Solid-phase Microextraction Arrow Research Articles

Carboxyl-functionalized mesoporous silica-coated solid-phase microextraction Arrow for the determination of six biogenic amines in animal-derived meat

Mesoporous silica materials, SBA-15 and SBA-16, that functionalized with the carboxyl, vinyl and amino groups were synthesized in this study. The spectroscopic analysis evaluated the physicochemical characteristics of these materials. These materials were coated on the arrow-typed solid phase microextraction (SPME Arrow) to extract biogenic amines (BAs). The influences of these materials' functional groups and spatial structure on their extraction efficiency were studied. Carboxyl group modified SBA-15 (SBA-15-C) exhibited the highest extraction capacity to BAs because of the size exclusion effect and the electrostatic interaction. The extraction and desorption parameters of the SPME Arrow method were optimized. The SBA-15-C-SPME Arrow was coupled with a gas chromatography-mass spectrometry (GC-MS) system for the determination of BAs in animal-derived meat samples, which showed good repeatability (RSD<15%), satisfactory linear range (0.01–1 mg kg–1), low limit of detection (0.001–0.004 mg kg–1), and high recovery (84–129%). This method showed excellent applicability for the quantitative and qualitative detection of six BAs in animal-derived meat samples. This study provides new insight into the development of new sorbents with high extraction capacity to BAs for the selective and sensitive determination of BAs in complex meat samples.

A novel headspace solid-phase microextraction arrow method employing comprehensive two-dimensional gas chromatography–mass spectrometry combined with chemometric tools for the investigation of wine aging

BackgroundOmics is used as an analytical tool to investigate wine authenticity issues. Aging authentication ensures that the wine has undergone the necessary maturation and developed its desired organoleptic characteristics. Considering that aged wines constitute valuable commodities, the development of advanced omics techniques that guarantee aging authenticity and prevent fraud is essential. ResultsΑ solid phase microextraction Arrow method combined with comprehensive two-dimensional gas chromatography-mass spectrometry was developed to identify volatiles in red wines and investigate how aging affects their volatile fingerprint. The method was optimized by examining the critical parameters that affect the solid phase microextraction Arrow extraction (stirring rate, extraction time) process. Under optimized conditions, extraction took place within 45 min under stirring at 1000 rpm. In all, 24 monovarietal red wine samples belonging to the Xinomavro variety from Naoussa (Imathia regional unit of Macedonia, Greece) produced during four different vintage years (1998, 2005, 2008 and 2015) were analyzed. Overall, 237 volatile compounds were tentatively identified and were treated with chemometric tools. Four major groups, one for each vintage year were revealed using the Hierarchical Clustering Analysis. The first two Principal Components of Principal Component Analysis explained 86.1% of the total variance, showing appropriate grouping of the wine samples produced in the same crop year. A two-way orthogonal partial least square – discriminant analysis model was developed and successfully classified all the samples to the proper class according to the vintage age, establishing 17 volatile markers as the most important features responsible for the classification, with an explained total variance of 88.5%. The developed prediction model was validated and the analyzed samples were classified with 100% accuracy according to the vintage age, based on their volatile fingerprint. SignificanceThe developed methodology in combination with chemometric techniques allows to trace back and confirm the vintage year, and is proposed as a novel authenticity tool which opens completely new and hitherto unexplored possibilities for wine authenticity testing and confirmation.

Electrospun of functionalized mesoporous UiO-66 as the selective coating of solid phase microextraction Arrow for the determination of nine alkylphenols.

A solid-phase microextraction (SPME) Arrow and high-performance liquid chromatography-UV detector (HPLC-UV, detection at 225nm) based method was developed for the selective determination of nine alkylphenols (APs) in milk. The functionalized mesoporous UiO-66 (4-meso-UiO-66) was utilized as the new coating material, which was synthesized by post-modification of pore-expanded UiO-66-NH2 by an esterification reaction with 4-pentylbenzoic acid. It was fully characterized by X-ray photoelectron spectroscopy (XPS), fourier transformation infrared spectrometry, nitrogen sorption-desorption test, scanning electron microscopy, transmission electron microscopy, and X-ray diffractometer. The characterization results showed the ester groups and benzene rings were introduced into the 4-meso-UiO-66, and the mesoporous structure was predominant in the 4-meso-UiO-66. The extraction mechanism of 4-meso-UiO-66 to APs is the synergistic effect of Zr-O electrostatic interaction and the size exclusion effect resulting from XPS, selectivity test, and nitrogen sorption-desorption test. The electrospinning technique was utilized to fabricate the 4-meso-UiO-66 coated SPME Arrow and polyacrylonitrile (PAN) was used as the adhesive. The mass rate of 4-meso-UiO-66 to PAN and the electrospinning time were evaluated. The extraction and desorption parameters were also studied. The linear range of this method was 0.2-1000μg L-1 with a coefficient of determination greater than 0.9989 under the optimal conditions. The detection limits were 0.05-1μg L-1, the inter-day and intra-day precision (RSD) were 2.8-11.5%, and the recovery was 83.6%-112%. The reusability study showed that the extraction performance of this new SPME Arrow could be maintained after 80 adsorption-desorption cycles. This method showed excellent applicability for the selective determination of APs in milk.

Extraction of volatile organic compounds liberated upon filament extrusion by 3D pen and its comparison with a desktop 3D printer using solid-phase microextraction fiber and Arrow

Desktop 3D printers that operate by the fused deposition modeling (FDM) mechanism are known to release numerous hazardous volatile organic compounds (VOCs) during printing, including some with potential carcinogenic effects. Operating in a similar manner to FDM 3D printers, 3D pens have gained popularity recently from their ability to allow users to effortlessly draw in the air or create various 3D printed shapes while handling the device like a pen. In contrast to numerous modern 3D printers, 3D pens lack their own ventilation systems and are often used in settings with minimum airflow. Their operation makes users more vulnerable to VOC emissions, as the released VOCs are likely to be in the breathing zone. Consequently, monitoring VOCs released during the use of 3D pens is crucial. In this study, VOCs liberated while extruding acrylonitrile butadiene styrene (ABS) filaments from a 3D pen were measured by solid-phase microextraction (SPME) combined with gas chromatography/mass spectrometry (GC/MS). SPME was investigated using the traditional fiber and Arrow geometries with the DVB/Carbon WR/PDMS sorbent while four different brands of ABS filaments—Amazon Basics, Gizmodork, Mynt 3D, and Novamaker—were used with the 3D pen. Heatmap analysis showed differentiation among these brands based on the liberated VOCs. The nozzle temperature and printing speed were found to affect the number and amount of released VOCs. This study goes a step further and presents for the first time a comparison between 3D pen and a desktop 3D printer based on liberated VOCs. Interestingly, the findings reveal that the 3D pen releases a greater number and amount of VOCs compared to the printer. The amounts of liberated VOCs, as indicated by the corresponding chromatographic peak areas, were found to be 1.4 to 62.6 times higher for the 3D pen compared to the 3D printer when using SPME Arrow.

Selective Sampling to and Desorption from Single Solid-Phase Microextraction Arrow Fiber for Replicative and Quantitative Analysis.

New analytical functionality is demonstrated with an enclosed interface that joins a solid phase microextraction (SPME) device, a direct analysis in real time (DART) probe, and a high-resolution mass spectrometer. With a single 20 mm long SPME Arrow, the interface is able to perform five discrete DART analyses on different areas of the same fiber in 1 min of practical operation time. Three-fiber replicates for 15 runs total produce 15% or better center of variance (CV) values for both volatile headspace sampling and direct immersion sampling of a solvated analyte. Chemometric analysis of rapidly acquired headspace data is able to distinguish volatile profiles. Selective desorption within the interface also confers the ability to selectively sample to discrete areas of a fiber, and three different headspace samples or five different liquid samples can be acquired and differentiated with one Arrow. A five-point standard addition curve is constructed to measure the concentration of the solvated analyte. Unmodified commercial components of the analysis system include the fiber itself, the Orbitrap and AccuTOF mass spectrometer platforms, and the conditioning gas chromatograph inlet. Machine diagrams for the SPME-DART interface and Arrow fiber holder are included.

Method Comparison for the Identification and Characterization of Odorants from Scots Pine (Pinus sylvestris L.) and Oriented Strand Boards (OSB) Made Thereof by GC-MS and GC-FID/O Using Different Headspace Techniques

Volatile organic compounds (VOCs) from wood and wood composites are important contributors to odor profiles of indoor environments and can significantly influence human health and well-being. GC-MS/FID and gas chromatography (GC) with olfactometric detection (GC-O) are employed for the identification and characterization of odorants. Four different sample preparation methods are evaluated on wood strands and isocyanate adhesive–based oriented strand boards (OSBs) made from Pinus sylvestris L.: among these, dynamic headspace extraction thermal desorption ((dynamic) HS-TD), head space solid phase microextraction (HS-SPME), head space solid phase microextraction Arrow (HS-SPME Arrow), and liquid injection of a CH2Cl2 solvent extract. The olfactometric investigation revealed over 30 odor-active substances of cyclic and acyclic monoterpene, monoterpenoid ketone, monoterpenoid aldehyde, monoterpenoid alcohol, monoterpenoid ester, aliphatic aldehyde, alcohol, and acid and phenolic chemistry. Compared to liquid injection, (dynamic) HS-TD was found to result in a similar number of odorants (20 vs. 24), whereas HS SPME Arrow shows good performance with minimal instrumental effort, notably for monoterpene and aldehyde compounds. Native wood vs. OSB showed high concentrations of saturated and unsaturated aldehydes for the wood board sample. These findings demonstrate the capability of headspace methods for odorant detection and their suitability for standardization towards a database for wood and wood composites.

Characterization of a hydrophilic-lipophilic balanced SPME material for enrichment of analytes with different polarities from aqueous samples

The choice of the extraction material is a critical step in solid-phase microextraction (SPME), especially the extraction of analytes which strongly differ in their polarity is challenging. This study is intended to give first insights into the headspace extraction of analytes with large differences in polarity by using a novel hydrophilic-lipophilic-balanced (HLB) SPME material with different particle sizes (5 µm, 5 + 30 µm, and 30 µm) in classical SPME, as well as SPME arrow format. The obtained results were compared to conventional and already established divinylbenzene carbon wide-range polydimethylsiloxane (DVB-CWR-PDMS) and PDMS SPME arrow fibers. The chosen model analytes toluene, indole, phenol, anisole, o-xylene, naphthalene, 2-heptanone, n-dodecane, and lindane are assigned to different substance classes with Kaw values ranging from -5.0–2.5 and Kow values from 1.5 to 7.5. The highest amount of the analytes was extracted by the HLB 5 + 30 µm arrow and the HLB 5 µm arrow, whereas the HLB SPME with a six times smaller phase volume compared to an SPME arrow, performed almost as well as the DVB-CWR-PDMS arrow. The 8-point calibration with the 5 + 30 µm HLB SPME arrow in the range of 5–70 µg L−1 of the analytes showed good linearity with R2 values ranging from 0.9765 to 0.9982, MDLs from 0.9 to 6.2 µg L−1 and RSDs from 2 to 31 %. For all of the observed analytes, the HLB material performed better than the conventional extraction materials and has great potential to replace the conventional extraction materials in many applications.

A New Perspective on SPME and SPME Arrow: Formaldehyde Determination by On-Sample Derivatization Coupled with Multiple and Cooling-Assisted Extractions.

Formaldehyde (FA) is a toxic compound and a human carcinogen. Regulating FA-releasing substances in commercial goods is a growing and interesting topic: worldwide production sectors, like food industries, textiles, wood manufacture, and cosmetics, are involved. Thus, there is a need for sensitive, economical, and specific FA monitoring tools. Solid-phase microextraction (SPME), with O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBHA) on-sample derivatization and gas chromatography, is proposed for FA monitoring of real-life samples. This study reports the use of polydimethylsiloxane (PDMS) as a sorbent phase combined with innovative commercial methods, such as multiple SPME (MSPME) and cooling-assisted SPME, for FA determination. Critical steps, such as extraction and sampling, were evaluated in method development. The derivatization was performed at 60 °C for 30 min, followed by 15 min sampling at 10 °C, in three cycles (SPME Arrow) or six cycles (SPME). The sensitivity was satisfactory for the method's purposes (LOD-LOQ at 11-36 ng L-1, and 8-26 ng L-1, for SPME and SPME Arrow, respectively). The method's linearity ranges from the lower LOQ at trace level (ng L-1) to the upper LOQ at 40 mg L-1. The precision range was 5.7-10.2% and 4.8-9.6% and the accuracy was 97.4% and 96.3% for SPME and SPME Arrow, respectively. The cooling MSPME set-up applied to real commercial goods provided results of quality comparable to previously published data.

Assessment of physicochemical properties of sorbent materials in passive and active sampling systems towards gaseous nitrogen-containing compounds

The adsorption and desorption behavior of volatile nitrogen-containing compounds in vapor phase by solid-phase microextraction Arrow (SPME-Arrow) and in-tube extraction (ITEX) sampling systems, were investigated experimentally using gas chromatography-mass spectrometry. Three different SPME-Arrow coating materials, DVB/PDMS, MCM-41, and MCM-41-TP and two ITEX adsorbents, TENAX-GR and MCM-41-TP were compared to clarify the selectivity of the sorbents towards nitrogen-containing compounds. In addition, saturated vapor pressures for these compounds were estimated, both experimentally and theoretically. In this study, the adsorption of nitrogen-containing compounds on various adsorbents followed the Elovich model well, while a pseudo-first-order kinetics model best described the desorption kinetics. Pore volume and pore sizes of the coating sorbents were essential parameters for the determination of the adsorption performance for the SPME-Arrow sampling system. MCM-41-TP coating with the smallest pore size gave the slowest adsorption rate compared to that of DVB/PDMS and MCM-41 in the SPME-Arrow sampling system. Both adsorbent and adsorbate properties, such as hydrophobicity and basicity, affected the adsorption and desorption kinetics in SPME-Arrow system. The adsorption and desorption rates of studied C6H15N isomers in the MCM-41 and MCM-41-TP sorbent materials of SPME-Arrow system were higher for dipropylamine and triethylamine (branched amines) than for hexylamine (linear chain amines). DVB/PDMS-SPME-Arrow gave fast adsorption rates for the aromatic-ringed pyridine and o-toluidine. All studied nitrogen-containing compounds demonstrated high desorption rates with DVB/PDMS-SPME-Arrow. Chemisorption and physisorption were the sorption mechanisms in MCM-41- and MCM-41-TP- SPME-Arrow, but additional experiments are needed to confirm this. An active sampling technique ITEX gave comparable adsorption and desorption rates on the selective MCM-41-TP and universal TENAX-GR sorbent materials for all the compounds studied. Vapor pressures of nitrogen-containing compounds were experimentally estimated by using retention index approach and these values were compared with the theoretical ones, calculated using the COnductor-like Screening MOdel for Real Solvent (COSMO-RS) model. Both values agreed well with those found in the literature proving that these methods can be successfully used in predicting VOC's vapor pressures, e.g. for the formation of secondary organic aerosols.

Evaluation of VOCs from fungal strains, building insulation materials and indoor air by solid phase microextraction arrow, thermal desorption–gas chromatography-mass spectrometry and machine learning approaches

Solid phase microextraction Arrow and thermal desorption–gas chromatography–mass spectrometry allowed the collection and evaluation of volatile organic compounds (VOCs) emitted by fungal cultures from building insulation materials and in indoor air. Principal component analysis, linear discriminant analysis and supported vector machine were used for visualization and statistical assessment of differences between samples. In addition, a screening tool based on the soft independent modelling of class analogies (SIMCA) was developed for identification of fungal contamination of indoor air. Ten different fungal strains, incubated under ambient and microaerophilic conditions, were analyzed for time period ranging from 5 to 29 days after inoculation resulting in a total of 140 samples. In addition, the effect of additives on the fungal growing media was studied. The total number of compounds and concentration values were used for the evaluation of the results. Clear differences were observed for VOC profiles emitted by different fungal strains by exploiting long chain alcohols (3-octanol, 1-hexanol and 2-octen-1-ol) and sesquiterpenes (farnesene, cuprene). The analysis of glass-wool and cellulose based building insulation materials (3 samples) gave clear differences, mainly for oxygenated compounds (ethyl acetate and hexanal) and benzenoids (benzaldehyde). Moreover, the comparison of indoor air and insulation materials collected from a house with fungal indoor air problems indicated that 42% of the VOCs were found in both samples. The analysis of 52 indoor air samples demonstrated clear differences in their VOC profiles, especially for hydrocarbons, and between control (44 samples) and indoor air problem houses (8 samples). Finally, the SIMCA model enabled to recognize differences between control and fungi contaminated houses with a prediction capacity over 84%.

Hydrophobic Mesoporous Silica-Coated Solid-Phase Microextraction Arrow System for the Determination of Six Biogenic Amines in Pork and Fish.

In this study, a functionalized mesoporous silica-coated solid-phase microextraction (SPME) Arrow system was developed for the enrichment of six biogenic amines (BAs) from pork and fish samples before gas chromatographic separation with a mass spectrometer as a detector. MCM-41 was utilized as the substrate material and thereby functionalized by titanate and sodium dodecyl sulfate to adjust its surface acidity and hydrophobicity, respectively. The functionalized MCM-41 (named as MCM-T-H) was coated on a bare SPME Arrow using the dipping method and polyacrylonitrile was used as the adhesive. The extraction capacity and selectivity of the MCM-T-H-SPME Arrow for six kinds of derivatized BAs were studied and compared with commercial SPME Arrows. Experimental parameters, e.g., sample volume, derivatization reagent amount, extraction time, and desorption time, which have a dramatic effect on SPME Arrow pretreatment, were optimized. Acidity enhanced MCM-T-H coating showed a much higher affinity to derivatized BAs compared to a commercial SPME Arrow in terms of extraction capacity. In addition, hydrophobicity modification significantly reduced the interference of water molecules on the interaction between MCM-T-H and the derivatized BAs. The MCM-T-H-SPME Arrow showed efficient separation and enrichment capacity for derivatized BAs from complex matrices and therefore, the sample pretreatment time was saved. According to the experimental results, the optimal condition was to add 10 μL derivatization reagent to a 10 mL sample and maintain an agitation speed of 1250 r min-1. The MCM-T-H-SPME showed excellent reproducibility (RSD < 9.8%) and fast adsorption kinetics (30 min) and desorption kinetics (5 min) for derivatized BAs under optimal conditions. In summary, the MCM-T-H-SPME Arrow based method was employed for accurate monitoring of the variations of BAs in pork and fish, and good results were achieved.

Solid-phase microextraction Arrow combined with comprehensive two-dimensional gas chromatography-mass spectrometry for the elucidation of the volatile composition of honey samples.

In this work, a solid-phase microextraction (SPME) Arrow method combined with comprehensive two-dimensional gas chromatography-mass spectrometry (GC × GC-MS) was developed for the elucidation of the volatile composition of honey samples. The sample preparation protocol was optimized to ensure high extraction efficiency of the volatile organic compounds (VOCs) which are directly associated with the organoleptic properties of honey and its acceptance by the consumers. Following its optimization, SPME Arrow was compared to conventional SPME in terms of sensitivity, precision, and number of extracted VOCs. The utilization of SPME Arrow fibers enabled the determination of 203, 147, and 149 compounds in honeydew honey, flower honey, and pine honey, respectively, while a significantly lower number of compounds (124, 94, and 111 for honeydew honey, flower honey, and pine honey, respectively) was determined using conventional SPME. At the same time, the utilization of SPME Arrow resulted in enhanced sensitivity and precision. All things considered, SPME Arrow and GC × GC-MS can be considered as highly suitable for the elucidation of the volatile composition of complex food samples resulting in high sensitivity and separation efficiency.

Optimization and automation of rapid and selective analysis of fatty acid methyl esters from aqueous samples by headspace SPME arrow extraction followed by GC–MS/MS analysis

The analysis of fatty acid methyl esters (FAMEs) is of high relevance for monitoring and control of various industrial processes and biological systems. In this study, a novel, green analytical approach for the determination of 24 FAMEs from aqueous samples is proposed, which is based on a headspace solid-phase microextraction (SPME) arrow followed by gas chromatography coupled to tandem mass spectrometry (GC–MS/MS). The method was substantially accelerated to a run time of 44 min per sample by thorough optimization and automation of the relevant parameters. The limiting parameters, mostly based on expediting equilibrium attainment, were found to be parameters of extraction: material, pH, time, and temperature, which were optimized to divinylbenzene polydimethylsiloxane (DVB-PDMS), pH 2, 20 min, and 70 °C, respectively. The optimization and automation of the method led to low method detection limits (9–437 ng L−1) and high selectivity. Evaluation of the method on real samples was done by analyzing the aqueous phase of a bioreactor, whereby the matrix effect could be greatly reduced due to dilution and headspace sampling. The rapid, sensitive, selective, and matrix-reduced approach is found to be not only a novel method for water analysis but is promising for further applications, e.g., with solid and gaseous samples containing FAMEs.Graphical abstract

Exploring the volatile profile of whiskey samples using solid-phase microextraction Arrow and comprehensive two-dimensional gas chromatography-mass spectrometry

We present a novel sample preparation method for the extraction and preconcentration of volatile organic compounds from whiskey samples prior to their determination by comprehensive two-dimensional gas chromatography (GC × GC) coupled to mass spectrometry (MS). Sample preparation of the volatile compounds, important for the organoleptic characteristics of different whiskeys and their acceptance and liking by the consumers, is based on the use of the solid-phase microextraction (SPME) Arrow. After optimization, the proposed method was compared with conventional SPME regarding the analysis of different types of whiskey (i.e., Irish whiskey, single malt Scotch whiskey and blended Scotch whiskey) and was shown to exhibit an up to a factor of six higher sensitivity and better repeatability by a factor of up to five, depending on the compound class. A total of 167 volatile organic compounds, including terpenes, alcohols, esters, carboxylic acids, ketones, were tentatively-identified using the SPME Arrow technique, while a significantly lower number of compounds (126) were determined by means of conventional SPME. SPME Arrow combined with GC × GC-MS was demonstrated to be a powerful analytical tool for the exploration of the volatile profile of complex samples, allowing to identify differences in important flavour compounds for the three different types of whiskey investigated.

Investigating volatiles as the secondary metabolome of Piper methysticum from root powder and water extracts using comprehensive two-dimensional gas chromatography

Ethnopharmacological relevanceKava (Piper methysticum G. Forst) is a plant grown in the Pacific that is used in traditional medicines. The roots are macerated and powdered for consumption as a beverage in social settings as well as in ceremonies. Other types of preparations can also be used as traditional medicines. There has been an increase in demand for kava as there is continued traditional use and as it is becoming utilized more both socially and medicinally outside of Oceania. Currently, most research of this plant has focused on bioactive kavalactones and flavokawains, and there are few studies focusing on the other compounds that kava contains, such as volatile and semivolatile components. Aim of the studyThis study investigated the kava volatile organic compound (VOC) profile from nine different commercially available samples of dried, powdered kava root sourced across the Pacific region. Materials and methodsThe headspace above the kava samples was analyzed, both from the root powder as originally purchased and by performing a scaled-down extraction into water mimicking traditional preparation of the beverage. The headspace of each sample was extracted using solid-phase microextraction arrow (SPME Arrow), followed by analysis using comprehensive two-dimensional gas chromatography – quadrupole mass spectrometry/flame ionization detection (GC×GC-qMS/FID). The superior peak capacity of GC×GC was invaluable in effectively separating the complex mixture of compounds found in all samples, which enabled improved monitoring of minor differences between batches. ResultsDry root powder samples contained high levels of β-caryophyllene while water extracted samples showed high levels of camphene. Many alcohols, aldehydes, ketones, terpenes, terpenoids, and aromatics were also characterized from both types of samples. All water extracted samples from the different brands followed similar trends in terms of compounds being detected or not. Additional major compounds found in water extracts included benzaldehyde, hexanal, methoxyphenyloxime, camphor, limonene, 1-hexanol, endoborneol, and copaene. While some samples could be differentiated based on brand, samples did not group by purported geographic origin. ConclusionsThis study provides foundational data about a different subset of compounds within kava than previous research has studied, and also informs the community of the compounds that transfer into the consumed beverage during the traditional means of preparing kava.

Characterization of N,O-heterocycles in green tea during the drying process and unraveling the formation mechanism

N,O-Heterocycles play an important role in the characteristic flavor of green tea owing to their strong odors and low odor thresholds. In this study, a rapid and sensitive method was developed to determine seven N,O-heterocycles in green tea by using headspace solid-phase microextraction Arrow (HS-SPME-Arrow) coupled with gas chromatography-triple quadrupole-tandem mass spectrometry. The HS-SPME-Arrow extraction was performed using a Carbon WR SPME Arrow fiber. Good linear ranges (5–1000 ng/mL) were obtained, with correlation coefficients (R2) higher than 0.99 for all target compounds. LODs and LOQs were in the range of 0.44–5.12 and 1.48–17.04 μg/kg, respectively. The recoveries of seven N,O-heterocycles were found to vary from 83.1% to 117.3%, with RSDs being lower than 10%. The dynamic changes of N,O-heterocycles during the drying process revealed that 25- and 40-min-long drying processes were key transition points. Furfural could be used as a key indicator compound for evaluating the extent of the drying. Moreover, furfural and 2-methylfuran revealed a significant positive correlation with proline (p < 0.05). The possible formation mechanisms of N,O-heterocycles were further elaborated by simulated Maillard reactions. Our results provide a theoretical foundation for the improvement and directional regulation of aroma quality of green tea during manufacturing.

Untargeted analysis of microbial metabolites and unsaturated fatty acids in salmon via hydrophilic-lipophilic balanced solid-phase microextraction arrow

The ability to detect spoilage and the nutrient content of salmon is critical for ensuring food safety and determining market value. In this paper, we document the development of a hydrophilic-lipophilic balanced solid-phase microextraction arrow that offers better extraction performance than two other commercial devices. The devices were also compared using two operational models: headspace microextraction and direct immersion. The multidimensional statistical analysis and heatmap analysis for the headspace microextractions showed that the content levels of volatile metabolites including hydrocarbons, alcohols, ketones, acids, amino acids, and ethers increased with longer storage times, indicating an increase in the activity of spoilage-associated bacteria, such as gram-negative bacteria. For the direct immersion tests, important nutrients, including lipids, sterols, and squalene, were directly extracted from the salmon fillets with high efficiency. Thus, the developed method provides a simple and easy time-domain monitoring strategy for testing the freshness and quality of salmon for consumers.

Solventless Microextration Techniques for Pharmaceutical Analysis: The Greener Solution.

Extensive efforts have been made in the last decades to simplify the holistic sample preparation process. The idea of maximizing the extraction efficiency along with the reduction of extraction time, minimization/elimination of hazardous solvents, and miniaturization of the extraction device, eliminating sample pre- and posttreatment steps and reducing the sample volume requirement is always the goal for an analyst as it ensures the method’s congruency with the green analytical chemistry (GAC) principles and steps toward sustainability. In this context, the microextraction techniques such as solid-phase microextraction (SPME), stir bar sorptive extraction (SBSE), microextraction by packed sorbent (MEPS), fabric phase sorptive extraction (FPSE), in-tube extraction dynamic headspace (ITEX-DHS), and PAL SPME Arrow are being very active areas of research. To help transition into wider applications, the new solventless microextraction techniques have to be commercialized, automated, and validated, and their operating principles to be anchored to theory. In this work, the benefits and drawbacks of the advanced microextraction techniques will be discussed and compared, together with their applicability to the analysis of pharmaceuticals in different matrices.

INNOVATIVE GAS CHROMATOGRAPHIC DETERMINATION OF FORMALDEHYDE BY MINIATURIZED EXTRACTION AND ON-FIBER DERIVATIZATION, VIA SPME AND SPME ARROW

Formaldehyde (FA) is a carbonyl compound, ubiquitous in the environment and among the most widespread pollutants: it has exhibited toxic properties and is classified as a human carcinogen. FA is released from several sources, both temporary (e.g., combustion processes) and permanent (e.g., building products). This work proposes an innovative fully-automated application of headspace solid-phase microextraction (SPME) with on-fiber derivatization for the analysis of airborne FA emitted from liquid solutions or solid manufacts, in static mode, via gas chromatography-mass spectrometry. The method was tested in a wide range of airborne FA concentrations, using SPME and SPME Arrow fibers: the inter-day LOD and LOQ for SPME and SPME Arrow were evaluated, resulting in 0.072 and 0.215 ppm and 0.014 and 0.042 ppm, respectively. Moreover, other conventional detectors, such as Electron Capture Detector (ECD), Thermoionic Specific Detector (TSD), Photoionization Detector (PID), and Flame Ionization Detector (FID), were tested to set an analytical method to meet different requirements. The sensitivity and linearity of PID, FID and MS were comparable, while TSD and ECD were not suitable for the developed method, due to issues of response or linearity. MS results to be the most suitable and perfoming detector, however PID and FID result to be cheaper valid alternatives.

Quantitative analysis and spatial and temporal distribution of volatile organic compounds in atmospheric air by utilizing drone with miniaturized samplers

Our second generation air sampling drone system, allowing the simultaneous use of four solid phase microextraction (SPME) Arrow and four in-tube extraction (ITEX) units, was employed for collection of atmospheric air samples at different spatial and temporal dimensions. SPME Arrow coated with two types of materials and ITEX with 10% polyacrylonitrile as sorbent were used to give a more comprehensive chemical characterization of the collected air samples. Before field sampling, miniaturized samplers went through quality control and assurance in terms of reproducibility (RSD ≤14.1%, N = 4), equilibrium time (≥10 min), breakthrough volume (1.8 L) and storage time (up to 48 h). 128 air samples were collected under optimal sampling conditions from July to September 2019 at the SMEAR II station and Qvidja farm, Finland. 347 VOCs were identified in the air samples either on-site or in the laboratory by thermal desorption gas chromatography - mass spectrometry, and they were quantified/semiquantified using Partial Least Squares Regression models. Individual models were developed for the different coatings and packing materials using gas phase standards obtained by an automatic permeation system. Average gas phase VOC concentrations ranged from 0.1 (toluene, the SMEAR II station) to 680 ng L−1 (acetone, Qvidja farm). Average VOC concentrations in aerosols ranged from 0.1 (1,4-cyclohexadiene, the SMEAR II station) to 2287 ng L−1 (megastigma-4,6,8-triene, Qvidja farm). Clear differences in results were seen for samples collected at the SMEAR II station and Qvidja farm, between VOC compositions in gas phase and aerosols, and between the sampling site and height.