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.

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.

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.

Magnet integrated fabric phase sorptive extraction as a stand-alone extraction device for the monitoring of benzoyl urea insecticides in water samples by HPLC-DAD.

Benzoyl urea insecticides are a class of pesticides used in agriculture for the inhibition of chitin synthesis in pests. These compounds are persistent in environmental samples, and thus their monitoring is necessary to avoid detrimental effects to human health and the environment. Magnet integrated fabric phase sorptive extraction (MI-FPSE) is a recently introduced sample preparation technique that combines sample stirring and analyte extraction into one stand-alone device. However, the applicability and the potential benefits of this technique in environmental analysis remain unexplored. In the present study, MI-FPSE was employed for the first time for the extraction and preconcentration of benzoyl urea insecticides (i.e., diflubenzuron, triflumuron, hexaflumuron, lufenuron and chlorfluazuron) from environmental water samples prior to their determination by high performance liquid chromatography-diode array detection (HPLC-DAD). The main factors affecting the performance of the proposed methodology were thoroughly investigated and optimized and the MI-FPSE-HPLC-DAD method was validated. The proposed method enabled the handling of relatively high sample quantity resulting in high preconcentration factors (501 and 731) and good sensitivity. Under optimum conditions, the limits of detection and the limits of quantification for the benzoyl urea insecticides were 0.06 ng mL-1 and 0.20 ng mL-1, respectively. Moreover, the relative standard deviations were less than 6.1% for intra-day study and less than 8.2% for inter-day study showing good method precision. After its validation, the herein developed method was successfully employed for the analysis of tap, mineral, river, and lake water samples. In addition, the ComplexGAPI index was used to present the green potential of developed method from the step of MI-FPSE device preparation to final determination. All things considered, MI-FPSE could potentially serve as an efficient tool for the monitoring of pollutants in environmental analysis.

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.

Exploring sol-gel zwitterionic fabric phase sorptive extraction sorbent as a new multi-mode platform for the extraction and preconcentration of triazine herbicides from juice samples.

Triazine herbicides are a class of common pesticides which are widely used to control the weeds in many agricultural crops. Although many studies have described methodologies for the determination of triazine herbicides in aqueous samples, the attention given to agricultural crops and their products is far more limited. In this study, a novel sol-gel zwitterionic multi-mode fabric phase sorptive extraction (FPSE) platform was developed for the matrix clean-up, extraction and preconcentration of five triazine herbicides from fruit juice samples prior to their determination by high performance liquid chromatography-diode array detection (HPLC-DAD). The novel zwitterionic multi-mode sorbent was characterized and its performance for fruit juice analysis was evaluated. Compared to other sol-gel sorbents, the novel zwitterionic sorbent helped cleaning all the acidic interferences from fruit juices. The herein reported FPSE protocol was optimized and validated. Under optimum conditions, the FPSE method showed good accuracy, precision and sensitivity. The limits of detection and limits of quantification for all analytes were 0.15 ng mL-1 and 0.50 ng mL-1, respectively. The enhancement factors of this method ranged between 36.7 and 51.8. The relative standard deviation for intra-day precision was below 5.6% and for inter-day precision was below 8.8%. Finally, the proposed FPSE-HPLC-DAD method was successfully employed for the analysis of various fruit juice samples.

Recent advances in the extraction of triazine herbicides from water samples.

Pesticides are excessively used in agriculture to improve the quality of crops by eliminating the negative effects of pests. Among the different groups of pesticides, triazine pesticides are a group of compounds that contain a substituted C3 H3 N3 heterocyclic ring, and they are widely used. Triazine pesticides can be dangerous for humans as well as for the aquatic environment because of their high toxicity and endocrine disrupting effect. However, the concentration of these chemical compounds in water samples is low. Moreover, other compounds that may exist in the water samples can interfere with the determination of triazine pesticides. As a result, it is important to develop sample preparation methods that provide preconcentration of the target analyte and sufficient clean-up of the samples. Recently, a wide variety of novel microextraction and miniaturized extraction techniques (e.g., solid-phase microextraction and liquid-phase microextraction, stir bar sorptive extraction, fabric phase sorptive extraction, dispersive solid-phase extraction, and magnetic solid-phase extraction) have been developed. In this review, we aim to discuss the recent advances regarding the extraction of triazine pesticides from environmental water samples. Emphasis will be given to novel sample preparation methods and novel sorbents developed for sorbent-based extraction techniques.

Designing a moderately hydrophobic sol-gel monolithic Carbowax 20 M sorbent for the capsule phase microextraction of triazine herbicides from water samples prior to HPLC analysis.

The determination of triazine herbicides in water samples is of utmost importance, due to their persistence and excessive use. However, since the concentration of triazine pesticides in real samples is low, an extraction/preconcentration step is typically required. Capsule phase microextraction (CPME) is a recently introduced sample preparation technique in which highly efficient sol-gel sorbents are encapsulated in a tubular polymer membrane. This particular design integrates the filtration and stirring mechanism into one extraction device, enabling the application of CPME for in situ sampling. In this study, CPME coupled to high performance liquid chromatography-diode array detection (HPLC-DAD) was employed for the first time for the determination of six triazine herbicides (i.e., simazine, cyanazine, atrazine, prometryn, terbuthylazine and propazine) in water samples. Microextraction capsules containing a moderately hydrophobic sol-gel Carbowax 20 M sorbent provided the highest extraction efficiency towards the examined pesticides. The main parameters affecting the adsorption and desorption steps of the CPME procedure were investigated and optimized. Under the selected conditions, limits of detection (signal/noise = 3.3) were 0.15 ng mL-1 for the target analytes. Moreover, the relative standard deviation for the within-day and between-days repeatability were less than 7.2% and 9.9%, respectively. The method was successfully applied to the analysis of mineral water, tap water, rainwater and lake water samples. The reported protocol could overcome the need for sample filtration prior to the sample preparation of the water samples, resulting in simplification of the overall sample handling, improved data quality with minimal loss of analytes and reduced sample preparation cost.

Multi-Element Analysis Based on an Automated On-Line Microcolumn Separation/Preconcentration System Using a Novel Sol-Gel Thiocyanatopropyl-Functionalized Silica Sorbent Prior to ICP-AES for Environmental Water Samples.

A sol-gel thiocyanatopropyl-functionalized silica sorbent was synthesized and employed for an automated on-line microcolumn preconcentration platform as a front-end to inductively coupled plasma atomic emission spectroscopy (ICP-AES) for the simultaneous determination of Cd(II), Pb(II), Cu(II), Cr(III), Co(II), Ni(II), Zn(II), Mn(II), Hg(II), and V(II). The developed system is based on an easy-to-repack microcolumn construction integrated into a flow injection manifold coupled directly to ICP-AES's nebulizer. After on-line extraction/preconcentration of the target analyte onto the surface of the sorbent, successive elution with 1.0 mol L-1 HNO3 was performed. All main chemical and hydrodynamic factors affecting the effectiveness of the system were thoroughly investigated and optimized. Under optimized experimental conditions, for 60 s preconcentration time, the enhancement factor achieved for the target analytes was between 31 to 53. The limits of detection varied in the range of 0.05 to 0.24 µg L-1, while the limits of quantification ranged from 0.17 to 0.79 µg L-1. The precision of the method was expressed in terms of relative standard deviation (RSD%) and was less than 7.9%. Furthermore, good method accuracy was observed by analyzing three certified reference materials. The proposed method was also successfully employed for the analysis of environmental water samples.

Green Bioanalytical Applications of Graphene Oxide for the Extraction of Small Organic Molecules.

Bioanalysis is the scientific field of the quantitative determination of xenobiotics (e.g., drugs and their metabolites) and biotics (e.g., macromolecules) in biological matrices. The most common samples in bioanalysis include blood (i.e., serum, plasma and whole blood) and urine. However, the analysis of alternative biosamples, such as hair and nails are gaining more and more attention. The main limitations for the determination of small organic compounds in biological samples is their low concentration in these matrices, in combination with the sample complexity. Therefore, a sample preparation/analyte preconcentration step is typically required. Currently, the development of novel microextraction and miniaturized extraction techniques, as well as novel adsorbents for the analysis of biosamples, in compliance with the requirements of Green Analytical Chemistry, is in the forefront of research in analytical chemistry. Graphene oxide (GO) is undoubtedly a powerful adsorbent for sample preparation that has been successfully coupled with a plethora of green extraction techniques. GO is composed of carbon atoms in a sp2 single-atom layer of a hybrid connection, and it exhibits high surface area, as well as good mechanical and thermal stability. In this review, we aim to discuss the applications of GO and functionalized GO derivatives in microextraction and miniaturized extraction techniques for the determination of small organic molecules in biological samples.

Exploring the volatile metabolome of conventional and organic walnut oils by solid-phase microextraction and analysis by GC-MS combined with chemometrics.

It is challenging to establish a correlation between the agronomical practices and the volatile profile of high-value agricultural products. In this study, the volatile metabolome of walnut oils from conventional and organic farming type was explored by HS-SPME-GC-MS. The SPME protocol was optimized after evaluating the effects of extraction time, extraction temperature, and sample mass. The optimum parameters involved the extraction of 0.500 g walnut oil at 40 °C within 60 min. Twenty Greek walnut oils produced with conventional and organic farming were analyzed and 41 volatile compounds were identified. The determined compounds were semi-quantified, and further processed with chemometrics. Agglomerative hierarchical clustering (AHC) and principal component analysis (PCA) were used. A robust classification model was developed using sparse partial least squares-discriminant analysis (sPLS-DA) for the discrimination of walnut oils into conventional and organic, establishing volatile markers that could be used to guarantee the type of farming.

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.).

Rare Earths as Authenticity Markers for the Discrimination of Greek and Turkish Pistachios Using Elemental Metabolomics and Chemometrics.

Pistachios are a nutritionally beneficial food source widely consumed all over the world. Pistachios exhibit high content of antioxidants, vitamins and other beneficial micronutrients, including nutrient elements and rare earth elements (REEs). Considering that the concentration of REEs depends on the climate and soil characteristics that vary among different geographical regions, REEs could constitute markers responsible for the geographical discrimination of this nut type. In this study, Greek pistachios with a protected designation of origin (PDO) label from Aegina Island and Fthiotida and Turkish pistachios from Adana were analyzed with inductively coupled plasma mass spectrometry (ICP-MS) to assess their REE profile. La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb were determined and quantified. The quantification results were further analyzed using the main effect plot, permutational analysis of variance (PERMANOVA), nonmetric multidimensional scaling (nMDS), principal component analysis (PCA) and hierarchical clustering (HCA) to investigate the similarities between the pistachios. A decision tree (DT) was developed for the classification of pistachios according to their geographical origin proving to be a promising and reliable tool for verifying the authenticity of food products on the basis of their REE profile.

On the use of metal-organic frameworks for the extraction of organic compounds from environmental samples.

The determination of trace metals and organic contaminants in environmental samples, such as water, air, soil, and sediment, is until today a challenging process for the analytical chemistry. Metal-organic frameworks (MOFs) are novel porous nanomaterials that are composed of metal ions and an organic connector. These materials are gaining more and more attention due to their superior characteristics, such as high surface area, tunable pore size, mechanical and thermal stability, luminosity, and charge transfer ability between metals and ligands. Among the various applications of MOFs are gas storage, separation, catalysis, and drug delivery. Recently, MOFs have been successfully introduced in the field of sample preparation for analytical chemistry and they have been used for sample pretreatment of various matrices. This review focuses on the applications of MOFs as novel adsorbents for the extraction of organic compounds from environmental samples.

Magnetic solid-phase extraction of caffeine from surface water samples with a micro-meso porous activated carbon/Fe3O4 nanocomposite prior to its determination by GC-MS.

A novel micro-meso porous activated carbon/Fe3O4 (Bm) composite was synthesized from the active charcoal precursor BAX-1500 and used in the magnetic solid-phase extraction (MSPE) of caffeine prior to its determination by gas chromatography-mass spectrometry (GC-MS). The main factors affecting the extraction and desorption steps of the MSPE procedure were investigated and optimized. These factors include extraction time, sorbent mass and salt addition for the adsorption step and type of eluent, desorption time and volume of desorption solution for the desorption step. Under optimum conditions, the absolute extraction recovery was found to be 91.1% and good linearity was observed in the investigated concentration range of 0.6-12.5 ng mL-1 (R 2 = 0.9997). The limit of detection was 0.18 ng mL-1 and the limit of quantification was 0.60 ng mL-1. The method was successfully applied to the analysis of surface water samples. The proposed MSPE method is simple, rapid, sensitive and environmentally friendly.

Effect of Sintering Temperature of Bioactive Glass Nanoceramics on the Hemolytic Activity and Oxidative Stress Biomarkers in Erythrocytes.

INTRODUCTION: The nature of the surface is critical in determining the biological activity of silica powders. A novel correlation between toxicity and surface properties of bioactive glass ceramics (BGCs) synthesized via the sol-gel method was attempted in this study. METHODS: The behavior of BGCs after their attachment to the surface of red blood cells (RBCs) was evaluated and their toxic effects were determined based on hemolysis, membrane injury via anti-phosphotyrosine immunoblot of Band 3, lipid peroxidation, potential to generate reactive oxygen species, and antioxidant enzyme production. In particular, three BGCs were synthesized and treated at three sintering temperatures (T1 = 835 °C, T2 = 1000 °C and T3 = 1100 °C) to investigate possible relation between surface charge or structure and hemolytic potential. RESULTS: Their toxicity based on hemolysis was dose dependent, while BGC-T2 had the best hemocompatibility in compare with the other BGCs.No BGCs in dosages lower than 0.125 mg/mL could damage erythrocytes. On the other hand, all BGCs promoted the production of reactive oxygen species in certain concentrations, with the BGC-T2 producing the lowest ROS and increasing the glutathione levels in RBCs protecting their damage. CONCLUSIONS: The results suggest that various factors such as size, a probable different proportion of surface silanols, a balanced mechanism between calcium and magnesium cellular uptake or the different crystalline nature may have contributed to this finding; however, future research is needed to clarify the underlying mechanisms.

Recent Advances in the Extraction of Polycyclic Aromatic Hydrocarbons from Environmental Samples.

Polycyclic aromatic hydrocarbons (PAHs) comprise a group of chemical compounds consisting of two or more fused benzene rings. PAHs exhibit hydrophobicity and low water solubility, while some of their members are toxic substances resistant to degradation. Due to their low levels in environmental matrices, a preconcentration step is usually required for their determination. Nowadays, there is a wide variety of sample preparation techniques, including micro-extraction techniques (e.g., solid-phase microextraction and liquid phase microextraction) and miniaturized extraction techniques (e.g., dispersive solid-phase extraction, magnetic solid-phase extraction, stir bar sorptive extraction, fabric phase sorptive extraction etc.). Compared to the conventional sample preparation techniques, these novel techniques show some benefits, including reduced organic solvent consumption, while they are time and cost efficient. A plethora of adsorbents, such as metal-organic frameworks, carbon-based materials and molecularly imprinted polymers, have been successfully coupled with a wide variety of extraction techniques. This review focuses on the recent advances in the extraction techniques of PAHs from environmental matrices, utilizing novel sample preparation approaches and adsorbents.

Sample Preparation Using Graphene-Oxide-Derived Nanomaterials for the Extraction of Metals.

Graphene oxide is a compound with a form similar to graphene, composed of carbon atoms in a sp2 single-atom layer of a hybrid connection. Due to its significant surface area and its good mechanical and thermal stability, graphene oxide has a plethora of applications in various scientific fields including heterogenous catalysis, gas storage, environmental remediation, etc. In analytical chemistry, graphene oxide has been successfully employed for the extraction and preconcentration of organic compounds, metal ions, and proteins. Since graphene oxide sheets are negatively charged in aqueous solutions, the material and its derivatives are ideal sorbents to bind with metal ions. To date, various graphene oxide nanocomposites have been successfully synthesized and evaluated for the extraction and preconcentration of metal ions from biological, environmental, agricultural, and food samples. In this review article, we aim to discuss the application of graphene oxide and functionalized graphene oxide nanocomposites for the extraction of metal ions prior to their determination via an instrumental analytical technique. Applications of ionic liquids and deep eutectic solvents for the modification of graphene oxide and its functionalized derivatives are also discussed.