Evaluation of Cryogen-Free Thermal Modulation-Based Enantioselective Comprehensive Two-Dimensional Gas Chromatography for Stereo-Differentiation of Monoterpenes in Citrus spp. Leaf Oils.

This study evaluates the applicability of enantioselective gas chromatography (eGC) and enantioselective comprehensive two-dimensional gas chromatography (eGC×GC) coupled with flame ionization detection for the stereospecific analysis of designated chiral monoterpenes within essential oils distilled from the leaves of Citrus hystrix (CH), C. limon (CL), C. pyriformis (CP), and C. microcarpa (CM). A cryogen-free solid-state modulator with a combination of enantioselective first-dimension and polar second-dimension column arrangements was used to resolve potential interferences in Citrus spp. leaf oils that can complicate the accurate determination of enantiomeric compositions. Interestingly, considerable variations were observed for the enantiomeric fractions (EFs) of the chiral terpenes. (+)-limonene was identified as the predominant enantiomer (60.3-98.9%) in all Citrus oils, (+)-linalool was the major enantiomer in CM (95.9%), (-)-terpenin-4-ol was the major isomer in CM (66.4%) and CP (61.1%), (-)-α-pinene was the dominant antipode in CL (55.5%) and CM (92.1%). CH contained (-)-citronellal (100%) as the pure enantiomer, while CL and CP have lower proportions (9.0-34.6%), and citronellal is absent in CM. The obtained enantiomeric compositions were compared and discussed with results from eGC using the same enantioselective column. To our knowledge, this work encapsulates the first report that details the EFs of these chiral monoterpenes in Citrus spp. leaf oil.

Quasi-Stop-Flow Modulation Strategy for Comprehensive Two-Dimensional Gas Chromatography.

An easy-to-implement strategy of differential flow modulation for comprehensive two-dimensional gas chromatography was innovated. With this approach, an independent auxiliary pneumatic control device for flow modulation was not a prerequisite. The strategy involved splitting the carrier gas stream into two separate streams before reaching the inlet embodiment. One stream was employed as a mobile phase for chromatographic separation. The other stream, for flow modulation, was routed to one of the ports of a three-way solenoid valve. The modulation stream flowed onward to a fluidic path and a T-junction that joined the primary and secondary dimension columns. With this arrangement and depending on the configuration of the three-port valve, the analytical platform can be operated in three different modes: bypass stop-flow, vent stop-flow, and quasi-stop flow. Quasi-stop-flow mode was demonstrated to have a significantly better chromatographic performance, as demonstrated in various types of real-life petroleum samples such as gasoline and light cycle oil. In the light cycle oil sample, a respectable separation between compound classes was achieved with peak width at half height of 34 ms or less for alkanes on a second dimension with polyethylene glycol stationary phase. Excellent repeatability was shown with normal alkanes standards of nC8-nC25. Relative standard deviations for retention times are almost zero in 1D, less than 0.2% in 2D, and less than 3.5% for peak areas (n = 9).

Thermal Independent Modulator for Comprehensive Two-Dimensional Gas Chromatography.

We introduce a modulation strategy for comprehensive two-dimensional gas chromatography (GC×GC) with complete thermal independence between the cooling and heating stages and without the need for GC oven heat for remobilization. Based on this approach, a compact thermal independent modulator (TiM) with thermoelectric cooling and micathermic heating has been successfully innovated for use in GC×GC. The device operates externally to a gas chromatograph, does not require liquid cryogen, and has minimal consumables requirements. The augmentation of an additional gas flow stream results in a number of critical chromatographic parameter improvements such as the decoupling of flows of first- and second-dimension columns to attain both efficiency and speed optimized flow in each dimension, the potential for independent retention time locking or scaling in either dimension, the improvement of modulator reinjection efficiency, as well as facilitating back-flushing for the first dimension to enhance system cleanliness and throughput. TiM was found to be useful for chromatographic applications over a volatility range equivalent to nC6 to nC24 under conditions used. Repeatability of retention time for model compounds such as benzene, toluene, ethyl benzene, and xylenes were found to be quite satisfactory with relative standard deviations of less than 0.009% in (1)D and less than 0.008% in (2)D (n = 10). Typical peak widths of 120 ms or less with a relative standard deviation of less than 4.7% were achieved for the aromatic model compounds. In this article, the performance of the modulator is demonstrated and a series of challenging chromatographic applications are presented to illustrate usefulness of the apparatus.

Characterization and Benzo[a]pyrene Content Analysis of Camellia Seed Oil Extracted by a Novel Subcritical Fluid Extraction.

A novel continuous subcritical n-butane extraction technique for Camellia seed oil was explored. The fatty acid composition, physicochemical properties, and benzo[a]pyrene content of Camellia seed oil extracted using this subcritical technique were analyzed. Orthogonal experiment design (L9(34)) was adopted to optimize extraction conditions. At a temperature of 45 °C, a pressure of 0.5 MPa, a time of 50 min and a bulk density of 0.7 kg/L, an extraction yield of 99.12 ± 0.20 % was obtained. The major components of Camellia seed oil are oleic acid (73.12 ± 0.40 %), palmitic acid (10.38 ± 0.05 %), and linoleic acid (9.15 ± 0.03 %). Unsaturated fatty acids represent 83.78 ± 0.03 % of the total fatty acids present. Eight physicochemical indexes were assayed, namely, iodine value (83.00 ± 0.21 g I/100 g), saponification value (154.81 ± 2.00 mg KOH/g), freezing-point (-8.00 ± 0.10 °C), unsaponifiable matter (5.00 ± 0.40 g/kg), smoke point (215.00 ± 1.00 °C), acid value (1.24 ± 0.03 mg KOH/g), refrigeration test (transparent, at 0 °C for 5.5 h), and refractive index (1.46 ± 0.06, at 25 °C). Benzo[a]pyrene was not detected in Camellia seed oil extracted by continuous subcritical n-butane extraction. In comparison, the benzo[a]pyrene levels of crude Camellia seed oil extracted by hot press extraction and refined Camellia seed oil were measured at 26.55 ± 0.70 and 5.69 ± 0.04 µg/kg respectively.

Characterization of key odor-active compounds in commercial high-salt liquid-state soy sauce by switchable GC/GC × GC-olfactometry-MS and sensory evaluation.

Activity of odor compounds of soy sauces has not been fully determined so far. Herein, a new switchable GC/GC × GC-olfactometry-mass spectrometry system for simultaneous GC × GC-MS analysis and sniffing of each odor-active substance through a single injection was used for the aroma extract dilution analysis of five regular high-salt liquid-state soy sauces (HLS). Methional, maltol, guaiacol, 4-ethylguaiacol, 2-acetylpyrrole, 2-acetylfuran, 2-phenylethanol, and 4-hydroxy-2,5-dimethyl-3(2H)-furanone showed high flavor dilution (FD) factors. The FD factors of all odor-active compounds in different odor attributes were summed up (score) to evaluate the odor characteristics of the samples. Cooked potato-like odor was the most important characteristic. The difference in the odor characteristics were mainly reflected in the balance of caramel-like/sweet, roasted/roasted nut-like, spicy/burnt, and unpleasant odor intensity; the fruity odor intensity was the weakest. This study will provide a better understanding of the odor characteristics and key odor-active compounds in Chinese regular commercial HLS.

Comprehensive two-dimensional gas chromatography mass spectrometry with a solid-state thermal modulator for in-situ speciated measurement of organic aerosols.

Thermal desorption aerosol gas chromatography mass spectrometry is capable of online measuring speciated organics in atmospheric aerosols. Compared to the one-dimensional gas chromatography, comprehensive two-dimensional gas chromatography increases the resolution and the sensitivity, mitigates the unresolved complex mixture and co-elution occurred in one-dimensional gas chromatography. In this study, we report a quartz filter-based thermal desorption aerosol comprehensive two-dimensional gas chromatography mass spectrometry (2D-Q-TAG). It combines a solid-state thermal modulator with a quartz filter-based thermal desorption aerosol gas chromatography mass spectrometry. The solid-state thermal modulator conducts modulation independently from the chromatographic oven without using cryogens or compressed air, which makes the system readily adaptive for field measurement. The 2D-Q-TAG was evaluated using C7-C40 n-alkanes and 16 polycyclic aromatic hydrocarbons (PAHs). It has low limits of detection from 0.001 to 0.104 ng. The instrument was then deployed to measure atmospheric PM2.5 (particulate matter with an equivalent aerodynamic diameter  ≤  2.5 µm) in urban Beijing. It allows in-situ detection of speciated organics in atmospheric aerosols with hourly time resolution. Organic classes including alkanes, furanones, alcohols, aldehydes, ketones, acids, PAHs, oxy-PAHs, and alkyl-naphthalenes were well separated and detected. The total mass concentration of n-alkanes ranged from 122.1 to 629.9 ng/m3. Diurnal variation of n-alkanes was captured due to the high time resolution of the instrument.

Analysis of volatile organic compounds using cryogen-free thermal modulation based comprehensive two-dimensional gas chromatography coupled with quadrupole mass spectrometry.

A single-channel comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry (GCxGC-qMS) system was developed using a recently introduced solid-state thermal modulator. By modulation on a special column, extremely light hydrocarbons down to C2 can be successfully modulated without use of any cryogens. Paired with a polar secondary dimension column, a hybrid primary dimension column was developed to provide complete two-dimensional separation of all target volatile organic compounds (VOCs) from C2 to C12. This single-channel GCxGC-qMS system is used to analyze VOC standards containing 57 PAMS and 64 TO-15 gas mixtures, as well as real-world samples. This study demonstrates that a low resource GCxGC-qMS system may serve as a feasible tool for routine VOCs monitoring.

A simple and efficient approach for calculating permeability coefficients and HETP for rectangular columns.

There had been little progress in development of the theoretical basis of rectangular chromatography columns until Spangler made great progress by using a more exact model than Golay's. Unfortunately, there was a deficiency in his calculations, which led to a conclusion inconsistent with the previous theories. In this paper, a simpler formula with defined variables was first established to calculate the mean permeability coefficient for a rectangular GC column. A formula was also established to calculate the height equivalent to a theoretical plate (HETP) for a rectangular column based on this work and the correction of Spangler's theory. By comparing both our predictions and Spangler's predictions with Golay's, respectively, we could demonstrate that our theory is more exact. Further, one parameter (A) was found to be not monotonous. This finding leads to the conclusion that the square column has the highest performance among all the rectangular-shaped columns used for chromatography, and that a width/depth ratio of around three is desirable if the column is used for mixing reactants in lab-on-a-chip systems, instead of for chromatography. The conclusions are applicable not only for gas but also for liquid chromatography columns.