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.

BACKGROUND: Omics 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. RESULTS: Α 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. SIGNIFICANCE: The 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.

A flow-batch lab-in-syringe foam microextraction platform for the simultaneous preconcentration and in situ membraneless gas-liquid separation of mercury prior to cold vapor atomic absorption spectrometry.

Herein, the proof-of-concept of a novel lab-in-syringe (LIS) foam microextraction platform is presented as a front-end to cold vapor atomic absorption spectrometry (CVAAS) for the simultaneous preconcentration and membraneless gas-liquid separation (GLS) of inorganic mercury in biological samples. The proposed method is based on the on-line formation of the ammonium pyrrolidine dithiocarbamate complex with mercury that was retained in the pores of polyurethane foam immobilized on the piston of the LIS system. Metal complex elution and in situ mercury vapor generation are accomplished inside the microsyringe in a flow-batch format, while the separation of vapor species is achieved via the membraneless GLS found at the top of the syringe's barrel. Under optimized operation conditions, for 90 s preconcentration time, the limit of detection was 0.02 µg L-1 and the repeatability (RSD) was 3.8% (at the 0.5 µg L-1 concentration level), within a working range extending up to 4.0 µg L-1. The practicality of the novel manifold was demonstrated using the Blue Applicability Grade Index, while the accuracy of the method was evaluated using certified reference materials and spiked samples.

An integrated automatic lab-in-syringe sol-gel coated foam microextraction platform as a front-end to high performance liquid chromatography for the migration studies of bisphenol A.

The proof-of-concept of an integrated automatic foam microextraction lab-in-syringe (FME-LIS) platform coupled to high performance liquid chromatography is presented. Three different sol-gel coated foams were synthesized, characterized, and conveniently packed inside the glass barrel of the LIS syringe pump, as an alternative approach for sample preparation, preconcentration and separation. The proposed system efficiently combines the inherent benefits of lab-in-syringe technique, the good features of sol-gel sorbents, the versatile nature of foams/sponges, as well as the advantages of automatic systems. Bisphenol A (BPA) was used as model analyte, due to the increasing concern for the migration of this compound from household containers. The main parameters that affect the extraction performance of the system were optimized and the proposed method was validated. The limit of detection for BPA were 0.5 and 2.9 µg L-1, for a sample volume of 50 mL and 10 mL, respectively. The intra-day precision was <4.7% and the inter-day precision was <5.1% in all cases. The performance of the proposed methodology was evaluated for the migration studies of BPA using different food simulants, as well as for the analysis of drinking water. Good method applicability was observed based on the relative recovery studies (93-103%).

Design and development of second-generation fabric phase sorptive extraction membranes: Proof-of-concept for the extraction of organophosphorus pesticides from apple juice prior to GC-MS analysis.

In this work, different sol-gel sorbent-coated second-generation fabric phase sorptive extraction (FPSE) membranes were synthesized using titania-based sol-gel precursors. The proposed membranes were tested for their efficiency to extract eleven selected organophosphorus pesticides (OPPs) from apple juice samples. Among the examined materials, sol-gel C18 coated titania-based FPSE membranes showed the highest extraction efficiency. These membranes were used for the optimization and validation of an FPSE method prior to analysis by gas chromatography-mass spectrometry. The detection limits for OPPs ranged between 0.03 and 0.08 ng mL-1. Moreover, the relative standard deviation was < 8.2% and 8.4% for intra-day and inter-day studies, respectively. The relative recoveries were 91-110% (intra-day study) and 90-106% (inter-day study) for all the target analytes, demonstrating good overall method accuracy. Moreover, the novel membranes were reusable at least 5 times. The titania-based membranes were compared to the conventional silica-based membranes and their utilization resulted in higher extraction recoveries.

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.

Designing an "all-in-one" microextraction capsule device for the liquid chromatographic-fluorescence determination of doxorubicin and its metabolites in rat plasma.

In this study, an "all-in-one" microextraction device was designed and fabricated for the extraction of doxorubicin and its two metabolites from rat plasma prior to their determination by high performance liquid chromatography coupled to fluorescence detector. A sol-gel-based sorbent was synthesized in situ and incorporated within two conjoined porous polypropylene tubes together with a cylindrical magnetic bar in order to avoid the need of an external stirring bar. Among other sorbents investigated, the moderately polar sol-gel poly(tetrahydrofuran) was found to be advantageous due to its high affinity toward the target analytes. Systematic investigation of the critical parameters affecting the adsorption and the desorption step was carried out. Due to the "built-in" filtration mechanism of the porous microextraction capsules, the isolation of the analytes was performed directly in the plasma matrix without any previous sample pretreatment (i.e., protein precipitation, centrifugation, etc.). The proposed method was validated in terms of linearity, accuracy, precision, specificity, sensitivity, and stability according to the FDA guidelines. The limits of detection ranged between 1 - 2 ng mL-1 while the lower limits of quantitation of the analytes were calculated as 10 ng mL-1. The accuracy (% relative error) was found within -9.7 - 15.3% under both intra- and inter-day conditions. The precision was better than 13.4% in all cases. ComplexGAPI index was employed to present the green attributes of the developed protocol from the preparation of the microextraction device to the final determination of the analytes. Finally, the applicability of the fabricated stand-alone extraction device was demonstrated in the analysis of the target analytes in rat plasma after intravenous administration of doxorubicin in order to assess its pharmacokinetic profile.

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.

Headspace Solid-Phase Microextraction Followed by Gas Chromatography-Mass Spectrometry as a Powerful Analytical Tool for the Discrimination of Truffle Species According to Their Volatiles.

This study provides the first assessment of the volatile metabolome map of Tuber Aestivum and Tuber Borchii originating from Greece using headspace solid-phase micro-extraction (HS-SPME) coupled to gas chromatography-mass spectrometry (GC-MS). For the extraction of the volatile fraction, the SPME protocol was optimized after examining the effects of sample mass, extraction temperature, and extraction time using the one-variable at-a-time approach (OVAT). The optimum parameters involved the extraction of 100 mg of homogenized truffle for 45 min at 50°C. Overall, 19 truffle samples were analyzed, and the acquired data were normalized and further processed with chemometrics. Agglomerative hierarchical clustering (HCA) was used to identify the groups of the two species. Partial least squares-discriminant analysis (PLS-DA) was employed to develop a chemometric model that could discriminate the truffles according to the species and reveal characteristic volatile markers for Tuber Aestivum and Tuber Borchii grown in Greece.

Fabric phase sorptive extraction combined with gas chromatography-mass spectrometry as an innovative analytical technique for the determination of selected polycyclic aromatic hydrocarbons in herbal infusions and tea samples.

This study presents a fabric phase sorptive extraction (FPSE) protocol for the isolation and preconcentration of four selected polycyclic aromatic hydrocarbons from tea samples and herbal infusions, followed by their separation and quantification by gas chromatography-mass spectrometry (GC-MS). In FPSE, extraction of the target analytes is performed utilizing a flexible fabric substrate that is coated with a highly efficient sol-gel sorbent. In this work, eighteen different FPSE membranes were examined, with the highest extraction recoveries being observed with the sol-gel C18 coated FPSE membrane. The main parameters that influence the adsorption and desorption of the PAHs were optimized and the proposed method was validated. The detection limits and the quantification limits were 0.08-0.17 ng mL-1 and 0.25-0.50 ng mL-1, respectively, for the different target compounds with a 10 mL sample. The relative standard deviations for intra-day and inter-day repeatability were less than 7.9% and 8.5%, respectively. The sol-gel C18 coated FPSE membrane could be used for at least 5 subsequent sample preparation cycles. Finally, the proposed protocol was successfully employed for the determination of PAHs in a wide range of tea and herbal infusion samples.

Green bioanalytical sample preparation: fabric phase sorptive extraction.

Fabric phase sorptive extraction (FPSE) is a recently introduced sample preparation technique that has attracted substantial interest of the scientific community dealing with bioanalysis. This technique is based on a permeable and flexible substrate made of fabric, coated with a sol-gel organic-inorganic sorbent. Among the benefits of FPSE are its tunable selectivity, adjustable porosity, minimized sample preparation workflow, substantially reduced organic solvent consumption, rapid extraction kinetics and superior extraction efficiency, many of which are well-known criteria for Green Analytical Chemistry. As such, FPSE has established itself as a leading green sample preparation technology of 21st century. In this review, we discuss the principal steps for the development of an FPSE method, the main method optimization strategies, as well as the applications of FPSE in bioanalysis for the extraction of a wide range of analytes (e.g., estrogens, benzodiazepines, androgens and progestogens, penicillins, anti-inflammatory drugs, parabens etc.).