Evaluation of Gas Chromatography Columns with Radially Elongated Pillars as Second-Dimension Columns in Comprehensive Two-Dimensional Gas Chromatography.

The present study investigated the use of a dedicated gas chromatography (GC) column (L = 70 cm, 75 µm deep, and 6.195 mm wide) with radially elongated pillars (REPs) as the second column in a comprehensive two-dimensional gas chromatography (GC × µGC) system. Three stationary phases [apolar polydimethylsiloxane (PDMS), medium polar room-temperature ionic liquid (RTIL) based on monocationic phosphonium, and polar polyethylene glycol (PEG-1000)] have been coated using the static method at constant pressure or using an original vacuum pressure program (VPP) from 400 to 4 mbar. The best efficiency reached up to N = 62,000 theoretical plates for a film thickness of 47 nm at 100 °C for an iso-octane peak (k = 0.16) at an optimal flow rate of 4.8 mL/min. The use of the VPP improved the efficiency by approximately 15%. Efficiencies up to 28,000 and 47,000 were obtained for PEG-1000 and RTIL, respectively. A temperature-programmed separation of a mixture of 11 volatile compounds on a PDMS-coated chip was obtained in less than 36 s. The PDMS-, PEG-1000-, and RTIL-coated chips were tested as the second column using a microfluidic reverse fill/flush flow modulator in a GC × µGC system. The REP columns were highly compatible with the operating conditions in terms of flow rate and with more than 30,000 plates for the iso-octane peak. Moreover, a commercial solvent called white spirit containing alkanes and aromatic compounds was injected in three sets of columns in normal and reverse modes, demonstrating the great potential of the chip as a second-dimension separation column.

Reinvestigating the Preferential Enrichment of DL-Arginine Fumarate: New Thoughts on the Mechanism of This Far from Equilibrium Crystallization Phenomenon.

Preferential enrichment (PE) is a crystallization process, starting from either a racemic of slightly enantio-enriched solution (ca. +5%) that results in a high enantiomeric excess in the liquid phase (>+90%ee) and a slight opposite excess in the deposited crystals (−2 to −5%ee). The mechanism(s) of this symmetry-breaking phenomenon is (are) still a matter of debate since it eludes rationalization by phase diagram formalism. In this publication, we thoroughly reinvestigate the PE phenomenon of arginine fumarate by using a new approach: the process is monitored by introducing isotopically labeled arginine enantiomers into the crystallization medium to better understand the mass exchanges during crystallization. These experiments are supported by chiral HPLC-MS/MS. This study permits re-evaluating the criteria that were thought mandatory to perform PE. In particular, we show that PE occurs by a continuous exchange between the solution and the crystals and does not require the occurrence of a solvent-mediated solid−solid phase transition.

Comparison of Different d-SPE Sorbent Performances Based on Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) Methodology for Multiresidue Pesticide Analyses in Rapeseeds.

Pesticide extraction in rapeseed samples remains a great analytical challenge due to the complexity of the matrix, which contains proteins, fatty acids, high amounts of triglycerides and cellulosic fibers. An HPLC-MS/MS method was developed for the quantification of 179 pesticides in rapeseeds. The performances of the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method were evaluated using different dispersive solid-phase extraction (d-SPE) sorbents containing common octadecylsilane silica/primary-secondary amine adsorbent (PSA/C18) and new commercialized d-SPE materials dedicated to fatty matrices (Z-Sep, Z-Sep+, and EMR-Lipid). The analytical performances of these different sorbents were compared according to the SANTE/12682/2019 document. The best results were obtained using EMR-Lipid in terms of pesticide average recoveries (103 and 70 of the 179 targeted pesticides exhibited recoveries within 70-120% and 30-70%, respectively, with low RSD values). Moreover, the limits of quantification (LOQ) range from 1.72 µg/kg to 6.39 µg/kg for 173 of the pesticides. Only the recovery for tralkoxydim at 10 µg/kg level was not satisfactory (29%). The matrix effect was evaluated and proved to be limited between -50% and 50% for 169 pesticides with this EMR-Lipid and freezing. GC-Orbitrap analyses confirmed the best efficiency of the EMR-Lipid sorbent for the purification of rapeseeds.

Turbulent Supercritical Fluid Chromatography in Open-Tubular Columns for High-Throughput Separations.

A method utilizing turbulent flow to perform ultrafast separations and screen chiral compounds in supercritical fluid chromatography (SFC) is described. Carbon dioxide at high flow rates (up to 4.0 mL/min) is delivered into gas chromatography (GC) open-tubular columns (OTC, 0.18 mm i.d., 20 m long, ∼0.2 µm stationary film thickness) to establish turbulent flow at Reynolds numbers (Re) as high as 9000. Postcolumn dispersion is eliminated by using a modified UV detector that takes measurements directly on column. Upon crossing the laminar-to-turbulent flow transition regime, a significant reduction in plate height is observed resulting in a nearly 3-fold increase in peak capacity from the laminar regime. This is explained by the massive reduction of the mass transfer resistance in the mobile phase due to a flatter flow profile and faster analyte dispersion across the open-tubular column (OTC) i.d.. Demonstrated in this work is a 9 s separation of four polycyclic aromatic hydrocarbons (PAHs) over a 2.2 s separation window using a poly(dimethylsiloxane-co-methylphenylsiloxane) coated OTC. Additionally, three chiral compounds and three chiral cyclodextrin-incorporated OTCs were evaluated at high temperatures (90-120 °C) and CO2 flow rates (3.3-3.7 mL/min) to demonstrate column stability and application of this method for rapid screening. Turbulent SFC provides a separation method for users desiring to achieve separation speeds above what is currently available with very high-pressure LC systems and do so without the resolution loss commonly observed at maximum allowable speed.

Deracemization in a Complex Quaternary System with a Second-Order Asymmetric Transformation by Using Phase Diagram Studies.

A productive deracemization process based on a quaternary phase diagram study of a naphthamide derivative is reported. New racemic compounds of an atropisomeric naphthamide derivative have been discovered, and a quaternary phase diagram has been constructed that indicated that four solids are stable in a methanol/H2 O solution. Based on the results of a heterogeneous equilibria study showing the stable domain of the conglomerate, a second-order asymmetric transformation was achieved with up to 97 % ee. Furthermore, this methodology showcases the chiral separation of a stable racemic compound forming system and does not suffer from any of the typical limitations of deracemization, although application is still limited to conglomerate-forming systems. We anticipate that this present study will serve as a fundamental model for the design of sophisticated chiral separation processes.

Deracemization in a Complex Quaternary System with a Second-Order Asymmetric Transformation by Using Phase Diagram Studies.

Invited for the cover of this issue is the group of Gérard Coquerel at Université de Rouen Normandie. The image depicts a pyramid-like tetrahedron of the quaternary phase diagram showing where symmetry breaking can take place. Read the full text of the article at 10.1002/chem.201903338.

A sensitive LC-MS/MS method for the quantification of regioisomers of epoxyeicosatrienoic and dihydroxyeicosatrienoic acids in human plasma during endothelial stimulation.

Epoxyeicosatrienoic acids (EETs) are vasodilating lipid mediators metabolized into dihydroxyeicosatrienoic acids (DHETs) by soluble epoxide hydrolase. We aimed to develop a LC-MS/MS method to quantify EETs and DHETs in human plasma and monitored their levels during vascular endothelial stimulation. Plasma samples, collected from 14 healthy and five hypertensive subjects at baseline and during radial artery endothelium-dependent flow-mediated dilatation, were spiked with internal standards. Lipids were then extracted by a modified Bligh and Dyer method and saponified to release bound EETs and DHETs. Samples were purified by a second liquid-liquid extraction and analyzed by LC-MS/MS. The assay allowed identification of (±)8(9)-epoxy-5Z,11Z,14Z-eicosatrienoic acid (8,9-EET); (±)11(12)-epoxy-5Z,8Z,14Z-eicosatrienoic acid (11,12-EET); (±)14(15)-epoxy-5Z,8Z,11Z-eicosatrienoic acid (14,15-EET); (±)8,9-dihydroxy-5Z,11Z,14Z-eicosatrienoic acid (8,9-DHET); (±)11,12-dihydroxy-5Z,8Z,14Z-eicosatrienoic acid (11,12-DHET); and (±)14,15-dihydroxy-5Z,8Z,11Z-eicosatrienoic acid (14,15-DHET). (±)5(6)-epoxy-5Z,11Z,14Z-eicosatrienoic acid (5,6-EET) was virtually undetectable due to its chemical instability. The limits of quantification were 0.25 ng/mL for DHETs and 0.5 ng/mL for EETs. Intra- and inter-assay variations ranged from 1.6 to 13.2%. Heating induced a similar increase in 8,9-EET, 11,12-EET, and 14,15-EET levels and in corresponding DHET levels in healthy but not in hypertensive subjects. We validated a sensitive LC-MS/MS method for measuring simultaneously plasma EET and DHET regioisomers in human plasma and showed its interest for assessing endothelial function.

Enantiomerization of Allylic Trifluoromethyl Sulfoxides Studied by HPLC Analysis and DFT Calculations.

Enantiomerization of allylic trifluoromethyl sulfoxides occurs spontaneously at room temperature through the corresponding allylic trifluoromethanesulfenates via a [2,3]-sigmatropic rearrangement. Dynamic enantioselective high-performance liquid chromatography (HPLC) analysis revealed the stereodynamics of these sulfoxides ranging from chromatographic resolution to peak coalescence at temperatures between 5 and 53 °C. The rate constant of enantiomerization and activation parameters were determined and compared with Density Functional Theory (DFT) calculations.

Evaluation of thermally pretreated silica stationary phases under hydrophilic interaction chromatography conditions.

Three novel hydrophilic interaction chromatography columns packed with bare silica 2.6 µm superficially porous particles were evaluated. These stationary phases undergo a different pretreatment temperature (400, 525, and 900°C) that might influence their kinetic performance and thermodynamic properties. In the first instance, we demonstrated that the performance of these columns was inferior to the commercial ones in the low plate count range (10 000 plates), but was more favorable for N values beyond 40 000 plates. Thanks to its high permeability and reasonable flow resistance (φ = 695), together with a minimum reduced heights equivalent to a theoretical plate value of only 2.4, the stationary phase pretreated at 400°C was particularly attractive for N > 70 000 plates with a remarkably low impedance value (E = 2488). In a second step, the impact of pretreatment temperature was evaluated using two mixtures of polar substances, namely nucleobases and derivatives, as well as nicotine and derivatives. Retentions and selectivities achieved on the tested stationary phases were appropriate, but selectivity differences were minor when modifying pretreatment temperature from 400 to 525°C. When we increased the pretreatment temperature up to 900°C, the surface chemistry was more seriously modified. Finally, the columns presented a good stability even at high temperature (70°C), especially for the phases pretreated at 400 and 525°C.

Anion Exchange Chromatography Coupled to Electrospray-Mass Spectrometry: An Efficient Tool for Food, Environment, and Biological Analysis.

For over 50 years, ion chromatography has been demonstrated to be a successful technique used to quantify a wide range of ions and ionizable compounds, either organic or inorganic, in various matrices using conductimetric or electrochemical detection. It was only since 1996 that ion chromatography was coupled to electrospray-mass spectrometry, opening the field to new applications in complex matrices and the detection of compounds at trace levels. This review covers the recent developments of ion exchange chromatography and mass spectrometry. It focuses on the choice of mobile phases, column geometry, suppressors, make-up solvents and type of ionization sources reported in the literature. A brief overview of a large range of applications in food analysis, environmental analysis and bioanalysis is presented, and performances are discussed.

Evaluation of Asphalt Aging Using Multivariate Analysis Applied to Saturates, Aromatics, Resins, and Asphaltene Determinator Data.

Asphalt is subjected to aging, leading to physical and chemical modifications reducing its performance. Recently, the Western Research Institute developed the SAR-AD method that allowed the separation of asphalt into eight fractions (saturates, aromatics 1, aromatics 2, aromatics 3, resins, asphaltenes 1, asphaltene 2, and asphaltenes 3). In this work, this analytical method was used to study asphalt aging processes in greater detail. Several asphalts of different origins and reconstituted blends were studied. These products were aged during several durations using a PAV (pressure aging vessel) between 0 and 48 h to collect information on the evolution of each SAR-AD fraction. Different evolutions were observed according to the initial asphalt composition and SAR-AD fraction studied. The saturated subfamily seemed to be slightly impacted by aging. The amount of three aromatic subfamilies decreased with a larger decrease of aromatics 3 than aromatics 2, itself larger than aromatics 1. The content of the resin subfamily increased after 48 h of PAV aging. The asphaltene 1 and asphaltene 2 subfamilies exhibited an increasing trend. Moreover, the quantity of asphaltenes 2 created seemed to correlate to the initial asphaltene content. The evolutions of the asphaltene 3 subfamily were not significant. However, a specific behavior was highlighted for the most asphaltenic sample. For this specific sample, the increase of resin content was weaker, the mass of asphaltenes 1 decreased, and the amount of asphaltenes 3 increased during aging. Given the large amount of data generated, an original approach was developed to statistically identify the most affected SAR-AD subfamily and determine correlations among them. Two PCAs (Principal Component Analysis) were conducted on asphalt SAR-AD data. This statistical analysis indicated two generic asphalt aging pathways. The first aging pathway could be the conversion of aromatics 2 into resins, with no evidence that resins could contribute to asphaltene creation. The second aging pathway showed the conversion of aromatics 3 directly into asphaltenes 2. These two aging pathways highlighted that the conversion of molecules in more polar ones during aging could skip SAR-AD subfamilies, meaning that asphaltenes could be created without involving resins.

Investigation of Oxidation Homogeneity in Asphalt Puck after Simulation of Long-Term Aging (Pressure Aging Vessel).

For decades, it has been known that the creation of oxygenated functional groups, especially carbonyl and sulfoxide, is among the main causes of chemical aging and degradation of asphalt. However, is the oxidation of a bitumen homogeneous? The focus of this paper was to follow the oxidation phenomena through an asphalt puck during a pressure aging vessel (PAV) test. According to the literature, the asphalt oxidation process that leads to the creation of oxygenated functions can be divided into the following successive main steps: the absorption of oxygen in asphalt at the air/asphalt interface, diffusion into the matrix, and reaction with asphalt molecules. To study the PAV oxidation process, the creation of carbonyl and sulfoxide functional groups in three asphalts were investigated after various aging protocols by Fourier transform infrared spectroscopy (FTIR). From these experiments performed on different layers of asphalt puck, it was observed that PAV aging resulted in a nonhomogeneous oxidation level inside the entire matrix. Compared to the upper surface, the lower section exhibited carbonyl and sulfoxide indices 70% and 33% lower, respectively. Moreover, the difference in the oxidation level between the top and bottom surfaces increased when the thickness and viscosity of the asphalt sample increased.

Comparison of new approach of GC-HRMS (Q-Orbitrap) to GC-MS/MS (triple-quadrupole) in analyzing the pesticide residues and contaminants in complex food matrices.

Performances of multiresidue analysis of one hundred of pesticides and contaminants, using GC-Q-Orbitrap method in full scan mode were compared to those obtained with GC-triple-quadrupole method in multiple reaction monitoring mode. In terms of sensitivity, 86% of molecules exhibited lower limit of detection values using GC-Q-Orbitrap than using GC-triple-quadrupole. For the GC-Q-Orbitrap method, more than 85% of the pesticides and contaminants showed good recovery [70-120%] in wheat samples, with relative standard deviation values < 20%. GC-Q-Orbitrap method appeared the most sensitive for most pesticides studied in wheat with limit of quantification values ranged between 0.1 µg/kg and 4 µg/kg. Moreover, the matrix effect was acceptable in wheat extracts for 84 molecules but strong suppression of the chromatographic signal was observed for 16 molecules for the GC-Q-Orbitrap method. The injection of unpurified wheat extracts spiked at 10 µg/kg proved the potential of the GC-Q-Orbitrap method for use in performing high-throughput pesticide screening.

Development of two-dimensional gas chromatography (GC×GC) coupled with Orbitrap-technology-based mass spectrometry: Interest in the identification of biofuel composition.

Comprehensive gas chromatography (GC) has emerged in recent years as the technique of choice for the analysis of volatile and semivolatile compounds in complex matrices. Coupling it with high-resolution mass spectrometry (MS) makes a powerful tool for identification and quantification of organic compounds. The results obtained in this study showed a significant improvement by using GC×GC-EI-MS in comparison with GC-EI-MS; the separation of chromatogram peaks was highly improved, which facilitated detection and identification. However, the limitation of Orbitrap mass analyzer compared with time-of-flight analyzer is the data acquisition rate; the frequency average was about 25 Hz at a mass resolving power of 15.000, which is barely sufficient for the proper reconstruction of the narrowest chromatographic peaks. On the other hand, the different spectra obtained in this study showed an average mass accuracy of about 1 ppm. Within this average mass accuracy, some reasonable elemental compositions can be proposed and combined with characteristic fragment ions, and the molecules can be identified with precision. At a mass resolving power of 7.500, the scan rate reaches 43 Hz and the GC×GC-MS peaks can be represented by more than 10 data points, which should be sufficient for quantification. The GC×GC-MS was also applied to analyze a cellulose bio-oil sample. Following this, a highly resolved chromatogram was obtained, allowing EI mass spectra containing molecular and fragment ions of many distinct molecules present in the sample to be identified.

Desymmetrization of a meso-allylic acetal by enantioselective conjugate elimination.

An unprecedented enantioselective deprotonation/conjugate elimination sequence, which transforms an allylic meso-dioxepane into a chiral diene, is described. The best desymmetrization conditions (ee up to 70%) involve s-BuLi and sparteine at -78 degrees C in THF.

Separation and quantitative analysis of alkyl sulfate ethoxymers by HPLC.

Separation of alkyl sulfate ethoxymers is investigated on various high-performance liquid chromatography (HPLC) stationary phases: Acclaim C18 Surfactant, Surfactant C8, and Hypercarb. For a fixed alkyl chain length, ethoxymers are eluted in the order of increasing number of ethoxylated units on Acclaim C18 Surfactant, whereas a reversed elution order is observed on Surfactant C8 and Hypercarb. Moreover, on an Acclaim C18 Surfactant column, non-ethoxylated compounds are eluted in their ethoxymers distribution and the use of sodium acetate additive in mobile phase leads to a co-elution of ethoxymers. HPLC stationary phases dedicated to surfactants analysis are evaluated by means of the Tanaka test. Surfactant C8 presents a great silanol activity whereas Acclaim C18 Surfactant shows a high steric selectivity. For alkyl sulfates, linearity of the calibration curve and limits of detection and quantitation are evaluated. The amount of sodium laureth sulfate raw material found in commercial body product is in agreement with the specification of the manufacturer.

Use of comprehensive two-dimensional gas chromatography for the broad screening of hazardous contaminants in urban wastewaters.

The list of priority chemicals included in various regulations such as the European Water Framework Directive, as well as the list of hazardous contaminants identified in the aquatic environment, are increasing at an accelerated pace. Therefore, there is a need for broad spectrum methods capable of simultaneously determining hundreds, if not thousands, of contaminants. For the analysis of non-polar or semi-polar contaminants, comprehensive two-dimensional gas chromatography (GC x GC) is more powerful than conventional gas chromatography thanks to a separation on two different stationary phases. This paper reports the use of GC x GC for a broad screening of hazardous contaminants in an urban wastewater plant. Comparison between the raw and treated wastewater has been carried out using a semi-quantitative approach. A variety of drugs, personal care products, pesticides, carcinogens and compounds toxic for reproduction, were identified. Most of these compounds were removed or decreased by this wastewater treatment plant. Preliminary results from this single plant will need to be confirmed by a more extensive study before drawing conclusions on the removal efficiency of 2D-GC amenable compounds.

Development and validation of a pneumatic model for the reversed-flow differential flow modulator for comprehensive two-dimensional gas chromatography.

The development of the reversed fill/flush modulator represents a significant advancement in flow-modulated, comprehensive two-dimensional gas chromatography (GC × GC). Compared to the forward flush/fill modulator, the reversed-flow modulator is less susceptible to baseline anomalies and peak tailing as a result of modulator channel overfilling or insufficient purging of high concentration analytes. Flow reversal requires the addition of a bleed capillary not present in the forward-flow modulator. Selecting the appropriate restriction of the bleed capillary is critical. If the bleed capillary is too restrictive, eluate from the first-dimension column can split between the modulator channel and second-dimension column, which also results in baseline artifacts. To gain a better understanding of the reversed-flow modulator, a comprehensive pneumatic model was developed. The model was validated by comparing calculated and measured hold-up times. The errors in calculated hold-up times were less than 1% of the measured values. The model can be used to predict first-dimension eluate splitting and determine the optimal bleed capillary dimensions to prevent its occurrence. Calculation of the modulator hold-up time can be used to determine the maximum collection time to ensure comprehensive analysis and optimal flush times for partial fill operation.

The effect of high concentration additive on chiral separations in supercritical fluid chromatography.

Supercritical Fluid Chromatography is frequently used to efficiently handle separations of enantiomers. The separation of basic analytes usually requires the addition of a basic additive in the mobile phase to improve the peak shape or even to elute the compounds. The effect of increasing the concentration of 2-propylamine as additive on the elution of a series of basic compounds on a Chiralpak-AD stationary phase was studied. In this study, unusual additive concentrations ranging from 0.3% to 10% of 2-propylamine 2-propylaminein the modifier were explored and the effect on retention, peak shape, selectivity and resolution was evaluated. The addition of a large quantity of additive allowed to drastically improve the selectivity and the resolution, and even enantiomers elution order reversal was observed by changing the concentration of basic additive. The role of the ratio additive/modifier appeared a key to tune the enantioselectivity. Finally, the impact of these drastic conditions on the column material was evaluated.

Retention modeling and retention time prediction in gas chromatography and flow-modulation comprehensive two-dimensional gas chromatography: The contribution of pressure on solute partition.

This study aims at modelling and predicting solute retention in capillary Gas Chromatography (GC) and Flow Modulation comprehensive GC (FM-GCxGC). A new thermodynamic model, taking into account the effects of temperature and pressure, is proposed to describe the variation of the equilibrium partition constant of a solute during its elution. This retention model was challenged with the classical one, and both were applied to: (i) stationary phase film thickness indirect estimation; (ii) retention time (RT) prediction of a set of 11 model polycyclic aromatic hydrocarbons (PAHs) on the SLB-IL60 and DB-35MS columns, in temperature-programmed mode. Film thickness determination led to values about 2 times lower than those indicated by column nominal dimensions, whatever the employed model. Prediction of retention times in GC led to 0.84 and 0.26% mean errors using the classical and the extended models, respectively. Prediction in GCxGC gave 5.5 and 0.44% mean errors in 1st dimension RTs, and 7.3 and 2.2% mean errors in 2nd dimension RTs, using the classical and the extended models, respectively.