GC Retention Times Research Articles

The missing information of aliphatic-like & aromatic-like Unresolved Complex Mixtures (UCMs) in background oceanic atmosphere: occurrence, identification and deposition

Oceanic air samples (gas + particle phases) were collected over the Shanghai-Arctic background oceanic region during the Chinese Arctic Research expedition 2021. Full scan mode (semi-quantitative) and selective ion monitoring mode (quantitative) were used to analyze separately 72 polycyclic aromatic compounds (PACs) & C11–C35 n-Alkanes (n-Alks) and unresolved complex mixtures (UCMs, including aromatic-like and aliphatic-like compounds) in these samples. The concentration of ΣPACs in the gas-phase and particle-phase were 0.40–8.5 ng m−3 (2.4 ± 1.7 ng m−3) and 0.059–1.1 ng m−3 (0.21 ± 0.23 ng m−3), respectively. While Σn-Alks in the gas-phase and particle-phase were 2.2–80 ng m−3 (mean = 18 ± 24 ng m−3) and 2.2–20 ng m−3 (mean = 8.6 ± 5.0 ng m−3), respectively. The semi-quantitative result indicated that aromatic-like UCMs were 14–1400 times higher than those of ΣPACs in these two phases, while aliphatic-like UCMs were 1.2–25 times higher than those of Σn-Alks. Through three-dimensional identification of the one-dimensional GC-MS chromatogram (with the x-axis representing GC retention time, the y-axis representing m/z, and the z-axis representing peak intensity), we found that aromatic-like UCMs were primarily composed of phenanthrene & anthracene similar PACs, while aliphatic-like UCMs were predominated by long-chain alkanes. The source identification shows that oil-gas leakage was the dominant source of PACs, followed by petroleum & coal combustion and biomass combustion; n-Alks might be mainly originated from anthropogenic sources, while nature sources at high latitudes cannot be ignored as well. Aromatic-like UCMs had a decreasing latitude trend and the presence of 5–6 ring aromatic-like UCMs enclosed within organic aerosols could pose a significant ecological risk, particularly in high latitude regions. Net uptake of atmospheric carbon caused by dry deposition of aromatic-like & aliphatic-like UCMs varied significantly geographically with mid- and low-latitude seas. The non-polar and weakly polar substances were not the major components of organic carbon in oceanic air of high latitude areas.

Identification of the Sex Pheromone of the Asparagus Moth, Parahypopta Caestrum (Lepidoptera, Cossidae)

Chemical, electrophysiological, and field trapping experiments were carried out to identify the female-produced sex pheromone of the asparagus moth, Parahypopta caestrum, a very serious pests of asparagus cultivations in southern Europe. Gas chromatography coupled with mass spectrometry and electroantennogram detection (GC-MS-EAD) analysis of hexane and solid-phase microextraction (SPME) extracts of sex pheromone glands of calling females consistently detected four compounds eliciting EAG responses in male moth antennae. According to their GC retention times, mass spectra, and comparative EAG analyses with reference standards, these EAD-active compounds were identified as (Z)-9-tetradecenol (Z9-14:OH), (Z)-5-tetradecenyl acetate (Z5-14:Ac), (Z)-7-tetradecenyl acetate (Z7-14:Ac), and (Z)-9-tetradecenyl acetate (Z9-14:Ac), respectively. In the SPME extracts from the head-space of individual abdominal tips, Z9-14:Ac, Z5-14:Ac, Z7-14:Ac, and Z9:14 OH were detected in the ratio of 82:9:5:4. In EAG dose-response experiments, Z9-14:Ac was the strongest antennal stimulant at different doses tested. In field trapping experiments, Z9-14:Ac, Z7-14:Ac, and Z5-14:Ac proven to be essential for male attraction and a their 85:5:10 blend loaded onto green rubber septum dispensers was significantly more effective than single-, two-, and any other three-component blend of these compounds. The addition of Z9-14:OH to the optimal blend resulted in a significant reduction of male catches. The attractive blend here identified allowed for an effective and accurate monitoring of P. caestrum flight activity in southern Italy.

Compact GC-QEPAS for On-Site Analysis of Chemical Threats.

This paper reports on a compact, portable, and selective chemical sensor for hazardous vapors at trace levels, which is under development and validation within the EU project H2020 "RISEN". Starting from the prototype developed for a previous EU project, here, we implemented an updated two-stage purge and trap vapor pre-concentration system, a more compact MEMS- based fast gas-chromatographic separation module (Compact-GC), a new miniaturized quartz-enhanced photoacoustic spectroscopy (QEPAS) detector, and a new compact laser source. The system provides two-dimensional selectivity combining GC retention time and QEPAS spectral information and was specifically designed to be rugged, portable, suitable for on-site analysis of a crime scene, with accurate response in few minutes and in the presence of strong chemical background. The main upgrades of the sensor components and functional modules will be presented in detail, and test results with VOCs, simulants of hazardous chemical agents, and drug precursors will be reported and discussed.

Application of gas chromatographic data and 2D molecular descriptors for accurate global mobility potential prediction

Mobility is a key feature affecting the environmental fate, which is of particular importance in the case of persistent organic pollutants (POPs) and emerging pollutants (EPs). In this study, the global mobility classification artificial neural networks-based models employing GC retention times (RT) and 2D molecular descriptors were constructed and validated. The high usability of RT was confirmed based on the feature selection step performed using the multivariate adaptive regression splines (MARS) tool. Although RT was found to be the most important, according to Kruskal-Wallis ANOVA analysis, it is insufficient to build a robust model, which justifies the need to expand the input layer with 2D descriptors. Therefore the following molecular descriptors: MPC10, WTPT-2, AATS8s, minaaCH, GATS7c, RotBtFrac, ATSC7v and ATSC1p, which were characterized by a high predicting potential were used to improve the classification performance. As a result of machine learning procedure ten of the most accurate neural networks were selected. The external validation showed that the final models are characterized by a high general accuracy score (85.71–96.43%). The high predicting abilities were also confirmed by the micro-averaged Matthews correlation coefficient (MAMCC) (0.73–0.88). To evaluate the applicability of the models, new retention times of selected POPs and EPs including pesticides, polycyclic aromatic hydrocarbons, pharmaceuticals, fragrances and personal care products were measured and used for mobility prediction. Further, the classifiers were used for photodegradation and chlorination products of two popular sunscreen agents, 2-ethyl-hexyl-4-methoxycinnamate and 2-ethylhexyl 4-(dimethylamino)benzoate.

Determination of the Absolute Configuration of the Male-Produced Sex Pheromone of the Stink Bug Pellaea stictica, (2R,4R,8R)-2,4,8,13-Tetramethyltetradecan-1-ol by Stereoselective Synthesis Coupled with Enantiomeric Resolution.

In a previous study, we reported the identification and synthesis of a male-specific sex pheromone component of the stink bug, Pellaea stictica, as the alcohol 2,4,8,13-tetramethyltetradecan-1-ol (1). To establish the correlation between the stereochemistry of the pheromone and its bioactivity, it first was necessary to determine its absolute configuration. For this purpose, a series of syntheses were designed to: (a) furnish a mixture of all possible stereoisomers; (b) a narrowed down group of diastereomers, and (c) one specific enantiomer. A crucial step in the syntheses involved a coupling reaction between two key intermediates: a phosphonium salt and an aldehyde, through a Wittig olefination. Nuclear magnetic resonance data of a mixture of the synthetic pheromone diastereomers and further comparison of GC retention times with that of the natural product by gas chromatography suggested that the methyl branches at C2 and C4 were in a syn relationship, reducing the possibilities to only four of the eight possible stereoisomers. Employing GC analysis, chiral derivatization reagents and synthetic (8R)-2,4-syn-1 it was possible to confirm the configuration of the methyl branch at C8 as R, reducing the number of possible stereoisomers to two. After enantioselective synthesis of (2R,4R,8R)-1, the absolute configurations of all methyl branches of the natural compound were confirmed as R, fully identifying the male-produced sex pheromone of P. stictica as (2R,4R,8R)-2,4,8,13-tetramethyltetradecan-1-ol.

Synthesis and antifungal activity of the proposed structure of a volatile compound isolated from the edible mushroom Hypsizygus marmoreus.

We synthesized the proposed structure of an antifungal compound detected in the culture broth of the edible mushroom Hypsizygus marmoreus. Using the Evans aldol and Abiko–Masamune aldol reactions as the key steps, we synthesized all of the stereoisomers of the compound with high stereoselectivity. The GC retention times and the fragmentation patterns in the mass spectra of the synthesized isomers did not match those of the natural product. Therefore, this result may imply that it is necessary to reisolate the natural product and reconsider its structure. All of the synthesized isomers were found to exhibit antifungal activity against the phytopathogenic fungus Alternaria brassicicola. Due to their simple structures, the obtained isomers could be lead compounds for new pesticides.

Framework for nontargeted investigation of contaminants released by wildfires into stormwater runoff: Case study in the northern San Francisco Bay area

Wildfires can be extremely destructive to communities and ecosystems. However, the full scope of the ecological damage is often hard to assess, in part due to limited information on the types of chemicals introduced to affected landscapes and waterways. The objective of this study was to establish a sampling, analytical, and interpretive framework to effectively identify and monitor contaminants of emerging concern in environmental water samples impacted by wildfire runoff. A non-targeted analysis consisting of comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC/TOF-MS) was conducted on stormwater samples from watersheds in the City of Santa Rosa and Sonoma and Napa Counties after the three most destructive fires during the October 2017 Northern California firestorm. Chemicals potentially related to wildfires were selected from the thousands of chromatographic features detected through a screening method that compared samples from fire-impacted sites versus unburned reference sites. This screening led to high confidence identifications of 76 potentially fire-related compounds. Authentic standards were available for 48 of these analytes, and 46 were confirmed by matching mass spectra and GC×GC retention times. Of these 46 compounds, 37 had known commercial and industrial uses as intermediates or ingredients in plastics, personal care products, pesticides, and as food additives. Nine compounds had no known uses or sources and may be oxidation products resulting from burning of natural or anthropogenic materials. Preliminary examination of potential toxicity associated with the 46 compounds, conducted via online databases and literature review, indicated limited data availability. Regional comparison suggested that more structural damage may yield a greater number of unique, potentially wildfire-related compounds. We recommend further study of post-wildfire runoff using the framework described here, which includes hypothesis-driven site selection and non-targeted analysis, to uncover potentially significant stormwater contaminants not routinely monitored after wildfires and inform risk assessment. This article is protected by copyright. All rights reserved.

The Identification of New Triterpenoids in Eucalyptus globulus Wood.

Eight polyhydroxy triterpenoid acids, hederagenin, (4α)-23-hydroxybetulinic acid, maslinic acid, corosolic acid, arjunolic acid, asiatic acid, caulophyllogenin, and madecassic acid, with 2, 3, and 4 hydroxyl substituents, were identified and quantified in the dichloromethane extract of Eucalyptus globulus wood by comparing their GC-retention time and mass spectra with standards. Two other triterpenoid acids were tentatively identified by analyzing their mass spectra, as (2α)-2-hydroxybetulinic acid and (2α,4α)-2,23-dihydroxybetulinic acid, with 2 and 3 hydroxyl substituents. Two MS detectors were used, a quadrupole ion trap (QIT) and a quadrupole mass filter (QMF). The EI fragmentation pattern of the trimethylsilylated polyhydroxy structures of these triterpenoid acids is characterized by the sequential loss of the trimethylsilylated hydroxyl groups, most of them by the retro-Diels-Alder (rDA) opening of the C ring with a π-bond at C12-C13. The rDA C-ring opening produces ions at m/z 320 (or 318) and m/z 278 (or 277, 276, 366). Sequential losses of the hydroxyl groups produce ions with m/z from [M - 90] to [M - 90*y], where y is the number of hydroxyl substituents present (from 2 to 4). Moreover, specific cleavage in ring E was observed, passing from m/z 203 to m/z 133 and conducting other major fragments such as m/z 189.

Determination of atmospheric organochlorine pesticides using isotope dilution high-resolution gas chromatography/high-resolution mass spectrometry

建立了测定大气中25种有机氯农药(OCPs)的同位素稀释-高分辨气相色谱/高分辨质谱法(ID-HRGC/HRMS)。样品用正己烷/二氯甲烷(1:1, v/v)进行加速溶剂萃取(ASE)。通过柱洗脱实验、单柱和组合柱净化实验,最终确定样品的净化方案为弗罗里硅土固相萃取柱和石墨化炭黑固相萃取柱组合净化。样品萃取液净化后进行HRGC/HRMS分析。采用平均相对响应因子(RRF)法对样品中目标物进行定量,6点校准溶液RRF的相对标准偏差(RSD)均≤20%。线性范围为0.4~800 μg/L,相关系数R2均>0.992。对空白样品依次进行100 pg、400 pg和15 ng水平下的加标试验,各添加水平下OCPs测定值的RSD为0.64%~16%,加标回收率为67.2%~135%。穿透试验表明,滤膜+聚氨酯泡沫/聚氨酯泡沫作为吸附介质的大体积主动大气采样器(AAS)在采集环境空气时,五氯苯极易发生穿透,有效采样模式待进一步研究。在上述采样模式下,六氯苯的有效采样体积较小,标准状态(101.325 kPa, 273 K)采样体积应≤30 m3,其他OCPs应≤1200 m3。以上述体积计算,25种目标化合物的检出限为0.002~0.7 pg/m3。对北京环境空气样品分析测定,结果显示除反式-环氧七氯、异狄氏剂、顺式-九氯和4,4'-滴滴滴在部分样品中未检出外,其他OCPs均为100%检出;六氯苯浓度在514~563 pg/m3之间,其他OCPs的浓度在0.01~18.9 pg/m3之间;替代标回收率为33.9%~155%。由于现有相关监测标准的仪器灵敏度较低、方法检出限较高,已无法满足目前空气中痕量OCPs的测定需求,因此亟待修订新的高灵敏度监测方法标准。该方法适用于目前大气中OCPs的超痕量水平分析,为新标准的制订奠定基础,也为国家履行相关国际公约提供有力技术指导。

Identifying an unknown compound in flue gas of semiconductor industry – Forensics of a perfluorocarbon

This study investigated the source of a false positive signal in the measurement of total non-methane organic compounds (TNMOCs) by an on-line analyzer based on flame ionization detection (FID) in the flue gas released from a semiconductor fabrication plant. Since no release of volatile organic compounds (VOCs) into the waste gas stream in acid/base ventilation was assured by the plant authority, the positive detection of VOCs became a subject of dispute. In addition to the TNMOC analysis of 5 samples, the investigation used the method that coupled thermal desorption (TD) with gas chromatography mass spectrometry (GC/MS), dubbed TD-GC/MS, to identify the substance that produced the FID signals of TNMOCs. The waste gas was collected with sampling canisters and analyzed by in-laboratory TD-GC/MS. However, mass scanning from 45 to 250 m/z to remove interference from air matrix of O2, N2 and CO2 forbid detecting any ion fragments smaller than 45 m/z and, thus, led to poor match in mass (MS) library search. As a result, a highly retentive porous layer open tubular (PLOT) capillary column was employed to separate the unknown away from the air peak. The success of acquiring all key ion fragments of 31, 50, 69, and 131 m/z resulted in an excellent match with octafluorocyclobutane (C4F8) in the NIST database. A gas standard was then prepared and injected to confirm the identity of C4F8 by the identical mass spectrum and GC retention time. The concentrations of C4F8 found in the 5 flue gas samples varying from 3.32 to 6.21 ppmv were very close to the NMOC range of 3.48–6.62 ppmv as reported by the TNMOC analyzer, proving that the FID signals observed from TNMOC method were mostly produced from C4F8. Consequently, the method of TD-GC/MS would be an ideal method to pre-screen the presence of PFCs before a non-distinguishable TNMOC analyzer is applied to approximate the VOC level as part of the integrated effort to monitor VOC in flue gas.

Structural elucidation of amino amide-type local anesthetic drugs and their main metabolites in urine by LC-MS after derivatization and its application for differentiation between positional isomers of prilocaine.

The demand for clinical toxicology analytical methods for identifying drugs of abuse and medicinal drugs is steadily increasing. Structural elucidation of amino amide-type local anesthetic drugs and their main metabolites by GC-EI-MS and LC-ESI-MS/MS is of great analytical challenge. These compounds exhibit only/mostly fragments/product ions representing the amine-containing residue, while the aromatic amide moiety remains unidentified. This task becomes even more complicated when discrimination between positional isomers of such compounds is required. Here, we report the development of a derivatization procedure for the differentiation and structural elucidation of a mixture of local anesthetic drugs and their metabolites that possess tertiary and secondary amines in water and urine. A method based on two sequential "in-vial" instantaneous derivatization processes at ambient temperature followed by LC-ESI-MS/MS analysis was developed. 2,2,2-Trichloro-1,1-dimethylethyl chloroformate (TCDMECF) was utilized to selectively convert the secondary amines into their carbamate derivatives, followed by hydrogen peroxide addition to produce the corresponding tertiary amine oxides. The resulting derivatives exhibited rich fragmentation patterns, enabling improved structural elucidation of the original compounds. The developed method was successfully applied to the differentiation and structural elucidation of prilocaine and its four positional isomers, which all possess similar GC and LC retention times and four of them exhibit almost identical EI-MS and ESI-MS/MS spectra, enabling their structural elucidation in a single LC-ESI-MS/MS analysis. The developed technique is fast and simple and enables discrimination between isomers based on different diagnostic ions/fragmentation patterns.

A high-repetition-rate, fast temperature-programmed gas chromatograph and its online coupling to a supercritical fluid chromatograph (SFC × GC).

We present a fast gas chromatographic system that can be used as a second dimension in comprehensive two-dimensional (supercritical fluid × gas) chromatography (SFC × GC). The temperature of the short (1 m long) capillary column is controlled by a resistively heated coaxial stainless-steel tube. The electrical resistance and, therefore, temperature of the stainless-steel tube are measured by continuous monitoring of the current/voltage ratio. Highly repeatable heating rates of up to 2100 °C min-1 (35 °C s-1) are obtained, which should be high enough for the most demanding fast chromatograms. To reduce the cooling time between temperature programs, the column is cooled by injecting evaporating carbon dioxide into the space between the coaxial heater and the column. This gives cooling rates of 5100 °C min-1 (85 °C s-1), which allows quick succession of temperature programs. More repeatable heating profiles with stable GC retention times together with faster cooling are significant improvements on previous SFC × GC systems. Cycle times of four gas chromatograms per minute could readily be achieved, which allows efficient coupling to high-resolution stop-flow SFC in the first dimension. We demonstrate the fast chromatograph by separating fatty acid methyl esters, yielding information that would be useful in the food and biodiesel industries.

Fatty Amides in Minutes: Direct Formation from Fatty Esters in a Green Synthetic Process

Fatty amides are used in the manufacture of drugs, cosmetics, plastics, insecticides, etc. but the synthetic process involves fatty ester-derived fatty acid steps with economic and environmental consequences. Fatty esters (vegetable oils) are available in abundance and renewable but have not been used directly or cost effectively in the production of fatty amides. The fatty ester is usually first stripped to fatty acids resulting in a two-step instead of a single step synthesis which requires high temperatures (100 – 240°C), long reaction time (3 – 72 hours) and the use of catalyst. We had previously reported on a novel green method for the direct formation of fatty amides from a fatty ester. In the present study, the functionality and applicability of this green method is evaluated using a culinary and non-culinary oil namely peanut and castor oils. Each oil sample was hydrolyzed with NaOH in a non-aqueous medium and reacted in-situ with NH4Cl at 50°C in a reaction time of 60 minutes with no catalyst added. Conversions of 83 and 79% were recorded for the reactions of peanut and castor oils, respectively. The products of synthesis were characterized by Fourier-transform infrared spectroscopy (FT-IR) and various concentrations of product samples and two reference samples - erucamide and oleamide obtained from Sigma Aldrich - were subjected to Gas chromatography – Mass spectrometry (GC/MS) analysis. The qualitative GC-MS reports revealed the presence of 9-octadecenamide (oleamide) and hexadecanamide (palmitamide) at retention times of 27.76 and 23.90 minutes, respectively for all samples, including the reference. The predominant component of the second reference sample, erucamide, was found to be 13-docosenamide (erucamide) appearing at GC retention time of 32.58 minutes. The IR spectra of the products are strongly indicative of the presence of amides. The GC-MS analysis of the product samples confirms the formation of fatty amides. The detection of oleamide and erucamide in the reference samples and the detection of methyl ricinoleate at GC retention time of 26.573 minutes in the castor oil product sample validates the GC-MS analysis and confirms the functionality and applicability of this novel method of synthesis.

A MEMS-Enabled Deployable Trace Chemical Sensor Based on Fast Gas-Chromatography and Quartz Enhanced Photoacousic Spectoscopy.

This paper reports on a portable selective chemical sensor for hazardous vapors at trace levels, which combines a two-stage purge and trap vapor pre-concentration system, a Micro-Electro-Mechanical-System (MEMS) based fast gas-chromatographic (FAST-GC) separation column and a miniaturized quartz-enhanced photoacoustic spectroscopy (QEPAS) detector. The integrated sensing system provides two-dimensional selectivity combining GC retention time and QEPAS spectral information, and was specifically designed to be rugged and suitable to be deployed on unmanned robotic ground vehicles. This is the first demonstration of a miniaturized QEPAS device used as spectroscopic detector downstream of a FAST-GC separation column, enabling real-world analyses in dirty environments with response time of a few minutes. The main modules of the GC/QEPAS sensor device will be described in detail together with the system integration, and successful test results will be reported and discussed.

Comparison of measured and recommended acceptance criteria for the analysis of seized drugs using Gas Chromatography–Mass Spectrometry (GC–MS)

Gas Chromatography–Mass Spectrometry (GC–MS) is a widely used analytical technique that has become a critical tool in many industries, including forensic science. Many governing bodies provide recommendations for the uncertainty of measurement for chemical substance identification, but existing guidelines often do not provide the numerical data to support the basis for their acceptance criteria. The guidelines therefore appear anecdotal and, if they are not continually updated, may not reflect modern instrument capabilities. This study provides data, with detailed interpretations, to assess the magnitudes and sources of measurement uncertainties of typical GC–MS data, as commonly practiced.Data analysis was conducted using 13 different drug standards from three different laboratories using five different GC–MS setups. The laboratories were not prescribed a set of instrumental parameters, but rather were asked to submit the parameters ordinarily practiced within their respective laboratories. An expanded uncertainty of two times the relative standard deviation (2σ) of replicate measurements was used to report the uncertainty of measurement for the retention time and relative ion abundance measurements made on each set-up.The retention time acceptance criteria currently recommended by many agencies are on the magnitude of ±2%, but such criteria are much wider than the measured within-week or within-month 2σ values, which are actually on the magnitude of ±0.20%. The measured uncertainties of relative ion abundances are similar to recommended acceptance criteria, but a careful assessment shows that ion abundances are not independently variable within a spectrum. Some ion abundances correlate with correlation co-efficients (R squared) that exceed 0.9. Acceptance criteria for the GC retention time measurements should therefore be stricter than most of the current recommended guidelines. The application of tighter acceptance criteria would provide: 1) an evidenced-based, statistical reason for making drug identifications; and 2) fewer type I errors (false positives) in seized drug analyses than provided by existing standards.

Qualitative characterization of three combustion-related standard reference materials for polycyclic aromatic sulfur heterocycles and their alkyl-substituted derivatives via normal-phase liquid chromatography and gas chromatography/mass spectrometry.

The research described here provides the most comprehensive qualitative characterization of three combustion-related standard reference materials (SRMs) for polycyclic aromatic sulfur heterocycles (PASHs) and some alkyl-substituted (alkyl-) derivatives to date: SRM 1597a (coal tar), SRM 1991 (coal tar/petroleum extract), and SRM 1975 (diesel particulate extract). An analytical approach based on gas chromatography/mass spectrometry (GC/MS) is presented for the determination of three-, four-, and five-ring PASH isomers and three- and four-ring alkyl-PASHs in the three SRM samples. The benefit of using a normal-phase liquid chromatography (NPLC) fractionation procedure prior to GC/MS analysis was demonstrated for multiple isomeric PASH groups. Using a semi-preparative aminopropyl (NH2) LC column, the three combustion-related samples were fractionated based on the number of aromatic carbon atoms. The NPLC-GC/MS method presented here allowed for the following identification breakdown: SRM 1597a - 35 PASHs and 59 alkyl-PASHs; SRM 1991-31 PASHs and 58 alkyl-PASHs; and SRM 1975-13 PASHs and 25 alkyl-PASHs. These identifications were based on NPLC retention data, the GC retention times of reference standards, and the predominant molecular ion peak in the mass spectrum. Prior to this study, only 11, 1, and 0 PASHs/alkyl-PASHs had been identified in SRM 1597a, SRM 1991, and SRM 1975, respectively. Graphical abstract NPLC-GC/MS analysis for the three- and four-ring parent PASH isomers in SRM 1597a.

A simple, fast, and accurate thermodynamic-based approach for transfer and prediction of GC retention times between columns and instruments Part II: Estimation of target column geometry.

The transfer of thermodynamic parameters governing retention of a molecule in gas chromatography from a reference column to a target column is a difficult problem. Successful transfer demands a mechanism whereby the column geometries of both columns can be determined with high accuracy. This is the second part in a series of three papers. In Part I of this work we introduced a new approach to determine the actual effective geometry of a reference column and thermodynamic-based parameters of a suite of compounds on the column. Part II, presented here, illustrates the rapid estimation of the effective inner diameter (or length) and the effective phase ratio of a target column. The estimation model based on the principle of least squares; a fast Quasi-Newton optimization algorithm was developed to provide adequate computational speed. The model and optimization algorithm were tested and validated using simulated and experimental data. This study, together with the work in Parts I and III, demonstrates a method that improves the transferability of thermodynamic models of gas chromatography retention between gas chromatography columns.

Pheromone synthesis. Part 262: Determination of the absolute configuration of the female sex pheromone [(1S,2S)-(−)-(1,2-dimethyl-3-methylenecyclopentyl) acetaldehyde] of the pineapple mealybug (Dysmicoccus brevipes) by synthesis coupled with X-ray analysis

The enantiomers of (anti-1,2-dimethyl-3-methylenecyclopentyl)acetaldehyde, one of which is the female sex pheromone of the pineapple mealybug (Dysmicoccus brevipes), were synthesized. Chirality was introduced by means of lipase-catalyzed asymmetric acetylation of (±)-2,3-dimethyl-2-cyclopenten-l-ol. X-ray analysis of (−)-camphanate ester of (1S,2S)-(−)-2-(1,2-dimethyl-3-methylenecyclopentyl)ethanol confirmed its (1S,2S)-absolute configuration. The natural pheromone was identified with the (1S,2S)-aldehyde by comparing the specific rotation, enantioselective GC retention time and pheromone activity.

Qualitative characterization of SRM 1597a coal tar for polycyclic aromatic hydrocarbons and methyl-substituted derivatives via normal-phase liquid chromatography and gas chromatography/mass spectrometry.

A normal-phase liquid chromatography (NPLC) fractionation procedure was developed for the characterization of a complex mixture of polycyclic aromatic hydrocarbons (PAHs) from a coal tar sample (Standard Reference Material (SRM) 1597a). Using a semi-preparative aminopropyl (NH2) LC column, the coal tar sample was separated using NPLC based on the number of aromatic carbons; a total of 14 NPLC fractions were collected. SRM 1597a was analyzed before and after NPLC fractionation by using gas chromatography/mass spectrometry (GC/MS) with a 50% phenyl stationary phase. The NPLC-GC/MS method presented in this study allowed for the identification of 72 PAHs and 56 MePAHs. These identifications were based on the NPLC retention times for authentic reference standards, GC retention times for authentic reference standards, and the predominant molecular ion peak in the mass spectrum. Most noteworthy was the determination of dibenzo[a,l]pyrene, which could not be measured directly by GC/MS because of low concentration and co-elution with dibenzo[j,l]fluoranthene. The NPLC-GC/MS procedure also allowed for the tentative identification of 74 PAHs and 117 MePAHs based on the molecular ion peak only. This study represents the most comprehensive qualitative characterization of SRM 1597a to date. Graphical abstract NPLC-GC/MS analysis for the six-ring MM 302 Da PAH isomers in SRM 1597a.

Fully automated determination of the sterol composition and total content in edible oils and fats by online liquid chromatography–gas chromatography–flame ionization detection

Sterol analysis of edible oils and fats is important in authenticity control. The gas chromatographic determination of the sterol distribution and total content is described by ISO norm 12228. Extraction, purification, and detection of the sterols are time-consuming and error-prone. Collaborative trials prove this regularly. Purification by thin-layer chromatography (TLC) and robust GC determination of all mentioned sterols is not straightforward. Therefore, a fully automated LC-GC-FID method was developed to facilitate the determination of sterols. The only manual step left was to weigh the sample into an autosampler vial. Saponification and extraction were performed by an autosampler while purification, separation, and detection were accomplished by online coupled normal-phase LC-GC-FID. Interlacing of sample preparation and analysis allowed an average sample throughput of one sample per hour. The obtained quantitative results were fully comparable with the ISO method with one apparent exception. In the case of sunflower oils, an additional unknown sterol was detected generally missed by ISO 12228. The reason was found in the omission of sterol silylation before subjection to GC-FID. The derivatization reaction changed the retention time and hid this compound behind a major sterol. The compound could be identified as 14-methyl fecosterol. Its structure was elucidated by GC–MS and ensured by HPLC and GC retention times. Finally, validation of the designed method confirmed its suitability for routine environments.