Retention indices are values that characterize the retention of a compound in gas chromatography. In practice, retention indices are often assumed to depend only on the structure of the molecule and the type of the stationary phase, but this approximation is incorrect. This study is devoted to studying the dependence of retention indices on the column heating rate in the linear temperature programming mode, using a large and diverse data set. In the NIST 20 database, most data records are recorded in this mode. For stationary phases based on poly(5%-diphenyl-95%-dimethyl)siloxane (5%-phenyl-PDMS), there is a high proportion of records with heating rates of 10-15 K/min. In practice, such a high heating rate is rarely used and the use of such data may cause errors. A search was made for groups of records that were taken from the same primary source, recorded for the same compound and the same stationary phase, but differing in a heating rate. For each of these groups, the value D, the angular coefficient (slope) of the dependence of the retention index on the heating rate, was calculated. This value can take both positive and negative values. The highest values and the greatest variation of D values are observed for polar stationary phases, but further consideration was performed for 5%-phenyl-PDMS due to its greater practical significance. For these stationary phases, the highest D values are observed for aromatic and polyaromatic molecules; oxygen-containing compounds, on the contrary, exhibit lower D values. Negative D values are observed for many trimethylsilyl derivatives. A data set of D values for 756 molecules was selected and published online. There is almost no correlation between D and the retention index, lipophilicity factor logP, and molecular weight. Significant correlations with the number of cycles, the number of rotatable bonds, and the number of aromatic atoms were observed. Linear equations quantitatively relating the molecular descriptors to the D value were constructed. A number of cycles and halogen atoms were shown to contribute positively to the D value, while a number of oxygen atoms and bonds subject to internal rotation contributed negatively. The strong influence of the values related to the conformational rigidity of molecules and the weak influence of polarity allow us to suppose that the entropic factor has a key influence on the D value. A simple empirical linear equation for estimating the value of D is derived and presented in this study. Several machine learning methods for predicting D are compared. The best results are shown by gradient boosting and a random forest. However, the random forest does not achieve high accuracy in predicting the retention indices themselves.

OBJECTIVE: Although the mouse is a widely used animal model in biomedical research, there are few published studies on its nasal aerodynamics, potentially due to its small size. It is not appropriate to assume that mice and rats\' nasal structure and airflow characteristics are the same because the ratio of nasal surface area to nasal volume and body weight is much higher in a mouse than in a rat. The aim of this work is to use anatomically accurate image-based computational fluid dynamic modeling to quantitatively reveal the characteristics of mouse nasal airflow and mass transport that haven\'t been detailed before and find key differences to that of rat nose, which will deepen our understanding of the mouse\'s physiological functions.
METHODS: We created an anatomically accurate 3D computational nasal model of a B6 mouse using postmortem high-resolution micro-CT scans and simulated the airflow distribution and odor transport patterns under restful breathing conditions. The deposition pattern of airborne particles was also simulated and validated against experimental data. In addition, we calculated the gas chromatograph efficiency of odor transport in the mouse employing the theoretical plate concept and compared it with previous studies involving cat and rat models.
RESULTS: Similar to the published rat model, respiratory and olfactory flow regimes are clearly separated in the mouse nasal cavity. A high-speed dorsal medial (DM) stream was observed, which enhances the delivery speed and efficiency of odor to the ethmoid (olfactory) recess (ER). The DM stream split into axial and secondary paths in the ER. However, the secondary flow in the mouse is less extensive than in the rat. The gas chromatograph efficiency calculations suggest that the rat may possess a moderately higher odorant transport efficiency than that of the mouse due to its more complex ethmoid recess structure and extensive secondary flow. However, the mouse\'s nasal structure seems to adapt better to varying airflow velocity.
CONCLUSIONS: Due to the inherent structural disparities, the rat and mouse models exhibit moderate differences in airflow and mass transport patterns, potentially impacting their olfaction and other behavioral habits.

Untargeted analysis of gas chromatography-high-resolution mass spectrometry (GC-HRMS) data is a key and time-consuming challenge for identifying metabolite markers in food authentication applications. Few studies have been performed to evaluate the capability of untargeted data processing tools for feature extraction, metabolite annotation, and marker selection from untargeted GC-HRMS data since most of them are focused on liquid chromatography (LC) analysis. In this framework, this study provides a comprehensive evaluation of data analysis tools for GC-Orbitrap-HRMS plant metabolomics data, including the open-source MS-DIAL software and commercial Compound Discoverer™ software (designed for Orbitrap data processing), applied for the geographical discrimination and search for thyme markers (Spanish vs. Polish differentiation) as the case study. Both approaches showed that the feature detection process is highly affected by unknown metabolites (Levels 4-5 of identification confidence), background signals, and duplicate features that must be carefully assessed before further multivariate data analysis for reliable putative identification of markers. As a result, Compound Discoverer™ and MS-DIAL putatively annotated 52 and 115 compounds at Level 2, respectively. Further multivariate data analysis allowed the identification of differential compounds, showing that the putative identification of markers, especially in challenging untargeted analysis, heavily depends on the data processing parameters, including available databases used during compound annotation. Overall, this method comparison pointed out both approaches as good options for untargeted analysis of GC-Orbitrap-HRMS data, and it is presented as a useful guide for users to implement these data processing approaches in food authenticity applications depending on their availability.

The aim of our study was to develop a gas chromatographic method coupled with mass spectrometry (GC-MS) for the determination of underivatised neutral (CBDs-N) and acidic (CBDs-A) cannabinoids (CBDs) and cholesterol (Chol). Emphasis was also placed on comparing our original GC-MS method with the currently developed C18-high-performance liquid chromatography with photodiode detection (C18-HPLC-DAD). A combination of a long GC column, shallow temperature column programme, and mass-spectrometry was employed to avoid issues arising from the overlap between CBDs and Chol and background fluctuations. The pre-column procedure for CBDs and Chol in egg yolks consisted of hexane extractions, whereas the pre-column procedure for CBDs in non-animal samples involved methanol and hexane extractions. CBDs-A underwent decarboxylation to CBDs during GC-MS analyses, and pre-column extraction of the processed sample with NaOH solution allowed for CBD-A removal. No losses of CBDs-N were observed in the samples extracted with NaOH solution. GC-MS analyses of the samples before and after extraction with NaOH solution enabled the quantification of CBDs-A and CBDs-N. CBDs-A did not undergo decarboxylation to CBDs-N during C18-HPLC-DAD runs. The use of the C18-HPLC-DAD method allowed simultaneous determination of CBDs-N and CBDs-A. In comparison to the C18-HPLC-DAD method, our GC-MS technique offered improved sensitivity, precision, specificity, and satisfactory separation of underivatised CBDs and Chol from biological materials of endogenous species, especially in hemp and hen egg yolk. The scientific novelty of the present study is the application of the GC-MS method for quantifying underivatised CBDs-A, CBDs-N, and Chol in the samples of interest.

The biological role of lipids goes far beyond the formation of a structural membrane bilayer platform for membrane proteins and controlling fluxes across the membranes. For example, in photosynthetic thylakoid membranes, lipids occupy well-defined binding niches within protein complexes and determine the structural organization of membrane proteins and their function by controlling generic physicochemical membrane properties. In this chapter, two-dimensional thin-layer chromatography (2D TLC) and gas chromatography (GC) techniques are presented for quantitative analysis of lipid classes and fatty acids in thylakoid membranes. In addition, lipid extraction methods from isolated thylakoid membranes and leaves are described together with a procedure for the derivatization of fatty acids to fatty acid methyl esters (FAME) that is required for GC analysis.

This study presents a method employing gas chromatography coupled with mass spectrometry and headspace solid-phase microextraction (HS-SPME-GC-MS), supplemented with chemometrics (Soft independent modelling of class analogies - SIMCA), to analyze volatile organic compound (VOCs) profiles in suspect whiskey samples. Furthermore, a sensory analysis of aroma and color was conducted with a panel of 52 non-trained volunteers to evaluate their ability to discriminate and preference for counterfeit whiskeys. The HS-SPME-GC-MS method successfully distinguished 41 seized samples from authentic beverages. Interestingly, sensory analysis revealed that panelists could differentiate between counterfeit and authentic samples with a reference standard but did not consistently show a preference for aroma. In some cases, there was even a preference for the color of counterfeit whiskeys. The findings suggest that sensorial tests alone may not effectively distinguish counterfeit from authentic whiskeys, especially for non-expert consumers, highlighting the need for analytical instrumentation methods in fraud detection.

Sevoflurane, also called fluoromethyl ether, is an inhalation anesthetic agent used to initiate and maintain general anesthesia for adults and pediatric patients during surgical procedures. Several analytical methods have previously been applied to follow the properties and quality of sevoflurane, including mass spectrometry and gas chromatography methods. These methods are practically tedious and need sophisticated apparatus. In the present work, an attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectrometric method was used for the quantitative determination of sevoflurane which is characterized as a fast, accurate, and available technique for most pharmaceutical laboratories, besides the gas chromatographic method which is the most suitable for the detection of impurities. Sevoflurane is a liquid and it is applied directly on the glass top of the ATR-FTIR either as a concentrated solution or diluted with hexane as a diluent, which did not interfere with sample determination within the specified wavelength range of the IR spectrum, particularly the wavelength of the ethereal group at 1200 cm-1. This method can be applied to the identification test and quantitative assay of sevoflurane since it is validated for the precision, accuracy, reproducibility, and specificity in the analysis of sevoflurane as a pharmaceutical product. However, still, there is a need for a gas chromatographic method to detect the impurities and degradation products during the stability study of sevoflurane.

OBJECTIVE: The discovery of objective indicators for recent epileptic seizures will help confirm the diagnosis of epilepsy and evaluate therapeutic effects. Past studies had shortcomings such as the inclusion of patients under treatment and those with various etiologies that could confound the analysis results significantly. We aimed to minimize such confounding effects and to explore the small molecule biomarkers associated with the recent occurrence of epileptic seizures using urine metabolomics.
METHODS: This is a multicenter prospective study. Subjects included pediatric patients aged 2 to 12 years old with new-onset, untreated epilepsy, who had had the last seizure within 1 month before urine collection. Controls included healthy children aged 2 to 12 years old. Those with underlying or chronic diseases, acute illnesses, or recent administration of medications or supplements were excluded. Targeted metabolome analysis of spot urine samples was conducted using gas chromatography (GC)- and liquid chromatography (LC)-tandem mass spectrometry (MS/MS).
RESULTS: We enrolled 17 patients and 21 controls. Among 172 metabolites measured by GC/MS/MS and 41 metabolites measured by LC/MS/MS, only taurine was consistently reduced in the epilepsy group. This finding was subsequently confirmed by the absolute quantification of amino acids. No other metabolites were consistently altered between the two groups.
CONCLUSIONS: Urine metabolome analysis, which covers a larger number of metabolites than conventional biochemistry analyses, found no consistently altered small molecule metabolites except for reduced taurine in epilepsy patients compared to healthy controls. Further studies with larger samples, subjects with different ages, expanded target metabolites, and the investigation of plasma samples are required.

Microbial skin infections, antibiotic resistance, and poor wound healing are major problems, and new treatments are needed. Our study targeted solving this problem with Nigella sativa (NS) oil and photodynamic therapy based on methylene blue (MB-PDT). Antibacterial activity and minimum inhibitory concentration (MIC) were determined via agar well diffusion assay and broth microdilution, respectively. Transmission electron microscopy (TEM) proved deformations in Staphylococcus aureus ATCC 6538. Gas chromatography-mass spectrometry identified useful compounds that were suggested to be responsible for the potency of the oil. NS oil was tested as an antivirus against low pathogenic coronavirus (229E). Therapies examined, MB-PDT, NS, and MB-PDT + NS oil, to accelerate wound healing. The antibacterial efficacy against S. aureus was promising, with a MIC of 12.5% and TEM showing injured cells treated with NS oil. This oil inhibited 229E virus up to 42.85% and 32.14%. All tested therapies were successful in accelerating wound healing. The most successful was combined therapy (MB-PDT + NS oil), with a faster healing time. The combined therapy (MB-PDT + NS oil) reduced bacterial counts, which may be a key factor in accelerating wound healing. Skin wound histology was investigated; blood hematology and biochemical analysis did not change significantly after the safe combination treatment. A combination treatment could facilitate healing in a simple and inexpensive way in the future. Based on the results of the in vitro and in vivo studies, it was determined that NS oil had antibacterial and anti-corona virus activity when used in conjunction with photodynamic treatment based on methylene blue to treat wound infections.

Preconcentration for on-site detection or subsequent determination is a promising technique for selective sensing explosive markers at low concentrations. Here, we report divinylbenzene monolithic polymer in its blank form (neat-DVB) and as a composite incorporated with sodalite topology zeolite-like metal-organic frameworks (3-ZMOF@DVB), as a sensitive, selective, and cost-effective porous preconcentrator for aliphatic nitroalkanes in the vapor phase as explosive markers at infinite dilution. The developed materials were fabricated as 18 cm gas chromatography (GC) monolithic capillary columns to study their separation performance of nitroalkane mixture and the subsequent physicochemical study of adsorption using the inverse gas chromatography (IGC) technique. A strong preconcentration effect was indicated by a specific retention volume adsorption/desorption ratio equal to 3 for nitromethane on the neat-DVB monolith host-guest interaction, and a 14% higher ratio was observed using the 3-ZMOF@DVB monolithic composite despite the low percentage of 0.7 wt.% of sod-ZMOF added. Furthermore, Incorporating ZMOF resulted in a higher percentage of micropores, increasing the degree of freedom more than bringing stronger adsorption and entropic-driven interaction more than enthalpic. The specific free energy of adsorption (ΔGS) values increased for polar probes and nitroalkanes, denoting that adding ZMOFs earned the DVB monolithic matrix a more specific character. Afterward, Lewis acid-base properties were calculated, estimating the electron acceptor (KA) and electron donor (KB) constants. The neat-DVB was found to have a Lewis basic character with KB/KA = 7.71, and the 3-ZMOF@DVB had a less Lewis basic character with KB/KA = 3.82. An increased electron-accepting nature can be directly related to incorporating sod-ZMOF into the DVB monolithic matrix. This work considers the initial step in presenting a portable explosives detector or preconcentrating explosive markers trace prior to more sophisticated analysis. Additionally, the IGC technique allows for understanding the factors that led to the superior adsorption of nitroalkanes for the developed materials.