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- Evaluation of the feasibility of the electronic tongue as a rapid analytical tool for wine age prediction and quantification of the organic acids and phenolic compounds. The case-study of Madeira winePublication . Rudnitskaya, A.; Rocha, S. M.; Legin, A.; Pereira, V.; Marques, J. C.A set of fourteen Madeira wines comprising wines produced from four Vitis vinifera L. varieties (Bual, Mal vasia, Verdelho and Tinta Negra Mole) that were 3, 6, 10 and 17 years old was analysed using HPLC and an electronic tongue (ET) multisensor system. Concentrations of 24 organic acids, phenolic and furanic compounds were determined by HPLC. The ET consisting of 26 potentiometric chemical sensors with plasticized PVC and chalcogenide glass membranes was used. Significance of the effects of age and vari ety on the ET response and wine composition with respect to the organic acids, phenolics and furanic derivatives were evaluated using ANOVA—Simultaneous Component Analysis (ASCA). Significance of the effects was estimated using a permutation test (1000 permutations). It was found that effects of age, grape variety and their interaction were significant for the HPLC data set and only the effect of age was significant for the ET data. Calibration models of the HPLC and ET data with respect to the wine age and of the ET data with respect to the concentration of the organic acids and phenolics were calculated using PLS1 regression. Models were validated using cross-validation. It was possible to predict wine age from HPLC and ET data with the accuracy in cross-validation of 2.6 and 1.8 years respectively. The ET was capable of detecting the following components (mean relative error in cross-validation is shown in the parentheses): tartaric (8%), citric (5%), formic (12%), protocatehuic (5%), vanillic (18%) and sinapic (14%) acids, catechin (6%), vanillin (12%) and trans-resveratrol (5%). The ET capability of predicting Madeira wine age with good accuracy (1.8 years) as well as quantify of some organic acids and phenolic compounds was demonstrated.
- Establishment of the varietal profile of Vitis vinifera L. grape varieties from different geographical regions based on HS-SPME/GC–qMS combined with chemometric toolsPublication . Perestrelo, Rosa; Barros, António S.; Rocha, Sílvia M.; Câmara, José S.The varietal volatile profiles of pulp and skin fractions from the main red and white Vitis vinifera L. grape varieties used in the production of Madeira wine (Portugal) were established by headspace solid phase microextraction (SPME) combined with gas chromatography–quadrupole mass spectrometry (GC–qMS) tandem with chemometric tools. A total of 60 varietal volatile compounds — 27 in pulp and 42 in skin of V. vinifera L. grapes studied, were identified, including 27 monoterpenic, 26 sesquiterpenic and 7 C13 norisoprenoid compounds. Principal Component Analysis (PCA) and Hierarchical Clusters Analysis (HCA) results demonstrated that, independently of grape fractions, a distribution by grape variety (white and red) as well as by Terroir effect, was attained using the varietal volatiles from skin grape fraction. Bual, Malvasia Cândida and Malvasia Branca (white varieties) exhibited different varietal volatile profiles, independently of grape fractions, skin or pulp. This difference could be explained by the highest sesquiterpenic level found in Bual grape variety, and monoterpenic level found in Malvasia Cândida and Malvasia Branca grape varieties. The obtained data suggests that climatic factors, such as altitude, temperature and humidity influenced the varietal profile from the target varieties, as the varietal profile of grapes cultivated at Estreito de Câmara de Lobos (32°39′50.59″N; 16°58′48.28″W) and Jardim da Serra (32°41′42.36″N; 16°59′37.32″W) showed qualitative and quantitative differences (expressed as GC peak area) when compared to varietal profile of grapes cultivated at Estreito da Calheta (32°44′0.09″N; 17°11′14.80″W), independently of the grape fractions (pulp or skin). Moreover, the cultivation of recommended grapes to produce Madeira wines — Malvasia Branca, Terrantez and Bastardo, should be promoted as their varietal volatile profile is quite similar to that found in noble varieties (Malvasia Cândida and Sercial, respectively).
- Phenolic profile of Sercial and Tinta Negra Vitis vinifera L. grape skins by HPLC–DAD–ESI-MSn: novel phenolic compounds in Vitis vinifera L. grapePublication . Perestrelo, Rosa Maria de Sá; Lu, Ying; Santos, Sónia A. O.; Silvestre, Armando J. D.; Neto, Carlos P.; Câmara, José S.; Rocha, Sílvia M.This study represents the first phytochemical research of phenolic components of Sercial and Tinta Negra Vitis vinifera L. The phenolic profiles of Sercial and Tinta Negra V. vinifera L. grape skins (white and red varieties, respectively) were established using high performance liquid chromatography–diode array detection–electrospray ionisation tandem mass spectrometry (HPLC–DAD–ESI-MSn), at different ripening stages (véraison and maturity). A total of 40 phenolic compounds were identified, which included 3 hydroxybenzoic acids, 8 hydroxycinnamic acids, 4 flavanols, 5 flavanones, 8 flavonols, 4 stilbenes, and 8 anthocyanins. For the white variety, in both ripening stages, hydroxycinnamic acids and flavonols were the main phenolic classes, representing about 80% of the phenolic composition. For red variety, at véraison, hydroxycinnamic acids and flavonols were also the predominant classes (71%), but at maturity, anthocyanins represented 84% of the phenolic composition. As far as we know, 10 compounds were reported for the first time in V. vinifera L. grapes, namely protocatechuic acid-glucoside, p-hydroxybenzoyl glucoside, caftaric acid vanilloyl pentoside, p-coumaric acid-erythroside, naringenin hexose derivate, eriodictyol-glucoside, taxifolin-pentoside, quercetin-glucuronide-glucoside, malylated kaempferol-glucoside, and resveratrol dimer. These novel V. vinifera L. grape components were identified based on their MSn fragmentation profile. This data represents valuable information that may be useful to oenological management and to valorise these varieties as sources of bioactive compounds.
- Optimisation of stir bar sorptive extraction and liquid desorption combined with large volume injection-gas chromatography–quadrupole mass spectrometry for the determination of volatile compounds in winesPublication . Coelho, Elisabete; Perestrelo, Rosa Maria de Sá; Neng, Nuno R.; Câmara, José S.; Coimbra, Manuel A.; Nogueira, J. M. F.; Rocha, Sílvia M.Stir bar sorptive extraction and liquid desorption followed by large volume injection coupled to gas chromatography–quadrupole mass spectrometry (SBSE–LD/LVI-GC–qMS) had been applied for the determination of volatiles in wines. The methodology was optimised in terms of extraction time and influence of ethanol in the matrix; LD conditions, and instrumental settings. The optimisation was carried out by using 10 standards representative of the main chemical families of wine, i.e. guaiazulene, E,E-farnesol, β-ionone, geranylacetone, ethyl decanoate, β-citronellol, 2-phenylethanol, linalool, hexyl acetate and hexanol. The methodology shows good linearity over the concentration range tested, with correlation coefficients higher than 0.9821, a good reproducibility was attained (8.9–17.8%), and low detection limits were achieved for nine volatile compounds (0.05–9.09 μg L−1), with the exception of 2-phenylethanol due to low recovery by SBSE. The analytical ability of the SBSE–LD/LVI-GC–qMS methodology was tested in real matrices, such as sparkling and table wines using analytical curves prepared by using the 10 standards where each one was applied to quantify the structurally related compounds. This methodology allowed, in a single run, the quantification of 67 wine volatiles at levels lower than their respective olfactory thresholds. The proposed methodology demonstrated to be easy to work-up, reliable, sensitive and with low sample requirement to monitor the volatile fraction of wine.
- Chromatographic-Based Platforms as New Avenues for Scientific Progress and SustainabilityPublication . Câmara, José S.; Martins, Cátia; Pereira, Jorge A. M.; Perestrelo, Rosa; Rocha, Sílvia M.Chromatography was born approximately one century ago and has undergone outstanding technological improvements in innovation, research, and development since then that has made it fundamental to advances in knowledge at different levels, with a relevant impact on the well-being and health of individuals. Chromatography boosted a comprehensive and deeper understanding of the complexity and diversity of human–environment interactions and systems, how these interactions affect our life, and the several societal challenges we are currently facing, namely those related to the sustainability of our planet and the future generations. From the life sciences, which allowed us to identify endogenous metabolites relevant to disease mechanisms, to the OMICS field, nanotechnology, clinical and forensic analysis, drug discovery, environment, and “foodprint”, among others, the wide range of applications of today’s chromatographic techniques is impressive. This is fueled by a great variability of powerful chromatographic instruments currently available, with very high sensitivity, resolution, and identification capacity, that provide a strong basis for an analytical platform able to support the challenging demands of the postgenomic and post COVID-19 eras. Within this context, this review aims to address the great utility of chromatography in helping to cope with several societal-based challenges, such as the characterization of disease and/or physiological status, and the response to current agri-food industry challenges of food safety and sustainability, or the monitoring of environmental contamination. These are increasingly important challenges considering the climate changes, the tons of food waste produced every day, and the exponential growth of the human population. In this context, the principles governing the separation mechanisms in chromatography as well the different types and chromatographic techniques will be described. In addition, the major achievements and the most important technological advances will be also highlighted. Finally, a set of studies was selected in order to evince the importance of different chromatographic analyses to understand processes or create fundamental information in the response to current societal challenges.
- Allergic asthma exhaled breath metabolome: a challenge for comprehensive two-dimensional gas chromatographyPublication . Caldeira, M.; Perestrelo, Rosa Maria de Sá; Barros, António S.; Bilelo, M. J.; Morête, A.; Câmara, J. S.; Rocha, Sílvia M.Allergic asthma represents an important public health issue, most common in the paediatric population, characterized by airway inflammation that may lead to changes in volatiles secreted via the lungs. Thus, exhaled breath has potential to be a matrix with relevant metabolomic information to characterize this disease. Progress in biochemistry, health sciences and related areas depends on instrumental advances, and a high throughput and sensitive equipment such as comprehensive two-dimensional gas chromatography–time of flight mass spectrometry (GC × GC–ToFMS) was considered. GC × GC–ToFMS application in the analysis of the exhaled breath of 32 children with allergic asthma, from which 10 had also allergic rhinitis, and 27 control children allowed the identification of several hundreds of compounds belonging to different chemical families. Multivariate analysis, using Partial Least Squares-Discriminant Analysis in tandem with Monte Carlo Cross Validation was performed to assess the predictive power and to help the interpretation of recovered compounds possibly linked to oxidative stress, inflammation processes or other cellular processes that may characterize asthma. The results suggest that the model is robust, considering the high classification rate, sensitivity, and specificity. A pattern of six compounds belonging to the alkanes characterized the asthmatic population: nonane, 2,2,4,6,6-pentamethylheptane, decane, 3,6-dimethyldecane, dodecane, and tetradecane. To explore future clinical applications, and considering the future role of molecular-based methodologies, a compound set was established to rapid access of information from exhaled breath, reducing the time of data processing, and thus, becoming more expedite method for the clinical purposes.
- In-depth search focused on furans, lactones, volatile phenols, and acetals as potential age markers of Madeira wines by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry combined with solid phase microextractionPublication . Perestrelo, Rosa Maria de Sá; Barros, António S.; Câmara, José S.; Rocha, Sílvia M.The establishment of potential age markers of Madeira wine is of paramount significance as it may contribute to detect frauds and to ensure the authenticity of wine. Considering the chemical groups of furans, lactones, volatile phenols, and acetals, 103 volatile compounds were tentatively identified; among these, 71 have been reported for the first time in Madeira wines. The chemical groups that could be used as potential age markers were predominantly acetals, namely, diethoxymethane, 1,1-diethoxyethane, 1,1-diethoxy-2-methyl-propane, 1-(1-ethoxyethoxy)-pentane, trans-dioxane and 2-propyl-1,3-dioxolane, and from the other chemical groups, 5-methylfurfural and cis-oak-lactone, independently of the variety and the type of wine. GC × GC-ToFMS system offers a more useful approach to identify these compounds compared to previous studies using GC−qMS, due to the orthogonal systems, that reduce coelution, increase peak capacity and mass selectivity, contributing to the establishment of new potential Madeira wine age markers. Remarkable results were also obtained in terms of compound identification based on the organized structure of the peaks of structurally related compounds in the GC × GC peak apex plots. This information represents a valuable approach for future studies, as the ordered-structure principle can considerably help the establishment of the composition of samples. This new approach provides data that can be extended to determine age markers of other types of wines.
- Profiling allergic asthma volatile metabolic patterns using a headspace-solid phase microextraction/gas chromatography based methodologyPublication . Caldeira, M.; Barros, António S.; Bilelo, M. J.; Parada, A.; Câmara, J. S.; Rocha, Sílvia M.Allergicasthmarepresentsanimportantpublichealthissuewithsignificantgrowthovertheyears,especially in the paediatric population. Exhaled breath is a non-invasive, easily performed and rapid method forobtainingsamplesfromthelowerrespiratorytract.Inthepresentmanuscript,themetabolicvolatile profiles of allergic asthma and control children were evaluated by headspace solid-phase microextraction combined with gas chromatography–quadrupole mass spectrometry (HS-SPME/GC–qMS). The lack ofstudiesinbreathofallergicasthmaticchildrenbyHS-SPMEledtothedevelopmentofanexperimental design to optimize SPME parameters. To fulfil this objective, three important HS-SPME experimental parameters that influence the extraction efficiency, namely fibre coating, temperature and time extractions were considered. The selected conditions that promoted higher extraction efficiency corresponding to the higher GC peak areas and number of compounds were: DVB/CAR/PDMS coating fibre, 22◦C and 60min as the extraction temperature and time, respectively. The suitability of two containers, 1L Tedlar® bags and BIOVOC®, for breath collection and intra-individual variability were also investigated. The developed methodology was then applied to the analysis of children exhaled breath with allergicasthma(35),fromwhich13hadalsoallergicrhinitis,andhealthycontrolchildren(15),allowing to identify 44 volatiles distributed over the chemical families of alkanes (linear and ramified) ketones, aromatic hydrocarbons, aldehydes, acids, among others. Multivariate studies were performed by Partial LeastSquares–DiscriminantAnalysis(PLS–DA)usingasetof28selectedmetabolitesanddiscrimination between allergic asthma and control children was attained with a classification rate of 88%. The allergic asthma paediatric population was characterized mainly by the compounds linked to oxidative stress, such as alkanes and aldehydes. Furthermore, more detailed information was achieved combining the volatile metabolic data, suggested by PLS–DA model, and clinical data.
- Comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry combined with solid phase microextraction as a powerful tool for quantification of ethyl carbamate in fortified wines. The case study of Madeira winePublication . Perestrelo, Rosa Maria de Sá; Petronilho, Silvia; Câmara, José S.; Rocha, Sílvia M.An analytical methodology based on headspace solid phase microextraction (HS-SPME) combined with comprehensive two-dimensional gas chromatography—time-of-flight mass spectrometry (GC × GC–ToFMS) was developed for the identification and quantification of the toxic contaminant ethyl carbamate (EC) directly in fortified wines. The method performance was assessed for dry/medium dry and sweet/medium sweet model wines, and for quantification purposes, calibration plots were performed for both matrices using the ion extraction chromatography (IEC) mode (m/z 62). Good linearity was obtained with a regression coefficient (r2) higher than 0.981. A good precision was attained (R.S.D. <20%) and low detection limits (LOD) were achieved for dry (4.31 μg/L) and sweet (2.75 μg/L) model wines. The quantification limits (LOQ) and recovery for dry wines were 14.38 μg/L and 88.6%, whereas for sweet wines were 9.16 μg/L and 99.4%, respectively. The higher performance was attainted with sweet model wine, as increasing of glucose content improves the volatile compound in headspace, and a better linearity, recovery and precision were achieved. The analytical methodology was applied to analyse 20 fortified Madeira wines including different types of wine (dry, medium dry, sweet, and medium sweet) obtained from several harvests in Madeira Island (Portugal). The EC levels ranged from 54.1 μg/L (medium dry) to 162.5 μg/L (medium sweet).
- Optimisation of solid-phase microextraction combined with gas chromatography–mass spectrometry based methodology to establish the global volatile signature in pulp and skin of Vitis vinifera L. grape varietiesPublication . Perestrelo, Rosa Maria de Sá; Barros, António S.; Rocha, Sílvia M.; Câmara, José S.The volatiles (VOCs) and semi-volatile organic compounds (SVOCs) responsible for aroma are mainly present in skin of grape varieties. Thus, the present investigation is directed towards the optimisation of a solvent free methodology based on headspace-solid-phase microextraction (HS-SPME) combined with gas chromatography–quadrupole mass spectrometry (GC–qMS) in order to establish the global volatile composition in pulp and skin of Bual and Bastardo Vitis vinifera L. varieties. A deep study on the extraction-influencing parameters was performed, and the best results, expressed as GC peak area, number of identified compounds and reproducibility, were obtained using 4 g of sample homogenised in 5 mL of ultra-pure Milli-Q water in a 20 mL glass vial with addition of 2 g of sodium chloride (NaCl). A divinylbenzene/carboxen/polydimethylsiloxane fibre was selected for extraction at 60 °C for 45 min under continuous stirring at 800 rpm. More than 100 VOCs and SVOCs, including 27 monoterpenoids, 27 sesquiterpenoids, 21 carbonyl compounds, 17 alcohols (from which 2 aromatics), 10 C13 norisoprenoids and 5 acids were identified. The results showed that, for both grape varieties, the levels and number of volatiles in skin were considerably higher than those observed in pulp. According to the data obtained by principal component analysis (PCA), the establishment of the global volatile signature of grape and the relationship between different part of grapes—pulp and skin, may be an useful tool to winemaker decision to define the vinification procedures that improves the organoleptic characteristics of the corresponding wines and consequently contributed to an economic valorization and consumer acceptance.