Chemical Profile, Antioxidant and Cytotoxic Activity of a Phenolic-Rich Fraction from the Leaves of Brassica fruticulosa subsp. fruticulosa (Brassicaceae) Growing Wild in Sicily (Italy).

Recently, our research team has started a study on Brassica fruticulosa subsp. fruticulosa, an edible plant traditionally used to treat various ailments, little investigated to date. Good in vitro antioxidant properties were highlighted for the leaf hydroalcoholic extract, with the secondary higher than the primary ones. In continuation of the ongoing research, this work was designed to elucidate the antioxidant properties of the phenolic compounds contained in the extract. For this purpose, a phenolic-rich ethyl acetate fraction (Bff-EAF) was obtained from the crude extract by liquid-liquid extraction. The phenolic composition was characterized by HPLC-PDA/ESI-MS analysis and the antioxidant potential was investigated by different in vitro methods. Furthermore, the cytotoxic properties were evaluated by MTT, LDH and ROS determinations on human colorectal epithelial adenocarcinoma cells (CaCo-2) and human normal fibroblasts (HFF-1). Twenty phenolic compounds (flavonoid and phenolic acid derivatives) were identified in Bff-EAF. The fraction exhibited good radical scavenging activity in the DPPH test (IC50 = 0.81 ± 0.02 mg/mL), and moderate reducing power (ASE/mL = 13.10 ± 0.94) and chelating properties (IC50 = 2.27 ± 0.18 mg/mL), contrary to what previously observed for the crude extract. Bff-EAF reduced in a dose-dependent manner CaCo-2 cell proliferation after 72 h of treatment. This effect was accompanied by the destabilization of the cellular redox state due to the antioxidant and pro-oxidant activities displayed by the fraction at lower and higher concentrations. No cytotoxic effect was observed on HFF-1 fibroblasts, used as control cell line.

Phytochemical profile and antioxidant capacity, α-amylase and α-glucosidase inhibitory activities of Oxalis pes-caprae extracts in alloxan-induced diabetic mice.

Diabetes and its complications are closely correlated with chronic hyperglycemia, causing severe oxidative stress and leading to glycation reaction with formation of advanced glycation end products. However, medicinal plants are still a source of inspiration for the discovery of new treatments of several diseases, including diabetes. The present study was aimed to evaluate the antioxidant and antidiabetic properties of Oxalis pes-caprae flowers extract in alloxan-induced diabetic mice. The phytochemical and antioxidant activities of both aqueous and methanolic extracts were assessed by in-vitro testing such as free radical scavenging assays (DPPH and ABTS+), ferrous ions (Fe2+) chelating activity and reducing power assay. Additionally, the detection of Amadori products and advanced glycation end products was used to determine the antiglycation potential. α-glucosidase and α-amylase inhibitory assessment was employed to determine the antidiabetic effect, while alloxan-induced diabetic mice were used to measure the in-vivo activities of antioxidants and carbohydrates enzymes. The effect of the methanolic extract on body weight and blood glucose level of extract-treated diabetic mice were also investigated. Among the tested extract, the methanolic extract was the richest in phenolic compounds which is directly related with their remarkable antioxidant, enzyme inhibitory and antiglycation activity. The oral administration of the two doses of Oxalis pes-caprae flowers (150 mg/kg and 250 mg/kg) daily for 3 weeks resulted in hypoglycemic effect compared to the reference drug, glibenclamide (10 mg/kg). Furthermore, the extract was shown to significantly increase the activities of antioxidants and glycolysis enzymes in the liver, kidney and spleen of diabetic mice, compared to diabetic control group. Therefore, Oxalis pes-caprae extract effectively exhibited hypoglycemic and antidiabetic effects as indicated by in-vitro and in-vivo studies, confirming the protective effects on hyperglycemia and oxidative damage.

Supercritical Fluid Extraction of Oils from Cactus Opuntia ficus-indica L. and Opuntia dillenii Seeds.

This study aimed to assess the capability of supercritical fluid extraction (SFE) as an alternative and green technique compared to Soxhlet extraction for the production of oils from Opuntia ficus-indica (OFI) seeds originating from Yemen and Italy and Opuntia dillenii (OD) seeds from Yemen. The following parameters were used for SFE extraction: a pressure of 300 bar, a CO2 flow rate of 1 L/h, and temperatures of 40 and 60 °C. The chemical composition, including the fatty acids and tocopherols (vitamin E) of the oils, was determined using chromatographic methods. The highest yield was achieved with Soxhlet extraction. The oils obtained with the different extraction procedures were all characterized by a high level of unsaturated fatty acids. Linoleic acid (≤62% in all samples) was the most abundant one, followed by oleic and vaccenic acid. Thirty triacylglycerols (TAGs) were identified in both OFI and OD seed oils, with trilinolein being the most abundant (29-35%). Vanillin, 4-hydroxybenzaldehyde, vanillic acid, and hydroxytyrosol were phenols detected in both OFI and OD oils. The highest γ-tocopherol content (177 ± 0.23 mg/100 g) was obtained through the SFE of OFI seeds from Yemen. Overall, the results highlighted the potential of SFE as green technology to obtain oils suitable for functional food and nutraceutical products.

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.

HPLC-PDA/ESI-MS Analysis of Phenolic Compounds and Bioactivities of the Ethanolic Extract from Flowers of Moroccan Anacyclus clavatus.

In this work, polyphenols were extracted from Anacylus clavatus flowers using a hydroethanolic solvent, and the obtained extract was studied for its total phenol and flavonoid contents and evaluated for its antioxidant and antibacterial capacities. The contents of total phenols and flavonoids were measured by employing gallic acid and quercetin as references, respectively, and the phenolic composition analysis was conducted using high-performance liquid chromatography combined with a photodiode array and electrospray ionization mass spectrometry (HPLC-PDA/ESI-MS). The antioxidant capacity of the extracts was tested using a potassium ferric reducing antioxidant power (PFRAP) assay, and the antibacterial activity assay was carried out against Gram-negative bacteria (Escherichia coli and Salmonella typhimirium) and Gram-positive bacteria (Staphyloccocus aureus and Listeria monocytogenes) using the broth microdilution assay. The phenolic and flavonoid contents of the extracts equaled 9.53 ± 0.48 mg GAE/g dm and 1.31 ± 0.06 mg QE/g dm, respectively. The chromatographic analysis of the phenolic profile detected 26 phenolic compounds belonging to phenolic acids, flavones and flavonols, and with the caffeoylquinic acid derivatives being the major phenolic compounds present in 12 isomers. Only one organic compound, viz. citric acid, was found. The extracts exhibited interesting antioxidant activity. Bacteriostatic activity towards Escherichia coli and bactericidal activity against Salmonella typhimirium, Staphyloccocus aureus and Listeria monocytogenes were determined. This study revealed that Anacyclus clavatus flower extracts contain phenolic compounds with interesting bioactivities.

A method for the determination of 70 pesticides in extra virgin olive oil based on a limited-volume solvent extraction step prior to comprehensive two-dimensional gas chromatography-tandem mass spectrometry.

The goal of the present research was to develop a method based on a miniaturized solvent extraction step (using only 500 µL of acetonitrile, with no further clean-up or concentration processes) prior to cryogenic-modulation comprehensive two-dimensional gas chromatography-tandem mass spectrometry for the determination of seventy pesticides in extra virgin olive oil, exploiting the enhanced specificity and sensitivity of this technique. Limits of quantification were always below European legislation residue limits, intra-day precision was between 0.3 and 4.9% (at the 50 and 100 µg kg-1 concentration levels), inter-day precision was between 1.6 and 6.1% (at the 100 µg kg-1 concentration level), recovery (at the 20, 50, and 100 µg kg-1 concentration levels) was in the 14-120% range, accuracy at the initial stage of the work (within repeatability conditions) was between 79 and 110%, while accuracy after 3 months (within intermediate precision conditions) was between 91 and 121% (at the 50 and 100 µg kg-1 concentration levels). Finally, the matrix effect was always positive, between 16 and 197%. The method was applied to the investigation of twenty samples, and eleven of these were found to be contaminated.

Rhus Coriaria L. Extract: Antioxidant Effect and Modulation of Bioenergetic Capacity in Fibroblasts from Parkinson's Disease Patients and THP-1 Macrophages.

Sumac, Rhus coriaria L., is a Mediterranean plant showing several useful properties, such as antioxidant and neuroprotective effects. Currently, there is no evidence about its possible neuroprotective action in Parkinson's disease (PD). We hypothesized that sumac could modulate mitochondrial functionality in fibroblasts of familial early-onset PD patients showing PARK2 mutations. Sumac extract volatile profile, polyphenolic content and antioxidant activity have been previously characterized. We evaluated ROS and ATP levels on sumac-treated patients' and healthy control fibroblasts. In PD fibroblasts, all treatments were effective in reducing H2O2 levels, while patients' ATP content was modulated differently, probably due to the varying mutations in the PARK2 gene found in individual patients which are also involved in different mitochondrial phenotypes. We also investigated the effect of sumac extract on THP-1-differentiated macrophages, which show different embryogenic origin with respect to fibroblasts. In THP-1 macrophages, sumac treatment determined a reduction in H2O2 levels and an increase in the mitochondrial ATP content in M1, assuming that sumac could polarize the M1 to M2 phenotype, as demonstrated with other food-derived compounds rich in polyphenols. In conclusion, Rhus coriaria L. extracts could represent a potential nutraceutical approach to PD.

Melissa officinalis L. as a Sprout Suppressor in Solanum tuberosum L. and an Alternative to Synthetic Pesticides.

The goal of this research was to screen plant essential oils (EOs) as sprout inhibitors or suppressors in potato (Solanum tuberosum L.). Three controlled environment experiments were conducted to screen 18 EOs and several pure compounds as sprout inhibitors. The EOs were applied using the wicked method on potato cv. Gala in 19 L plastic containers. The results indicated that Melissa officinalis L. EO inhibited sprouting, while Coriandrum sativum L. seed oil and the EO blend of Lavandula angustifolia Mill. and Salvia sclarea L. suppressed sprouting. The EOs of interest were analyzed using gas chromatography coupled to mass spectrometry (GC-MS) and/or a flame ionization detector (GC-FID); the detailed chemical profiles are provided. The M. officinalis EO was fractionated into seven fractions, and these were tested on minitubers. We identified two fractions (F and A) that suppressed potato sprouting better than the whole oil. The GC-MS-FID analyses of M. officinalis EO fraction A identified myrcene, Z-ocimene, E-ocimene, trans-caryophyllene, and α-humulene as the main constituents, while the main constituents of fraction F were α-terpineol, ß-citronellol, and geraniol. The pure isolated compounds, together with the major compound in M. officinalis EO (citral), were tested for sprout suppression on three potato cultivars (Ranger Russet, Terra Rosa, and Dakota TrailBlazer), which revealed that ß-citronellol reduced the sprout length and the number of sprouts in all three cultivars, while citral and (+)-α-terpineol reduced the sprout length and the number of sprouts in Ranger Russet relative to the two controls in all three cultivars. Myrcene had a stimulating effect on the number of sprouts in Cv. Terra Rosa. However, none of the pure compounds suppressed sprouting completely or were comparable to the EO of M. officinalis.

Chemical Composition, Antifungal and Anti-Biofilm Activities of Volatile Fractions of Convolvulus althaeoides L. Roots from Tunisia.

The antifungal drugs currently available and mostly used for the treatment of candidiasis exhibit the phenomena of toxicity and increasing resistance. In this context, plant materials might represent promising sources of antifungal agents. The aim of this study is to evaluate for the first time the chemical content of the volatile fractions (VFs) along with the antifungal and anti-biofilm of Convolvulus althaeoides L. roots. The chemical composition was determined by gas chromatography coupled to a flame ionization detector and mass spectrometry. In total, 73 and 86 chemical compounds were detected in the n-hexane (VF1) and chloroform (VF2) fractions, respectively. Analysis revealed the presence of four main compounds: n-hexadecenoic acid (29.77%), 4-vinyl guaiacol (12.2%), bis(2-ethylhexyl)-adipate (9.69%) and eicosane (3.98%) in the VF extracted by hexane (VF1). n-hexadecenoic acid (34.04%), benzyl alcohol (7.86%) and linoleic acid (7.30%) were the main compounds found in the VF extracted with chloroform (VF2). The antifungal minimum inhibitory concentrations (MICs) of the obtained fractions against Candida albicans, Candida glabrata and Candida tropicalis were determined by the micro-dilution technique and values against Candida spp. ranged from 0.87 to 3.5 mg/mL. The biofilm inhibitory concentrations (IBF) and sustained inhibition (BSI) assays on C. albicans, C. glabrata and C. tropicalis were also investigated. The VFs inhibited biofilm formation up to 0.87 mg/mL for C. albicans, up to 1.75 mg/mL against C. glabrata and up to 0.87 mg/mL against C. tropicalis. The obtained results highlighted the synergistic mechanism of the detected molecules in the prevention of candidosic biofilm formation.

Automated sample preparation and fast GC-MS determination of fatty acids in blood samples and dietary supplements.

The present research is focused on the optimization of an automatized sample preparation and fast gas chromatography-mass spectrometry (GC-MS) method for the analysis of fatty acid methyl esters (FAMEs) in blood samples and dietary supplements, with the primary objective being a significant reduction of the analysis time and, hence, an enhanced sample throughput. The mass spectrometer was operated in the scan/selected ion monitoring (SIM) acquisition method, thus enabling the obtainment of qualitative and (highly sensitive) quantitative data. The separation of FAMEs was obtained in about 11 min by using a micro-bore column of dimensions 15 m × 0.10 mm ID × 0.10 µm df with a polyethylene glycol stationary phase. The novelty of the research involves reducing analysis time by using the novel fast GC-MS method with increased identification reliability and sensitivity in a single chromatographic run. With regard to the figures of merit, linearity, accuracy, and limits of detection (LoD) and quantification (LoQ) were determined. Specifically, regression coefficients were between 0.9901 and 0.9996; the LoDs ranged from 0.05 to 1.02 µg g-1 for the blood analysis method, and from 0.05 to 0.26 mg g-1 in the case of the dietary supplement approach. With respect to LoQs, the values were in the ranges of 0.15-3.39 µg g-1 and 0.15-0.86 mg g-1 for blood and dietary supplements analysis methods, respectively. Accuracy was evaluated by analyzing certified reference materials (human plasma, fish oil).

Chemical profile, antibacterial, antioxidant, and anisakicidal activities of Thymus zygis subsp. gracilis essential oil and its effect against Listeria monocytogenes.

In this work, the chemical composition of Thymus zygis subsp. gracilis collected from Ifrane, Morocco, along with the evaluation of the antibacterial, anti-biofilm of Listeria monocytogenes activities, larvicidal effect against L3 larvae of Anisakis, and antioxidant properties of its essential oil (TZG-EO), are reported. GC-MS and GC-FID analyses highlighted the presence of 84 volatile components and strong bactericidal and anti-biofilm activities against L. monocytogenes at a concentration of 0.02 % were demonstrated. Also, larvicidal effect against Anisakis larvae at concentrations of 0.01 and 0.005 % was attained leading to the death of all tested larvae within 4 h. The in situ antibacterial activity of TZG-EO (0.01 and 0.005 %) in smoked fish showed high efficiency against L. monocytogenes growth. TZG-EO could be used as potential antibacterial and larvicidal agents for fighting against foodborne pathogens and extending shelf life of food products.

Rapid Evaporative Ionization Mass Spectrometry-Based Lipidomics for Identification of Canine Mammary Pathology.

The present work proposes the use of a fast analytical platform for the mass spectrometric (MS) profiling of canine mammary tissues in their native form for the building of a predictive statistical model. The latter could be used as a novel diagnostic tool for the real-time identification of different cellular alterations in order to improve tissue resection during veterinary surgery, as previously validated in human oncology. Specifically, Rapid Evaporative Ionization Mass Spectrometry (REIMS) coupled with surgical electrocautery (intelligent knife-iKnife) was used to collect MS data from histologically processed mammary samples, classified into healthy, hyperplastic/dysplastic, mastitis and tumors. Differences in the lipid composition enabled tissue discrimination with an accuracy greater than 90%. The recognition capability of REIMS was tested on unknown mammary samples, and all of them were correctly identified with a correctness score of 98-100%. Triglyceride identification was increased in healthy mammary tissues, while the abundance of phospholipids was observed in altered tissues, reflecting morpho-functional changes in cell membranes, and oxidized species were also tentatively identified as discriminant features. The obtained lipidomic profiles represented unique fingerprints of the samples, suggesting that the iKnife technique is capable of differentiating mammary tissues following chemical changes in cellular metabolism.

Determination of the Phenolic Profile, and Evaluation of Biological Activities of Hydroethanolic Extract from Aerial Parts of Origanum compactum from Morocco.

Origanum compactum belonging to the family Lamiaceae is widely used in food and pharmaceutical fields due to its biologically active substances. We aimed to investigate the total phenol and flavonoid contents and the phenolic composition, and to evaluate the antioxidant and antibacterial properties of hydroethanolic extract from of Origanum compactum. Total phenol and flavonoid contents were evaluated using gallic acid and quercetin as standards, respectively, and the phenolic profile was characterized using high-performance liquid chromatography coupled to a photodiode array and electrospray ionization mass spectrometry (HPLC-PDA-ESI/MS). The antioxidant activity was determined by two methods: ferric reducing power (FRAP) assay and the phosphomolybdate method. The antibacterial effect was evaluated against four bacteria (Escherichia coli, Salmonella typhimurium, Staphylococcus aureus and Listeria monocytogenes) using the broth microdilution method. The findings show that the total phenolic and flavonoid contents were 107.789 ± 5.39 mg GAE/g dm and 14,977 ± 0.79 mg QE/g dm, respectively. A total of sixteen phenolic compounds belonging to phenolic acids and flavonoids were detected. Furthermore, the extract showed strong antioxidant activity, and displayed a bacteriostatic effect against Escherichia coli and Salmonella typhimuriumn, and a bactericidal effect against Staphylococcus aureus and Listeria monocytogenes. Therefore, this study reveals that Origanum compactum extracts display potential as antibacterial and natural antioxidant agents for fighting against pathogenic bacteria and preventing oxidative stress.

Direct analysis of phthalate esters in vegetable oils by means of comprehensive two-dimensional gas chromatography combined with triple quadrupole mass spectrometry.

Phthalic acid esters (PAEs), known as phthalates, have a variety of industrial applications, mainly related to their ability to increase plastic softness,flexibility, and durability. With regard to toxicological aspects, several studies suggest that phthalates would act as endocrine-disrupting chemicals, and they have been correlated to several forms of cancer. Since the analysis of PAEs in food is challenging, the aim of this study was the development of a simple and direct method, with no sample preparation (only dilution withsolvent), for the analysis of targeted phthalates in vegetable oils, by using cryogenic-modulation comprehensive two-dimensional gas chromatography combined with triple quadrupole mass spectrometry. The method was characterized by good repeatability values, limit of quantification values ranging between 0.06 and 2.10 mg/kg, accuracy values ranging from -9.2 to 10.4%, and a matrix effectranging from -4 to 78%.The developed technique was used for the analysis of 27 vegetable oils.

Determination of the Phenolic Profile by Liquid Chromatography, Evaluation of Antioxidant Activity and Toxicity of Moroccan Erica multiflora, Erica scoparia, and Calluna vulgaris (Ericaceae).

This study aimed to investigate the phenolic profile and selected biological activities of the leaf and aerial extracts of three Ericaceae species, namely Erica multiflora, Erica scoparia, and Calluna vulgaris, collected from three different places in the north of Morocco. The phenolic composition of all extracts was determined by LC coupled with photodiode array and mass spectrometry detection. Among the investigated extracts, that of E. scoparia aerial parts was the richest one, with a total amount of polyphenols of 9528.93 mg/kg. Up to 59 phenolic compounds were detected: 52 were positively identified and 49 quantified-11 in C. vulgaris, 14 in E. multiflora, and 24 in E. scoparia. In terms of chemical classes, nine were phenolic acids and 43 were flavonoids, and among them, the majority belonged to the class of flavonols. The antioxidant activity of all extracts was investigated by three different in vitro methods, namely DPPH, reducing power, and Fe2+ chelating assays; E. scoparia aerial part extract was the most active, with an IC50 of 0.142 ± 0.014 mg/mL (DPPH test) and 1.898 ± 0.056 ASE/mL (reducing power assay). Further, all extracts were non-toxic against Artemia salina, thus indicating their potential safety. The findings attained in this work for such Moroccan Ericaceae species, never investigated so far, bring novelty to the field and show them to be valuable sources of phenolic compounds with interesting primary antioxidant properties.

Antioxidant and Anti-Inflammatory Effects of Thyme (Thymus vulgaris L.) Essential Oils Prepared at Different Plant Phenophases on Pseudomonas aeruginosa LPS-Activated THP-1 Macrophages.

Thyme (Thymus vulgaris L.) essential oil (TEO) is widely used as an alternative therapy especially for infections of the upper respiratory tract. TEO possesses antiviral, antibacterial, and antifungal properties. The emerging antibiotic resistance of bacterial strains, including Pseudomonas aeruginosa, has prompted the urge to find alternative treatments. In the present study, we examined the anti-inflammatory and antioxidant effects of thymol, the main compound of TEO, and two TEOs prepared at the beginning and at the end of the flowering period that may make these oils promising candidates as complementary or alternative therapies against P. aeruginosa infections. The activity measurements of the antioxidant enzymes peroxidase (PX), catalase (CAT), and superoxide dismutase (SOD) as well as the determination of total antioxidant capacity of P. aeruginosa-activated THP-1 cells revealed that thymol and both TEOs increased CAT and SOD activity as well as the antioxidant capacity of the THP-1 cells. The measurements of the proinflammatory cytokine mRNA expression and secreted protein level of LPS-activated THP-1 cells showed that from the two TEOs, only TEO prepared at the beginning of the flowering period acted as a potent inhibitor of the synthesis of IL-6, IL-8, IL-ß, and TNF-α. Our results suggest that not only thymol, but also the synergism or the antagonistic effects of the additional compounds of the essential oils are responsible for the anti-inflammatory activity of TEOs.

Determination of the polyphenolic content of berry juices using focusing-modulated comprehensive two-dimensional liquid chromatography coupled to mass spectrometry detection.

In this work, a comprehensive two-dimensional liquid chromatography system, comprised of a ZIC-HILIC and C18 columns in the first and second dimensions, respectively, was tuned and employed for attaining high resolution profiles of the polyphenolic pattern in seven commercial berry juices. The developed HILIC × RP-LC method was validated in terms of linearity range, correlation coefficients, limit of detection, limit of quantification, precision (intra- and inter-day), and recovery. A total of 104 polyphenolic compounds belonging to different chemical classes (hydroxybenzoic and cinnamic acid derivatives, flavone glycosides, flavonols, flavonol glycosides, dihydroflavonols, and anthocyanin glycosides) have been characterized and quantified in the juices investigated. Despite the constituents being similar, a notable quantitative variation among the analyzed berry species was observed. Elderberry contained the highest amount of polyphenols (918 ± 1.10 mg 100 mL-1), followed by chokeberry (516 ± 0.08 mg 100 mL-1). On the other hand, raspberry contained the lowest amount (104 ± 1.21 mg 100 mL-1). Further, total phenolic, flavonoid, and anthocyanin contents were determined spectrophotometrically, yielding consistent results. The free-radical scavenging activity (DPPH test) and reducing power of the juices, expressed as IC50 (µL mL-1) and mg ASE mL-1, varied from 2.79 ± 0.03 (honeyberry) to 31.66 ± 0.02 (blueberry) and from 1.71 ± 0.01 (blueberry) to 8.89 ± 0.12 (chokeberry), respectively. Such a ZIC-HILIC × C18 platform based on focusing modulation, never employed so far for berry juices, showed a remarkable separation capability with high values of corrected peak capacity (up to 1372) and orthogonality (Ao up to 0.80), thus providing a great applicability to be advantageously employed for other complex food samples.

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.