandem mass spectrometry condition resulting in the highest signal of respective selected product ion was selected to confirm each pharmaceutical, which was initially observed in the full scan mode. Results indicate that pharmaceuticals and personal care products found to be present in water-ways, may be incorporated into organisms that live in the environment of affected water streams.

Identification of Volatile Compounds and Selection of Discriminant Markers for Elephant Dung Coffee Using Static Headspace Gas Chromatography-Mass Spectrometry and Chemometrics.

Elephant dung coffee (Black Ivory Coffee) is a unique Thai coffee produced from Arabica coffee cherries consumed by Asian elephants and collected from their feces. In this work, elephant dung coffee and controls were analyzed using static headspace gas chromatography hyphenated with mass spectrometry (SHS GC-MS), and chemometric approaches were applied for multivariate analysis and the selection of marker compounds that are characteristic of the coffee. Seventy-eight volatile compounds belonging to 13 chemical classes were tentatively identified, including six alcohols, five aldehydes, one carboxylic acid, three esters, 17 furans, one furanone, 13 ketones, two oxazoles, four phenolic compounds, 14 pyrazines, one pyridine, eight pyrroles and three sulfur-containing compounds. Moreover, four potential discriminant markers of elephant dung coffee, including 3-methyl-1-butanol, 2-methyl-1-butanol, 2-furfurylfuran and 3-penten-2-one were established. The proposed method may be useful for elephant dung coffee authentication and quality control.

Incubation of Aquilaria subintegra with Microbial Culture Supernatants Enhances Production of Volatile Compounds and Improves Quality of Agarwood Oil.

Incubation with microbial culture supernatants improved essential oil yield from Aquilaria subintegra woodchips. The harvested woodchips were incubated with de man, rogosa and sharpe (MRS) agar, yeast mold (YM) agar medium and six different microbial culture supernatants obtained from Lactobacillus bulgaricus, L. acidophilus, Streptococcus thermophilus, Lactococcus lactis, Saccharomyces carlsbergensis and S. cerevisiae prior to hydrodistillation. Incubation with lactic acid bacteria supernatants provided higher yield of agarwood oil (0.45% w/w) than that obtained from yeast (0.25% w/w), agar media (0.23% w/w) and water (0.22% w/w). The composition of agarwood oil from all media and microbial supernatant incubations was investigated by using gas chromatography-mass spectrometry. Overall, three major volatile profiles were obtained, which corresponded to water soaking (control), as well as, both YM and MRS media, lactic acid bacteria, and yeast supernatant incubations. Sesquiterpenes and their oxygenated derivatives were key components of agarwood oil. Fifty-two volatile components were tentatively identified in all samples. Beta-agarofuran, α-eudesmol, karanone, α-agarofuran and agarospirol were major components present in most of the incubated samples, while S. cerevisiae-incubated A. subintegra provided higher amount of phenyl acetaldehyde. Microbial culture supernatant incubation numerically provided the highest yield of agarwood oil compared to water soaking traditional method, possibly resulting from activity of extracellular enzymes produced by the microbes. Incubation of agarwood with lactic acid bacteria supernatant significantly enhanced oil yields without changing volatile profile/composition of agarwood essential oil, thus this is a promising method for future use.

Switchable Enantioselective Three- and Four-Dimensional Dynamic Gas Chromatography-Mass Spectrometry: Example Study of On-Column Molecular Interconversion.

A novel hybrid online enantioselective four-dimensional dynamic GC (e4D-DGC) approach to study reversible molecular interconversion through specific isolation of a diastereo and enantiopure oxime, 2-phenylpropanaldehyde oxime, from prior multidimensional separation, is described. It incorporates a pre-enantioseparation step that applies comprehensive two-dimensional GC (GC × GC), prior to multiple microfluidic (Deans) switching for selection of components of a diastereomeric (E,Z) and enantiomeric (R,S) oxime into a third reactor column where isomerization occurs. This is followed by E/Z separation in a fourth analytical column. The enantioselective first dimension (1Denant) yields enantioseparation of E(R), Z(R), E(S), and Z(S) isomers, with a characteristic interconversion zone between the E and Z isomers. However, these are contaminated with underlying stereoisomers. Selected separation regions were then modulated and separated using a second dimension (2D) column via GC × GC, resolving the interfering stereoisomers. Individual pure enantiomers were then selectively heart-cut from within the 2D separation space, cryofocused, then eluted on a 3D reactor column for E ⇌ Z isomerization under controlled oven temperature and flow. Heart-cuts taken over the resulting interconversion distribution were cryotrapped at the inlet of a 4D column, on which achiral separation allows precise quantification of each E and Z isomer of the enantiomer. From peak areas and isomerization time, the forward and backward rate constants (kE→Z and kZ→E) were determined. The described methodology is suited to other configurationally labile molecules (for instance, hydrazones and imines), which exhibit isomerization, and can be used to isolate individual compounds from multicomponent samples, without requiring pure compound synthesis, or complex mathematical models or in-silico simulations.

Use of peak sharpening effects to improve the separation of chiral compounds with molecularly imprinted porous polymer layer open-tubular capillaries.

This investigation demonstrates the application of a new peak sharpening technique to improve the separation of difficult-to-resolve racemic mixtures in capillary electro-chromatography. Molecularly imprinted porous layer open tubular (MIP-PLOT) capillaries, prepared by a layer-on-layer polymerization approach with Z-l-Asp-OH as the template, were selected to validate the approach. SEM revealed that the polymer film thickness can be varied by changes in both the polymer composition and the layer-on-layer regime. Capillaries made with methacrylic acid as the functional monomer could not separate the Z-Asp-OH racemate, due to weak interactions between the MIP-PLOT material and the target analytes. In contrast, MIP-PLOT capillaries prepared with 4-vinylpyridine as the functional monomer resulted in increased ionic interactions with the target analytes. Separation of the enantiomers could be enhanced when a peak zone sharpening effect was exploited through the use of specific BGE compositions and by taking advantage of eigenpeak phenomena. In this manner, the position of a sharpening zone and the peak shape of the sample analytes could be fine-tuned, so that when the sharpening zone and the target analyte co-migrated the separation of the Z-l-Asp-OH enantiomer from its d-enantiomer in a racemic mixture could be achieved under overloading conditions.

Contribution of Eigenmobility Shifts to the Separation of Peptides in Capillary Electrophoresis with Aqueous-Acetonitrile Background Electrolytes.

In this investigation, the mobility of system eigenpeaks in capillary electrophoresis (CE) was experimentally found to decrease when the background electrolyte (BGE) contained higher percentages of acetonitrile. In order to explain this observation, the effects of changes in the pH and ionic strength of the BGE on the pKa and actual mobility of each constituent in the system were determined, and the results evaluated in terms of their theoretical basis. Utilizing the derived values of each of these parameters, the software Peakmaster was then applied to simulate the eigenpeak mobility. Although general trends for BGEs with different acetonitrile contents could be simulated, these simulations did not exactly match the experimental results. To account for this divergence between theory and experimental practice, the consequences of tube radial distribution of the organic solvent in an aqueous-organic system within the capillary and the effects of radial ion distribution leading to the electro-osmotic flow mobility (EOF) are proposed to be the cause of this deviation. Consequently, the Debye-Hückel approximation and Boltzmann distribution function were employed to calculate the amount of each constituent across the radius of the capillary. The inhomogeneous radial distributions of the constituents in the BGE and the organic solvent were simplified to a 1-dimensional problem based on a 4-constituent BGE approximation. A high level of correlation was then achieved between the experimental results and the corresponding CE separations simulated using Peakmaster. In addition, cancellation or suppression of the peak broadening was experimentally and theoretically demonstrated by taking advantage of the influence of a second independent system eigenpeak. The outcome from these studies was a new way to achieve sharpening of specific peaks in the CE separations of peptides.

In Silico Modeling of Hundred Thousand Experiments for Effective Selection of Ionic Liquid Phase Combinations in Comprehensive Two-Dimensional Gas Chromatography.

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.

Pressure Tuning of First Dimension Columns in Comprehensive Two-Dimensional Gas Chromatography.

The experimental approach and mechanism of pressure tuning (PT) are introduced for the first stage of a comprehensive two-dimensional gas chromatography (GC × GC) separation. The PT-GC × GC system incorporates a first dimension ((1)D) coupled column ensemble comprising a pair of (1)D columns ((1)D1 and (1)D2) connected via a microfluidic splitter device, allowing variable decompression of carrier gas across each (1)D column, and a conventional (2)D narrow bore column. By variation of junction pressure between the (1)D1 and (1)D2 columns, tunable total (1)D retentions of analytes are readily derived. Separations of a standard mixture comprising a number of different chemical classes (including alkanes, monoaromatics, alcohols, aldehydes, ketones, and esters) and Australian tea tree oil (TTO) were studied as practical examples of the PT-GC × GC system application. This illustrated the change of analyte retention time with experimental conditions depending on void time and retention on the different columns. In addition to void time change, variation of carrier gas relative decompression in the (1)D ensemble leads to tunable contribution of the (1)D1/(1)D2 columns that changes apparent polarity and selectivity of the ensemble. The resulting changes in (1)D elution order further altered elution temperature and thus retention of each analyte on the (2)D column in temperature-programmed GC × GC. 2D orthogonality measurements were then conducted to evaluate overall separation performance under application of different (1)D junction pressure. As a result, distribution and selectivity of particular target compounds, monoterpenes, sesquiterpenes, and oxygenated terpenes in 2D space, and thus orthogonality, could be adequately tuned. This indicates the potential of PT-GC × GC to be applicable for practical sample separation and provides a general approach to tune selectivity of target compounds.

Continuum in MDGC Technology: From Classical Multidimensional to Comprehensive Two-Dimensional Gas Chromatography.

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.