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.

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.

Society\'s concerns about the citizens\' exposure to possibly dangerous environments have recently risen; nevertheless, the assessment of indoor air quality still represents a major contemporary challenge. The volatile organic compounds (VOCs) are among the main factors responsible for deteriorating air quality conditions. These analytes are very common in daily-use environments and they can be extremely hazardous to human health, even at trace concentrations levels. For these reasons, their quick detection, identification, and quantification are crucial tasks, especially for indoor and heavily-populated scenarios, where the exposure time is usually quite long. In this work, a Gas Chromatography - Ion Mobility Spectrometry (GC-IMS) device was used for continuous monitoring indoor and ambient air environments at a large-scale, due to its outstanding levels of sensibility, selectivity, analytical flexibility, and almost real-time monitoring capability. A total of 496 spectra were collected from 15 locations of a university campus and posteriorly analysed. Overall, 23 compounds were identified among the 31 detected. Some of them, like Ethanol and 2-Propanol, were reported as being very hazardous to the human organism, especially in indoor environments. The achieved results confirmed the suitability of GC-IMS technology for air quality assessment and monitoring of VOCs and, more importantly, proved how dangerous indoor environments can be in scenarios of continuous exposure.

The gradual loss of ethanol over time in stored blood specimens under a variety of conditions has been well documented. An analysis of over 160 blood specimens from suspected impaired drivers was recently accomplished with the knowledge that the samples had previously been analyzed. These two analyses were performed independently, using different methods and instrumentation and by different individuals. Although in most cases there were two tubes available in each case, the tube used for the initial analysis was also used for the second analysis. Reported results from both laboratories were obtained and evaluated retrospectively. Over an average interval of approximately 13 months (range 34-1002 days), the average change of ethanol concentrations was a loss of 0.006 g/dL, with a maximum loss of 0.023 g/dL, and a maximum increase of 0.004 g/dL. The median difference was a loss of 0.005 g/dL. The percentage of samples that reported second concentrations equal to or less than the original reported concentrations (to the thousandths decimal place) was 96.4%. No correlation was observed between the net loss and the initial BAC value, but the amount of time between analyses did impact the extent of the loss of ethanol as determined by the second analysis. Our results indicate a smaller loss of ethanol, and hence stronger correlation between analytical events, than what has been experienced in similar work. Based on our analysis and review of previously opened and analyzed blood specimens, a previously opened blood tube can yield a strong correlation to the original analysis and may therefore be appropriate if a second tube is not available or compromised in some way.

Considering the characteristic chromatograms and quality value transmitting of three volatile components, this study investigated the changes in volatile components of Menthae Haplocalycis Herba in each heating process of personalized preparations and identified the critical control points for the application of volatile components from traditional Chinese medicine in such preparations. The characteristic chromatograms of volatile components in Menthae Haplocalycis Herba were established by gas chromatography, followed by the quantitative determination of three volatile components menthone, menthol, and piperitone and the comparison of retention rates of volatile components during the crushing, extraction, concentration and drying of preparation products and their change rules in characteristic peaks. The results showed that the volatile components of Menthae Haplocalycis Herba were reduced in each process. The loss rate was low in the crushing process when the volatile component peaks were present, but high in the extraction and concentration processes, manifested as the absence of partial component peaks and the presence of new component peaks. The changes in volatile components of Chuanxiong Chatiao Granule in the drying process were compared with those in Chuanxiong Chatiao Pill, both of which were prepared from the raw Menthae Haplocalycis Herba powder, and the findings demonstrated that Chuanxiong Chatiao Pill was superior to Chuanxiong Chatiao Granule. This study confirmed that the retention rates of volatile components in Menthae Haplocalycis Herba were mostly affected by the extraction and concentration processes, and the packing of preparations helped to reduce the loss of volatile components in Menthae Haplocalycis Herba powder, which has provided reference for the application of Chinese medicinal materials containing volatile components in the personalized preparations.

Every year, after grape harvesting, high quantities of vine-canes are generated. Due to the high amount of bioactive compounds present in this woody material, several studies reported their potential to be used in different sustainable applications. However, before employing vine-canes in this kind of products, their safety needs to be assessed. A robust method for identification and quantification of 30 environmental contaminants (12 organochloride pesticides (OCPs), 6 organophosphorus pesticides (OPPs), 5 polychlorinated biphenyls (PCBs) and 7 brominated flame retardants (BFRs)) in vine-canes was developed. For that, the extraction and clean-up procedures were optimized, namely the vine-canes size, the QuEChERS (quick, easy, cheap, effective, rugged and safe) composition and the amount of carbon used in the dispersive-solid phase extraction (d-SPE). Suitable analytical parameters were obtained: linearity (r2) >0.99 for all the studied compounds and for the solvent and matrix-matched standards; relative standard deviation (RSD) below 14%; and mean recoveries for two spiking levels (10 and 20 μg/kg) between 75 and 103%, excepting for the PCBs that ranged between 59 and 105%. The limit of detection (LOD) and quantification (LOQ) ranged between 0.38 and 1.09 and 1.26 to 3.64 μg/kg, respectively. Regarding the analysis of 19 vine-cane samples, corresponding to four different varieties (Touriga Nacional, Tinta Roriz, Alvarinho, and Loureiro) collected in four different years in the North of Portugal, five contaminants (aldrin, 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (p,p\'-DDE), α-hexachlorocyclohexane (α-HCH), 2,4,4\'-trichlorobiphenyl (PCB28), and 2,2\',4,5,5\'-pentachlorobiphenyl (PCB101)) were detected. However, only α-HCH (5.85 ± 0.32 to 5.99 ± 0.25 μg/kg) and aldrin (2.44 ± 0.15 μg/kg) were quantified above the LOQ. The screening of environmental contaminants in vine-canes is essential to waste valorization, especially if the goal is to apply them in products for human consumption.

Conventional and sparse partial least squares-discriminant analysis (PLS-DA and sPLS-DA) have been successfully tested in order to authenticate avocado samples in terms of three different geographical origins and six kinds of cultivar. For this, lipid chromatographic fingerprints of different avocado fruits have been acquired using gas chromatography coupled with flame ionization detector (GC-FID) and employed for building classification models. In addition, classification models concatenating strategy has been applied, which has proved to be successful to resolve multiclass problems in food authentication. Finally, fine performance metrics around of 0.95 were obtained for both multivariate classification methods.

Due to its multiple advantages, ion mobility spectrometry (IMS) is being considered as a complementary technique to mass spectrometry (MS). The goal of this work is to investigate and compare the capacity of IMS and MS in the classification of olive oil according to its quality. For this purpose, two analytical methods based on headspace gas chromatography (HS-GC) coupled with MS or with IMS have been optimized and characterized for the determination of volatile organic compounds from olive oil samples. Both detectors were compared in terms of sensitivity and selectivity, demonstrating that complementary data were obtained and both detectors have proven to be complementary. MS and IMS showed similar selectivity (10 out of 38 compounds were detected by HS-GC-IMS, whereas twelve compounds were detected by HS-GC-MS). However, IMS presented slightly better sensitivity (Limits of quantification (LOQ) ranged between 0.08 and 0.8 µg g-1 for HS-GC-IMS, and between 0.2 and 2.1 µg g-1 for HS-GC-MS). Finally, the potential of both detectors coupled with HS-GC for classification of olive oil samples depending on its quality was investigated. In this case, similar results were obtained when using both HS-GC-MS and HS-GC-IMS equipment (85.71 % of samples of the external validation set were classified correctly (validation rate)) and, although both techniques were shown to be complementary, data fusion did not improve validation results (80.95% validation rate).

OBJECTIVE: Complexities surrounding the manufacture and quality control of nanomedicines become increasingly apparent. This research article offers a case study to investigate how, at the laboratory scale, various stages of liposome and nanoparticle synthesis affect the amount of residual solvent found in the formulations. The objective is to bring insights on the reliability of each of these processes to provide final products which meet regulatory standards and facilitate identifying possible bottleneck early during the development process.
METHODS: The residual solvent at various stages of preparation and purification was measured by headspace gas chromatography. Liposomes were prepared by two different methods with and without solvent. Polymer nanoparticles prepared via nanoprecipitation and purified by ultrafiltration were studied. The effects of purification by size exclusion chromatography and dialysis were also investigated.
RESULTS: The complete removal of residual solvent requires processes which go beyond usual preparation methods.
CONCLUSIONS: This work might prove valuable as a reference for scientists of different fields to compare their own practices and streamline the translation of nanomedicines into efficacious and safe drug products.

Room temperature ionic liquids (ILs) are well established stationary phases (SPs) for gas chromatography (GC) in several fields of applications because of their unique and tunable selectivity, low vapor pressure and volatility, high thermal stability (over 300 °C), and good chromatographic properties. This study is focused on an IL based on a phosphonium derivative (trihexyl(tetradecyl)phosphonium chloride, [P66614+] [Cl-]), previously shown to be suitable as a gas chromatographic SP because of its unique selectivity. In particular, it aims to establish the operative conditions to apply [P66614+][Cl-] to routine analysis of samples containing medium to high volatility analytes with different polarity, organic functional groups and chemical structure. In the first part, the study critically evaluates long term [P66614+][Cl-] column stability and maximum allowable operating temperatures (MAOT). The relatively low MAOT (210 °C) requires the adoption of a dedicated approach for analytes eluting above this temperature based on a suitable combination of efficiency and selectivity, and column characteristics (length, inner diameter and film thickness) and operative conditions. The performance of [P66614+][Cl-] as a GC SP have been validated through the Grob test, a model mixture of 41 compounds of different polarity, structure, and with different organic functional groups in the flavor and fragrance field, a standard mixture of 37 fatty acid methyl esters, some essential oils containing pairs or groups of compounds of different volatility critical to separate in particular peppermint, thyme, oregano, sandalwood and frankincense. The above approach has produced highly satisfactory separations with all of the samples investigated.