Gas Chromatographic Separation Research Articles

Preparation of alkyl microporous organic network-based capillary column for an efficient gas chromatographic separation of position isomers.

The large surface area, excellent thermal stability and easy modification make microporous organic networks (MONs) good candidates in the field of gas chromatography (GC). Due to the limited species and highly conjugated networks of MONs, their applications are still in infancy and restricted. To accelerate their developments and to enrich their types in GC, here we report the first example of synthesizing alkyl MON and its capillary column for GC separation of position isomers. Linear 1,8-dibromooctane is used as the alkyl monomer instead of traditional aromatic ones to construct novel alkyl MON to decrease the inherent conjugated characteristic of MONs. The alkyl MON exhibits good thermal stability (up to 350°C), large surface area (1173m2g-1), and non-polar character, allowing good resolution for alkanes, alkyl benzenes, alcohols, ketones, and diverse position isomers, including dichlorobenzene, trichlorobenzene, bromotoluene, nitrotoluene, methylbenzaldehyde, and ionone with the limits of detection (0.003mgmL-1) and limits of quantitation of (0.10mgmL-1). The in situ growth-prepared alkyl MON column demonstrates remarkable duration time and precisions for the retention relative standard deviations, (RSDs%, intra-day, n=7), 0.06%-0.53% (intra-day, n=7), and 2.87%-10.59% (column-to-column, n=3). In addition, the fabricated alkyl MON-coated capillary column offers better resolution than three commercial GC columns for the resolution of methylbenzaldehyde, bromotoluene, and chlorotoluene isomers. This work reveals the practicability for synthesizing alkyl MONs and demonstrates their prospects for position isomers separation.

Chiral porous organic cage used as stationary phase for gas chromatographic separation of chiral and achiral compounds

Porous organic cages (POCs) are a new type of molecular material. The well-defined cavities, abundant host-guest recognition ability, and good solubility of POCs render them attractive for use in various fields such as molecular recognition, gas adsorption, molecular containers, sensing, catalysis, chromatographic separation. In this study, a chiral POC (CPOC) was synthesized via the Schiff base condensation of 4,4',4″,4″'-(ethene-1,1,2,2-tetrayl)tetrabenzaldehyde with (R,R)-1,2-cyclohexanediamine. CPOC was characterized using nuclear magnetic resonance (NMR) spectroscopy, Fourier transform-infrared (FT-IR) spectroscopy, mass spectroscopy (MS), and thermogravimetric analysis (TGA). The FT-IR spectrum of CPOC showed a strong peak at 1638 cm-1, which was attributed to imine (-C=N-) absorption, as well as absorption peaks at 2928 and 2856 cm-1, which were attributed to the stretching vibrations of -CH2- and -CH-, respectively. MS analysis of CPOC revealed peaks at m/z=1801.9797, m/z=901.9914, and m/z=601.6631, corresponding to [M+H]+, [M+2H]2+, and [M+3H]3+, respectively, and indicating a molecular formula of CPOC (C126H120N12). The TGA curve of CPOC indicated high thermal stability up to 360 ℃; thus, the material is suitable for use as a stationary phase for gas chromatography (GC). CPOC was coated on the inner wall of a capillary column using the static coating method to prepare a GC column. Scanning electron microscopy (SEM) was used to characterize the coating condition of the fabricated column. The SEM images showed that the column had a uniform coating with a thickness of approximately 200 nm. Column efficiency was determined to be 3500 plates/m using n-dodecane as a target at 120 ℃. The polarity of the CPOC stationary phase was evaluated using McReynolds constants, which were measured using benzene, 1-nitropropane, 2-pentanone, pyridine, and 1-butanol as probe molecules at 120 ℃. The average McReynolds constant was 152, indicating that CPOC is a moderately polar stationary phase. The ability of the column to separate organic mixtures, isomers, and chiral compounds was subsequently investigated. All components of the four organic mixtures (n-alkanes, aromatics, n-alcohols, and Grob mixtures) tested achieved baseline separation on the column. In addition, nine positional isomers of disubstituted benzenes were well separated, and seven (o,m,p-nitrotoluene, o,m,p-nitrochlorobenzene, o,m,p-nitrobromobenzene, o,m,p-bromotoluene, o,m,p-dichlorobenzene, o,m,p-chloroaniline, and o,m,p-bromoaniline) achieved baseline separation. Some polar and apolar structural isomers, such as pentanol, dimethylphenol, dimethylaniline, butanol, and C9 aromatic hydrocarbon isomers, were also well separated on the column. Five cis/trans-isomers (nerol/geraniol, cis/trans-1,3-dichloropropene, cis/trans-1,2,3-trichloropropene, cis/trans-citral, and cis/trans-decahydronaphthalene) were baseline-separated on the column. More importantly, the column successfully separated 12 chiral compounds, indicating good chiral separation ability. Among these chiral compounds, five (ethyl 3-hydroxybutyrate, a valine derivative, a glutamic acid derivative, 1,2-butanediol diacetate, and 1,2-epoxybutane) achieved baseline separation. Six of these chiral compounds (ethyl 3-hydroxybutyrate, the valine derivative, the glutamic acid derivative, 1,2-epoxybutane, epichlorohydrin, and epibromohydrin) could not be separated on a β-DEX 120 column but were well separated on the developed column. Moreover, the separation efficiency of 1,2-butanediol diacetate and the isoleucine derivative on this column was better than that on the β-DEX 120 column. Separation of the glutamic acid derivative and o,m,p-nitrotoluene was performed before and after the column was used for repeated injections to explore its repeatability. The retention times and selectivity observed after 80, 160, and 500 injections were nearly unchanged compared with those obtained following the first use of the column, indicating that the column has good repeatability. The column was conditioned at 280 ℃ for a certain period to examine its thermal stability. Separation of 3-hydroxybutyrate and o,m,p-nitrochlorobenzene after the column was conditioned at 280 ℃ for 2, 4, or 8 h revealed no obvious changes compared with the first use of the column, indicating that the column had good thermal stability. Thus, CPOC is a stationary phase with good application potential for GC.

High-Resolution Drift Tube Ion Mobility Spectrometer with Ultra-Fast Polarity Switching.

Besides safety and security applications, ion mobility spectrometry (IMS) is increasingly used in other fields such as medicine, environmental monitoring and food quality analysis. However, some applications require gas chromatographic separation before analysis by IMS. Furthermore, different compounds in the sample may form positive or negative ions during ionization and therefore simultaneous detection of both ion polarities is highly beneficial to avoid two chromatographic runs of the same sample. This can be achieved by ultra-fast polarity switching of a single drift tube IMS, allowing for quasi-simultaneous detection of both ion polarities. By using a ramped aperture voltage during the switching process, we overcome the issue of excessive displacement currents at the detector during polarity switching, which usually lead to overdriving the output signal of the high-gain transimpedance amplifier. Furthermore, mechanical aperture grid oscillations caused by polarity switching were also reduced through the ramped aperture voltage. This enables a polarity switching time of only 7 ms at a drift voltage of 8 kV and a drift length of 103 mm, leading to a high resolving power of RP = 117. Requiring 50 ms to acquire a pair of positive and negative spectrum, the IMS achieves an acquisition rate of 20 Hz. It reaches limits of detection of 20 pptv for dimethyl methylphosphonate and 40 pptv for methyl salicylate. For demonstration, different hop varieties were investigated and could be clearly differentiated by considering both, the positive and negative spectra.

Parallel coupling of gas chromatography to mass spectrometry and solid deposition Fourier transform infrared spectroscopy: an innovative approach to address challenging identifications.

The request for novel hyphenated instruments and techniques, capable of affording exhaustive information and results, is a focus continuously watched out. In this context, the present work aimed at the development of an integrated system combining gas chromatographic (GC) separation with mass spectrometry (MS) and (solid deposition) Fourier transform infrared spectroscopy (FTIR) detection. An external transfer line was designed inthelab for the parallel coupling of the two detectors, in such a way toobtain complementary analytical information consisting of anMS spectrum, anIR spectrum and linear retention indices (LRI), within a single analysis. The instrument performance was demonstrated for the analysis of a commercial mixture consisting of 139 hydrocarbons, comprising linear, branched, unsaturated and aromatic compounds. A 100-m poly(dimethylsiloxane) column was employed for the separation, and the outlet flow was split 95:5 between the IR and MS detectors using two uncoated capillaries. The IR spectra were acquired from solid deposits on a zinc selenide disc (-90 °C), over a spot (detector area) of about 0.1 mm2, in the range of 4000-700 cm-1 and at a resolution of 4 cm-1. Final identification of the separated compounds by alibrary search was achieved by excluding incorrect results, sequentially using a three-filter approach (85% similarity against reference MS and IR library spectra and ±10 LRI unit tolerance). Based on these preliminary results, the GC-MS/sd-FTIR system is a promising tool for the characterization of complex matrix constituents, for which identification is cumbersome, by using only one detection technique.

Comprehensive analysis of chemical and enantiomeric stability of terpenes in Cannabis sativa L. flowers.

Cannabis sativa L. is renowned for its medicinal and recreational uses. With the increasing global legalization of C.sativa L.-based products for medicinal purposes, there is a growing need for well-characterized products. While the stability of cannabinoids such as tetrahydrocannabinol and cannabidiol is well understood, information on the chemical and enantiomeric stability of terpenes remains scarce. This is despite the fact that terpenes are also thought to have pharmacological activity and may contribute to the overall effect of C.sativa L. To address these challenges, four analytical methods based on chiral, polar, and apolar gas chromatographic separation combined with either MS or FID detection were developed and validated. These methods successfully separated and quantified a total of 29 terpenes, including 13 enantiomers and 5 diastereomers specific to C.sativa L. Furthermore, terpenes and authentic C.sativa L. flowers and extracts were subjected to UV and heat treatments to observe potential degradation reactions over time. Each terpene generates a unique pattern of degradation products resulting in a diverse array of oxidation and cyclization products. P-cymene was identified as a major product of terpene aging. Notably, no enantiomeric conversion was detected, suggesting that the formation of (-)-α-pinene in cannabis extracts, for example, originates from other terpenes. Terpenes have different degradation rates, even though they are structurally similar. In addition, cultivar- and growth-condition-specific enantiomeric ratios were observed in C.sativa L., confirming that enantiomer production is species-specific and has to be considered for therapeutical applications.

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.

Recent progress for chiral stationary phases based on chiral porous materials in high-performance liquid chromatography and gas chromatography separation.

Chirality is a fundamental property of nature. Separation and analysis of racemates are of great importance in the fields of medicine and the production of chiral biopharmaceutical intermediates. Chiral chromatography has the characteristics of a wide separation range, fast separation speed, and high efficiency. The development and preparation of novel chiral stationary phases with good chiral recognition and separation capacity is the core and key of chiral chromatographic separation and analysis. In this work, the representative research progress of novel chiral porous crystal materials including chiral covalent organic frameworks, chiral porous organic cages, chiral metal-organic frameworks, and chiral metal-organic cages used as chiral stationary phases of capillary gas chromatography and high-performance liquid chromatography over the last 4 years is reviewed in detail. The chiral recognition and separation properties of the representative studies in this review are also introduced and discussed.

Dielectric barrier discharge ionization procures characteristic adducts of polyfluoroalkyl substances (PFAS) amenable by gas chromatography-mass spectrometry

Fluorotelomer alcohols (FTOHs) and acrylates (FTACs) have been reported as precursors of perfluoroalkyl acids and are known to contaminate biotic and abiotic compartments. Here, a detailed study was carried out for assessing the capability of dielectric barrier discharge ionization (DBDI) to be used as soft ionization technique, as alternative to the more energetic electron ionization (EI), for the quantitative determination of four FTOHs and two FTACs in environmental, biological or food samples by gas chromatography-mass spectrometry. While gas chromatography-EI-mass spectrometry (GC-EI-MS) shows significant fragmentation of the compounds, the ionization obtained by gas chromatography-DBDI-high resolution mass spectrometry (GC-DBDI-HRMS) affords dominant molecular adducts on the spectra. In the positive ion mode, the ion [M + H3O]+ and, of lower intensity, [M + H]+ are observed in the spectra of FTOHs, while the ion [M + H]+ is the most abundant in the spectra of FTACs and accompanied by a lower signal attributed to the ion [M + NO]+. In the negative ion mode, the FTOHs give rise to carbon dioxide and oxygen adducts observed with ions [M − H + CO2]- and [M + O2]-. Structure assignments were confirmed with stable isotope-labelled FTOH analogs and 13CO2. Gas chromatographic separation of the six compounds reveals room for development of methods applicable to soils, plants, water, food and biological materials.

Geochemical Characteristics of Mature to High-Maturity Shale Resources, Occurrence State of Shale Oil, and Sweet Spot Evaluation in the Qingshankou Formation, Gulong Sag, Songliao Basin

The exploration of continental shale oil in China has made a breakthrough in many basins, but the pure shale type has only been found in the Qingshankou Formation, Gulong Sag, Songliao Basin, and the evaluation of shale oil occurrence and sweet spot faces great challenges. Using information about the total organic carbon (TOC), Rock-Eval pyrolysis, vitrinite reflectance (Ro), kerogen elemental composition, carbon isotopes, gas chromatography (GC), bitumen extraction, and component separation, this paper systematically studies the organic geochemical characteristics and shale oil occurrence at the Qingshankou Formation. The G1 well, which was cored through the entire section of the Qingshankou Formation in the Gulong Sag, was the object of this study. On this basis, the favorable sweet spots for shale oil exploration are predicted. It is concluded that the shale of the Qingshankou Formation has high organic heterogeneity in terms of organic matter features. The TOC content of the source rocks in the Qingshankou Formation is enhanced with the increase in the burial depth, and the corresponding organic matter types gradually changed from Ⅱ2 and Ⅱ1 types to the Ⅰ type. The distribution of Ro ranges from 1.09% to 1.67%, and it is the mature to high-mature evolution stage that generates a large amount of normal crude oil and gas condensate. The high-quality source rocks of good to excellent grade are mainly distributed in the Qing 1 member and the lower part of the Qing 2 member. After the recovery of light hydrocarbons and the correction of pyrolytic heavy soluble hydrocarbons, it is concluded that the occurrence state of shale oil in the Qingshankou Formation is mainly the free-state form, with an average value of 6.9 mg/g, and there is four times as much free oil as adsorbed oil. The oil saturation index (OSI), mobile hydrocarbon content, Ro, and TOC were selected to establish the geochemical evaluation criteria for shale oil sweet spots in the Qingshankou Formation. The evaluation results show that interval 3 and interval 5 of the Qingshankou Formation in the G1 well are the most favorable sections for shale oil exploration.

Subcomponent self-assembly construction of tetrahedral cage FeII4L4 for high-resolution gas chromatographic separation

Metal organic cages (MOCs), as an emerging discrete supramolecular compounds, have received widespread attention in separation, biomedicine, gas capture, catalysis, and molecular recognition due to their porosity, adjustability and stability. Herein, we present a new chiral MOC FeII4L4 coated capillary column prepared for gas chromatographic (GC) separation of different types of organic compounds, including n-alkanes, n-alcohols, alkylbenzenes, isomers, especially for racemic compounds. There are 20 different kinds of racemates (e.g., alcohols, ethers, epoxides, esters, alkenes, and aldehydes) were well resolved on the FeII4L4 chiral column and a maximum resolution value for 1-phenyl-1-propanol reaches 6.17. The FeII4L4 coated column exhibited high column efficiency (3100 plates m−1 for n-dodecane) and good enantiomeric resolution complementary to that of a commercial β-DEX 120 column and the previously reported chiral MOC [Fe4L6] (ClO4)8 coated column. The relative standard deviation (RSDs) of the peak area and retention time of glycidol and nitrotoluene were below 1.2 %. This study reveals that chiral MOCs have good application prospects in chromatographic separation.

Optimizing COF crystallinity for high-resolution GC separation

This research explores the influence of crystallinity on gas chromatographic (GC) separation using covalent organic frameworks (COFs) as stationary phases. Three COF materials (CTF-DCBs) with varying crystallinity were synthesized and characterized. CTF-DCB-1, with superior crystallinity, demonstrated high-selectivity GC separation of benzene isomers as well as styrene/phenylacetylene mixtures, while CTF-DCB-2 and CTF-DCB-3 exhibited lower crystallinity and worse separation performance. Thermodynamic and kinetic tests showed that CTF-DCB-1 had the worst thermodynamic adsorption but low diffusion mass transfer resistance, which resulted in the best separation. Therefore, optimizing the crystallinity of COFs is necessary for balancing the kinetic diffusion and thermodynamic interactions towards the analytes, achieving high-performance GC stationary phases.

Theoretical calculation of the parameters of the three-parameter chromatographic phase characterization method I. Dispersion forces parameter – generalized charge

In this work we studied the flavonoid composition of tangerine skins using 10 kinds of tangerines from the selectivity of separation in gas chromatography is determined by the nature of the stationary phase. The authors previously proposed a model of intermolecular interactions and a theoretical method of three-parameter characterisation of stationary phases in liquid chromatography based on it. They were applied to quantify the ability of molecules to participate in dispersion and dipole-dipole interactions and hydrogen bonds. The method proved to be efficient to describe the properties of stationary phases based on hydrocarbons, polyethylene glycol, polysiloxanes, and ionic liquids. The properties of stationary phases and analyte molecules are described by two selectivity characteristics: polarity and hydrophilicity, which can be calculated as a direct problem using the structural formula of the substance, or as an inverse problem using experimental data in the form of the Kovacs retention indices or Rohrschneider and McReynolds constants. No contradictions have been found between the characteristics calculated by the two methods. Using the proposed method, the relationship between the molecular weight of the polymer molecule and the values of selectivity characteristics was revealed. We proposed a selectivity map as a convenient and illustrative way to classify the stationary phases. Backed by the principle of similarity of properties, it can be used to determine the most selective stationary phase for a given analyte, without any experiments. The aim of this work was to determine the generalised charge as the first and key parameter of the three-parameter characterisation method. The main tool was the theory of generalised charges developed earlier in the laboratory of sorption methods of GEOKHI RAS. This theory, derived from fundamental principles, describes van der Waals interactions in the form of a Lennard-Jones potential, using the characteristics of molecules determined from their molecular structure. Previously, it successfully described nonpolar chromatographic systems. In the present study, we defined generalised charges, showed their relation to physical and experimental values, and provided calculation formulas for isolated molecules and for liquid phases. We presented the results of a detailed calculation of the generalised charges of substances of different classes, including gas chromatographic stationary phases.

Ionic liquid-functionalized pillar[6]arene: A novel stationary phase of high selectivity towards a wide range of isomers

In this work, a novel pillar[6]arene bonded with octyl-imidazolium ionic liquids (IMP6A-C4) as a stationary phase for gas chromatographic (GC) separations was designed, synthesized, and characterized. The IMP6A-C4 capillary column, prepared by the static coating method, had medium polarity (133) and relatively high column efficiency of 4982 plates/m determined by n-dodecane at 120 ℃. As demonstrated, through the separation of the mixture of 17 aliphatic analytes and the mixture of 20 analytes with different polarities, the IMP6A-C4 column exhibited privileged retention and high resolving capacity for H-bonded and aromatic analytes, suggesting advantages over the P6A-C4 column and common polysiloxane HP-5 and HP-35 columns. Strikingly, it implemented high resolutions with good peak shapes for isomer mixtures of phenols, anilines, and benzaldehydes. These findings demonstrated that the excellent resolving performance of the IMP6A-C4 column can be attributed to the comprehensive interactions of its rigid 3D aromatic cavities and polar imidazolium ionic liquids, including π-π, ion-π, H-bonding, dipole–dipole interactions. On the other hand, the IMP6A-C4 capillary column exhibited good repeatability and reproducibility with the RSD% values in the range of 0.01–0.03% for run-to-run, 0.09–0.32% for day-to-day, and 2.72–5.23% for column-to-column. The satisfactory separation performance reveals the promising prospects of the IMP6A-C4 stationary phase in separation science.

A chiral metal–organic polyhedron used as stationary phase for gas chromatographic separations

Metal-organic polyhedra (MOPs), as a novel class of porous materials, exhibit distinctive application potential in molecular recognition, separation, catalysis, luminescent materials, drug delivery, and biomedicine owing to their tunable geometric shape and size, well-defined cavities, and discrete characteristics. In this study, we report that a chiral MOP [Cu12(LV)12(H2O)12] (V = L-valine) coated capillary column was used for gas chromatographic separations. The MOP coated capillary column offered the efficient separation of n-alkanes, alkylbenzenes, n-alcohols, multiple types of isomers, and enantiomers with high selectivity. Various enantiomers including esters, halogenated hydrocarbons, alcohols, ethers, aldehydes, and amino acid derivatives were well resolved on this chiral column, especially for some amino acid derivatives (e.g., Rs = 5.24 for tyrosine derivative). Compared with the commercial β-DEX 120 column for separation of the tested racemates, the chiral resolution performance of the MOP coated column can be complementary to that of β-DEX 120 column. Using 1,2-dichloropropane and o, m, p-dichlorobenzene as analytes, the MOP coated column exhibited good stability and reproducibility for gas chromatographic separations. The relative standard deviations (RSDs) of the retention time and peak area for repeated separation of 1, 2-dichloropropane and o, m, p-dichlorobenzene were less than 1.15 and 0.79 %, respectively. The results show that the chiral MOP holds great potential as a novel type of CSP for application in gas chromatography.

In silico Toxicity Assessment and Quantification of Potential Genotoxic Impurity in Olmesartan Medoxomil Drug Substance using GC-MS/MS

This study was designed to assess the in silico toxicity of 4-chloromethyl-5-methyl-1,3-dioxol-2-one (4-CMMD) in olmesartan medoxomil (OLM) using sophisticated advanced analytical GC-MS/MS method. The developed GC-MS/MS method is more sensitive as well as selective, for trace level analysis of genotoxic impurity 4-chloromethyl-5-methyl-1,3-dioxol-2-one (4-CMMD) in olmesartan medoxomil (OLM). In silico genotoxicity of 4-CMMD have been confimed by ICH M7 guidelines and tested to be “POSITIVE” in both knowledge and statistical based approaches. The conditions of gas chromatographic separation and mass spectrometry were optimized on stationary phase DB-35MS, helium carrier gas as at a flow rate of 1.5 mL/min. Quantification was performed in multiple reaction monitoring (MRM) mode. The absence of interference at the retention time of 4-CMMD indicates that the newly developed approach is very specific and selective for accurately measuring trace levels of impurities. Additionally, this method provided linear results which were validated by linearity solutions, with concentrations ranging from 3.74 to 45.12 ppm and an observed coefficient of regression of 0.9981. Sensitivity results shows this method is more sensitive detection limit (DL) achieved at 1.23 ppm and quantification limit (QL) achieved at 3.74 ppm. The developed method is precise and accurate according to the precision results, which show RSD values < 10% and recovery > 90%, both of which are within acceptable standards. The solution stability of the samples was assessed at both room temperature and refrigerated settings, and it was found to be stable for a period of 48 h. As a result, this method has been employed for the intented purpose of quantifying 4-CMMD at the trace levels in testing laboratories, pharmaceutical analytical laboratories, and quality control laboratories.

Catalytic flash pyrolysis of Scenedesmus sp. post-extraction residue using low-cost HZSM-5 catalyst with the perspective to produce renewable aromatic hydrocarbons.

Recovering renewable chemicals from de-fatted microalgal residue derived from lipid extraction within the algal-derived biofuel sector is crucial, given the rising significance of microalgal-derived biodiesel as a potential substitute for petroleum-based liquid fuels. As a circular economy strategy, effective valorization of de-fatted biomass significantly improves the energetic and economic facets of establishing a sustainable algal-derived biofuel industry. In this scenario, this study investigates flash catalytic pyrolysis as a sustainable pathway for valorizing Scenedesmus sp. post-extraction residue (SPR), potentially yielding a bio-oil enriched with upgraded characteristics, especially renewable aromatic hydrocarbons. In the scope of this study, volatile products from catalytic and non-catalytic flash pyrolysis were characterized using a micro-furnace type temperature programmable pyrolyzer coupled with gas chromatographic separation and mass spectrometry detection (Py-GC/MS). Flash pyrolysis of SPR resulted in volatile products with elevated oxygen and nitrogen compounds with concentrations of 46.4% and 26.4%, respectively. In contrast, flash pyrolysis of lyophilized microalgal biomass resulted in lower concentrations of these compounds, with 40.9% oxygen and 17.3% nitrogen. Upgrading volatile pyrolysis products from SPR led to volatile products comprised of only hydrocarbons, while completely removing oxygen and nitrogen-containing compounds. This was achieved by utilizing a low-cost HZSM-5 catalyst within a catalytic bed at 500°C. Catalytic experiments also indicate the potential conversion of SPR into a bio-oil rich in monocyclic aromatic hydrocarbons, primarily BETX, with toluene comprising over one-third of its composition, thus presenting a sustainable pathway for producing an aromatic hydrocarbon-rich bio-oil derived from SPR. Another significant finding was that 97.8% of the hydrocarbon fraction fell within the gasoline range (C5-C12), and 35.5% fell within the jet fuel range (C8-C16). Thus, flash catalytic pyrolysis of SPR exhibits significant promise for application in drop-in biofuel production, including green gasoline and bio-jet fuel, aligning with the principles of the circular economy, green chemistry, and bio-refinery.

High Selectivity of A Novel Pillar[5]arene with Ester Units as a Gas Chromatographic Stationary Phase toward Aromatic Isomers.

This work reports the first example of employing ester-functionalized pillar[5]arene (P5A-C10-OAc) stationary phase for gas chromatography (GC) separations. The as-fabricated P5A-C10-OAc column achieved improved column efficiency of 4270 plates/m and separation performance in contrast to the P5-C10-Br column. The P5A-C10-OAc column showed good separation performance for a wide range of analytes such as alkanes, bromoalkanes, ketones, fatty acid methyl esters, aldehydes, alcohols, halobenzenes, anilines, phenols, naphthalenes, and showed sharp and symmetrical peak shapes for analytes that are liable to peak-tailing in GC analysis. As testified by the challenging isomer mixtures (bromonitrobenzene, chloronitrobenzene, bromobenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde), the P5A-C10-OAc column exhibited comprehensively higher separation capability than the P5A-C10-Br, P5A-C10 and commercial HP-35 columns. This work demonstrates the great potential of pillararene-based stationary phases as a new type of stationary phases for GC separations.

Gas Chromatographic Determination of Residual Concentrations of a Mixture of Organochlorine Pesticides in Food Products

Purpose of research. The aim of the work is to optimize the conditions for gas chromatographic determination of a mixture of eight organochlorine pesticides: aldrin, hexachlorobenzene, heptachlor, α-hexachlorocyclohexane, γ-hexachlorocyclohexane, dichlorodiphenyltrichloromethylmethane, dichlorodiphenyldichloroethane and dichlorodiphenyldichloroethylene.Methods. For chromatographic studies of organochlorine pesticides we used a Shimadzu GC-2010Plus gas chromatograph (Shimadzu, Japan) equipped with an automatic equilibrium vapor sample dispenser NT200N, electron-capture detector based on 63Ni and quartz capillary nonpolar column "Chromatek" SPB-5 (30 m, 0.32 mm, film thickness on the basis of phenyl(5%) and dimethyl(95%) polysiloxanes 0.5 μm) with an operating temperature range of 60°C 320/340°C. The chromatograms were processed in the application LabSolutions GPC.Results. On the basis of experimentally obtained data the optimal conditions for gas chromatographic determination and separation of eight-component mixture of organochlorine pesticides were selected, namely: the value of mobile phase flow division 1:10, carrier gas flow rate – 1.0 ml/min, two-stage temperature programmable column mode from 160 to 240°C with the rate of increase of 5°C/min. The metrological characteristics of the analysis and validation of the results of the proposed technique with the method of high-performance liquid chromatography were evaluated. Good reproducibility of chromatography results with the possibility of detection of organochlorine pesticides at the level of 10-6 – 10-5 μg/cm3 was proved. Application of Fisher's test has shown absence of significant differences in reproducibility of sampled populations the investigated methods of chromatographic analysis of COPCs are equally accurate. Extraction sample preparation of samples of real objects was proposed, the calculated extraction degrees >84% allow to recommend the technique for quantitative determination of analytes.Conclusion. The method of gas chromatographic analysis was tested for determination of organochlorine pesticides in samples of drinking water and baby puree (Russia) by additive method. Exceeding the norms of residual contents of organochlorine pesticides in the samples of the food products under study was not detected.

Ester-functionalized pillar[6]arene as the gas chromatographic stationary phase with high-resolution performance towards the challenging isomers of xylenes, diethylbenzenes, and ethyltoluenes.

This work presents the first example of theutilization of polar ester group functionalized pillar[6]arene (P6A-C10-OAc) as a stationary phase for capillary gas chromatographic (GC) separations. The statically coated P6A-C10-OAc column showed a high column efficiency of 5393 plates/m and moderate polar nature. Its resolving capability and retention behaviors were investigated for a mixture of 20 analytes and more than a dozen isomers from apolar to polar innature. As evidenced, the P6A-C10-OAc column achieved high-resolution separations of all the analytes and good inertness. Importantly, it exhibited distinctly advantageous performance for high resolution of thechallenging isomers of xylenes, diethylbenzenes, ethyltoluenes, and halobenzenes over the commercial HP-5 (5% phenyl dimethyl polysiloxane), HP-35 (25% phenyl dimethyl polysiloxane), and PEG-20M (polyethylene glycol) columns.

Sample Preparation from Plant Tissue for Gas Chromatography-Mass Spectrometry (GC-MS)we.

Metabolites are intermediate products formed during metabolism. Metabolites play different roles, including providing energy, supporting structure, transmitting signals, catalyzing reactions, enhancing defense, and interacting with other species. Plant metabolomics research aims to detect precisely all metabolites found within tissues of plants through GC-MS. This chapter primarily focuses on extracting metabolites using chemicals such as methanol, chloroform, ribitol, MSTFA, and TMCS. The metabolic analysis method is frequently used according to the specific kind of sample or matrix being investigated and the analysis objective. Chromatography (LC, GC, and CE) with mass spectrometry and NMR spectroscopy is used in modern metabolomics to analyze metabolites from plant samples. The most frequently used method for metabolites analysis is the GC-MS. It is a powerful technique that combines gas chromatography's separation capabilities with mass spectrometry, offering detailed information, including structural identification of each metabolite. This chapter contains an easy-to-follow guide to extract plant-based metabolites. The current protocol provides all the information needed for extracting metabolites from a plant, precautions, and troubleshooting.