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Prostate cancer (PCa) continues to be the second most common malignant tumour and the main cause of oncological death in men. Investigating endogenous volatile organic metabolites (VOMs) produced by various metabolic pathways is emerging as a novel, effective, and non-invasive source of information to establish the volatilomic biosignature of PCa. In this study, headspace solid-phase microextraction combined with gas chromatography–mass spectrometry (HS-SPME/GC-MS) was used to establish the urine volatilomic profile of PCa and identify VOMs that can discriminate between the two investigated groups. This non-invasive approach was applied to oncological patients (PCa group, n = 26) and cancer-free individuals (control group, n = 30), retrieving a total of 147 VOMs from various chemical families. This included terpenes, norisoprenoid, sesquiterpenes, phenolic, sulphur and furanic compounds, ketones, alcohols, esters, aldehydes, carboxylic acid, benzene and naphthalene derivatives, hydrocarbons, and heterocyclic hydrocarbons. The data matrix was subjected to multivariate analysis, namely partial least-squares discriminant analysis (PLS-DA). Accordingly, this analysis showed that the group under study presented different volatomic profiles and suggested potential PCa biomarkers. Nevertheless, a larger cohort of samples is required to boost the predictability and accuracy of the statistical models developed.

Anthocyanins are widespread and biologically active water-soluble phenolic pigments responsible for a wide range of vivid colours, from red (acidic conditions) to purplish blue (basic conditions), present in fruits, vegetables, and coloured grains. The pigments’ stability and colours are influenced mainly by pH but also by structure, temperature, and light. The colour-stabilizing mechanisms of plants are determined by inter- and intramolecular co-pigmentation and metal complexation, driven by van der Waals, π–π stacking, hydrogen bonding, and metal-ligand interactions. This group of flavonoids is well-known to have potent anti-inflammatory and antioxidant effects, which explains the biological effects associated with them. Therefore, this review provides an overview of the role of anthocyanins as natural colorants, showing they are less harmful than conventional colorants, with several technological potential applications in different industrial fields, namely in the textile and food industries, as well as in the development of photosensitizers for dye-sensitized solar cells, as new photosensitizers in photodynamic therapy, pharmaceuticals, and in the cosmetic industry, mainly on the formulation of skin care formulations, sunscreen filters, nail colorants, skin & hair cleansing products, amongst others. In addition, we will unveil some of the latest studies about the health benefits of anthocyanins, mainly focusing on the protection against the most prevalent human diseases mediated by oxidative stress, namely cardiovascular and neurodegenerative diseases, cancer, and diabetes. The contribution of anthocyanins to visual health is also very relevant and will be briefly explored.

Finger lime is receiving growing attention as an ingredient of gastronomic preparations of haute cuisine for its delicious flavor and fragrance and for its appealing aspect. Volatile compounds play a crucial role in determining the organoleptic characteristics of the fruit and its pleasantness for consumers. The aim of the present study was to investigate the volatile profiles by headspace solid phase micro-extraction (HS-SPME) coupled to gas chromatography-mass spectrometry (GC-MS) in the peel and, for the first time, in the pulp of three Australian finger lime cultivars grown in Sicily (southern Italy): Pink Pearl, Sanguinea, and Faustrime, allowing to overall identify 84 volatile organic compounds (VOCs). The analytical data showed that the three cultivars were characterized by distinct volatile chemotypes: limonene/sabinene/bicyclogermacrene in the Pink Pearl, limonene/γ-terpinene/bicyclogermacrene in the Sanguinea, and limonene/β-phellandrene/γ-terpinene in the Faustrime. Moreover, some volatiles, found exclusively in one cultivar, could be considered potential markers of the individual cultivar. PCA allowed us to clearly discriminate the samples into three clusters: the first related to the Sanguinea peel, the second to the Faustrime peel, and a third group associated with the Pink Pearl peel along with the pulp of the three cultivars. Accordingly, the VOCs that mostly contributed to the differentiation of the three finger lime cultivars were also identified. Among them, D-limonene, sabinene γ-terpinene, α-pinene, α-phellandrene, β-myrcene, p-cymene, linalool, δ-elemene, ledene, bicyclogermacrene β-citronellol, α-bergamotene, α-caryophillene, and β-bisabolene, have been previously reported to exhibit important biological activities, suggesting that these cultivars, in addition to possessing unique volatile profiles, can show promise for several applications in pharmaceutical and food industry, namely for development of functional foods.

Atropine and scopolamine belong to the tropane alkaloid (TA) family of natural toxins. They can contaminate teas and herbal teas and appear in infusions. Therefore, this study focused on analyzing atropine and scopolamine in 33 samples of tea and herbal tea infusions purchased in Spain and Portugal to determine the presence of these compounds in infusions brewed at 97 °C for 5 min. A rapid microextraction technique (µSPEed®) followed by high-performance liquid chromatography–tandem mass spectrometry (HPLC–MS/MS) was used to analyze the selected TAs. The results showed that 64% of the analyzed samples were contaminated by one or both toxins. White and green teas were generally more contaminated than black and other herbal teas. Of the 21 contaminated samples, 15 had concentrations above the maximum limit for liquid herbal infusions (0.2 ng/mL) set by Commission Regulation (EU) 2021/1408. In addition, the effects of heating conditions (time and temperature) on atropine and scopolamine standards and naturally contaminated samples of white, green, and black teas were evaluated. The results showed that at the concentrations studied (0.2 and 4 ng/mL), there was no degradation in the standard solutions. Brewing with boiling water (decoction) for 5 and 10 min allowed for higher extraction of TAs from dry tea to infusion water.

The overuse of antibiotics in the healthcare, veterinary, and agricultural industries has led to the development of antimicrobial resistance (AMR), resulting in significant economic losses worldwide and a growing healthcare problem that urgently needs to be solved. Plants produce a variety of secondary metabolites, making them an area of interest in the search for new phytochemicals to cope with AMR. A great part of agri-food waste is of plant origin, constituting a promising source of valuable compounds with different bioactivities, including those against antimicrobial resistance. Many types of phytochemicals, such as carotenoids, tocopherols, glucosinolates, and phenolic compounds, are widely present in plant by-products, such as citrus peels, tomato waste, and wine pomace. Unveiling these and other bioactive compounds is therefore very relevant and could be an important and sustainable form of agri-food waste valorisation, adding profit for local economies and mitigating the negative impact of these wastes’ decomposition on the environment. This review will focus on the potential of agri-food waste from a plant origin as a source of phytochemicals with antibacterial activity for global health benefits against AMR.

Background The Quality Index Method (QIM) is a widely used approach for fish sensory grading, based on a structured scaling for freshness measurements, providing information concerning the fish freshness status, as a prediction of the remaining shelf-life for specific species or products. However, its tendency to be used in an oversimplified way and other common misapplications could lead to discredit of a methodology with great potential. Scope and approach Review the principles of QIM methodology, discussing its concept, applications, and understand their limits, as a useful strategy to propose improvements, reinforce its predictive power and consequent acceptability. Key findings and conclusions: QIM methodology is based on a compromise between the number of fish samples necessary and the number of attributes, with sensory relevance in fish spoilage, that allows verifying if quality requirements are fulfilled. However, the assumptions inherent to the method, undermine the reliability of the shelf-life predictions. Determination of the variability associated with assessors, product, and correct structure of datasets for statistical analysis, will improve the predictive power of the method. However, it could lead to an increase in the method complexity that would drive it away from the industry's needs for fast and easily implemented methods.

Despite the spectacular advances in molecular medicine, including genomics, proteomics, transcriptomics, lipidomics, and personalized medicine, supported by the discovery of the human genome, prostate cancer (PCa) remains the most frequent malignant tumor and a leading cause of oncological death in men. New methods for prognostic, diagnostic, and therapy evaluation are mainly based on the combination of imaging techniques with other methodologies, such as gene or protein profiling, aimed at improving PCa management and surveillance. However, the lack of highly specific and sensitive biomarkers for its early detection is a major hurdle to this goal. Apart from classical biomarkers, the study of endogenous volatile organic metabolites (VOMs) biosynthesized by different metabolic pathways and found in several biofluids is emerging as an innovative, efficient, accessible, and non-invasive approach to establish the volatilomic biosignature of PCa patients, unravelling potential biomarkers. This review provides a brief overview of the challenges of PCa screening methods and emergent biomarkers. We also focus on the potential of volatilomics for the establishment of PCa biomarkers from non-invasive matrices.

The popularity of new psychoactive substances among drug users has become a public health concern worldwide. Among them, synthetic cannabinoids (SCs) represent the largest, most diversified and fastest growing group. Commonly known as ‘synthetic marijuana’ as an alternative to cannabis, these synthetic compounds are easily accessible via the internet and are sold as ‘herbal incenses’ under different brand names with no information about the chemical composition. In the present work, we aim to integrate gas chromatography-tandem mass spectrometry (GC-MS) and nuclear magnetic resonance (NMR) data as useful strategy for the identification and confirmation of synthetic cannabinoids present in nine seized herbal incenses. The analysis of all samples allowed the initial identification of 9 SCs, namely 5 napthoylindoles (JWH-018, JWH-073, JWH-122, JWH-210, MAM-2201), APINACA, XLR-11 and CP47,497-C8 and its enantiomer. JWH-018 was the most frequently detected synthetic compound (8 of 9 samples), while APINACA and XLR-11 were only identified in one herbal product. Other non-cannabinoid drugs, including oleamide, vitamin E and vitamin E acetate, have also been detected. Oleamide and vitamin E are two adulterants, frequently added to herbal products to mask the active ingredients or added as preservatives. However, to our knowledge, no analytical data about vitamin E acetate was reported in herbal products, being the first time that this compound is identified on this type of samples. The integration data obtained from the used analytical technologies proved to be useful, allowing the preliminary identification of the different SCs in the mixture. Furthermore, the examination of mass spectral fragment ions, as well as the results of both 1D and 2D NMR experiments, enabled the identification and confirmation of the molecular structure of SCs.

In recent years, the concerns and demands by consumers for the high quality and safety for natural and processed plant-based and animal foods has increased significantly [...]

Produced in Madeira Island from regional sugarcane cultivars through a traditional manufacturing and storage process, sugarcane honey (SCH) is a black syrup recognized by its excellent quality. Its economic value has led to the emergence of adulterated SCH, whereby the identification of molecular markers became an essential task in order to overcome the fraudulent activities, protect its authenticity, and guarantee the consumer safety. In the present study, an analytical strategy based on ultrasound-assisted liquid-liquid extraction (USA-LLE) followed by reversed-phase liquid chromatography with a refractive index detector (LC-RI) was developed for the determination of sugars (glucose, fructose, sucrose, xylose, and mannose) in SCH samples from certified producers, supported on analytical quality-by-design (AQbD) approach, as a useful tool to establish its typicality. The application of AQbD was based on analytical risk assessment, multivariate statistics and quality control procedures for definition of the Method Operable Design Region (MODR). The optimal conditions into MODR were accomplished using BEH Amide column operating at a temperature of 80 °C and a flow rate of 300 μL min−1, with a mobile phase composed by acetone and water (85:15, v v−1) at a flow rate of 1.0 mL min−1. The robustness was determined by Monte Carlo simulation and capability analysis. The concentration-response function for all sugars was described by polynomial models. Accuracy was presented by recovery values between 98.2 and 119.5%. The analytical figures of merit validated the utility of AQbD in the systematic design of a LC-RI method with fine sensitivity for sugar analysis in SCH.

One of the hallmarks of cancer cells is the demand of supply for the synthesis of new membranes involved in cell proliferation and lipids have an important role in cellular structure, signaling pathways and progression of cancer. In this sense, lipid studies have become an essential tool allowing the establishment of signatures associated with breast cancer (BC). In this regard, some metabolic processes including proteins, nucleic acids and lipid synthesis are enhanced as part of cancer-associated metabolic reprogramming, as a requirement for cell growth and proliferation. Pairwise samples of breast active carcinoma (BAC) and breast cancer-free tissues were collected from n = 28 patients and analyzed by MALDI-TOF MS. Major lipid species are identified in the MALDI-TOF mass spectra, with certain phosphatidylinositols (PIs) detectable only in BAC. Statistical analysis revealed significant differences (p

Background Phenolic compounds have been studied for a variety number of bioactivities using in vitro, ex vivo, and in vivo protocols. Most of the studies dealing with phenolic compounds deal with in vitro antioxidant, antihypertensive, anti-inflammatory, antipyretic, antihemolytic effects in human erythrocytes, hypolipidemic, and antiproliferative activities. Scope and approach Companies have used the overall understanding of the beneficial effects of polyphenols to develop “functional” foods and ingredients. However, the main question that arises is still the target of warm discussions: Is the higher ingestion of phenolic compounds the best dietary strategy? Our commentary focuses on this question and we list some examples in which phenolic compounds show deleterious effects in vivo. Key findings and conclusions Two main conclusions arise: (i) any presumption of “functional effects” based on test-tube studies should be avoided as these results do not represent the real biological effect in humans; (ii) at high concentrations and in specific populations, polyphenols may have several potential adverse health effects presumably associated to their pro-oxidative capacity. All in one, the dietary supplementation containing high doses of polyphenols should be well justified in each case until a consensus is reached supported on medical, nutritional and toxicological data.

Background The multiple health promoting effects associated with the consumption of dietary polyphenols have increased research interest in recent years to develop advanced and environmentally friendly analytical approaches for correctly identify and quantify these compounds in different foodstuffs. However, food samples are highly complex matrices, what hinders determination of these compounds, which additionally, are usually found in food at low concentration levels, therefore a preliminary sample preparation method which provides adequate isolation and enrichment of analytes, as well as effective clean-up from matrices interferences, is often required prior to further analysis. Scope and approach Current trends in sample preparation involves moving towards cheaper, cost-effective and more environmentally friendly procedures, by minimizing the number of steps and reducing the consumption of sample and organic solvents, replacing toxic solvents by non-toxic ones, and improving extraction efficiency and selectivity with the application of new advanced sorbents materials and micro-extraction techniques that overcome limitations of conventional sample preparation methods. Key findings and conclusions This review provides an overview of the most relevant achievements and improvements in sample preparation and extraction methodologies applied for the determination of dietary polyphenols in food products, regarding the preparation of novel silica-based sorbent materials and the development of new micro-extraction methodologies, giving some recent examples from the last five years. The review gives an updated overview that emphasizes the new developments achieved, providing a broad view of the current trends and the future perspectives in the analysis of dietary polyphenols and expanding knowledge related to food quality.

For a long time, the importance of sample preparation and extraction in the analytical performance of the most diverse methodologies have been neglected. Cumbersome techniques, involving high sample and solvent volumes have been gradually miniaturized from solid-phase and liquid-liquid extractions formats and microextractions approaches are becoming the standard in different fields of research. In this context, this review is devoted to the analysis of bioactive compounds in foods using different microextraction approaches reported in the literature since 2015. But microextraction also represents an opportunity to mitigate the environmental impact of organic solvents usage, as well as lab equipment. For this reason, in the recent literature, phenolics and alkaloids extraction from fruits, medicinal herbs, juices, and coffee using different miniaturized formats of solid-phase extraction and liquid-liquid microextraction are the most popular applications. However, more ambitious analytical limits are continuously being reported and emergent sorbents based on carbon nanotubes and magnetic nanoparticles will certainly contribute to this trend. Additionally, ionic liquids and deep eutectic solvents constitute already the most recent forefront of innovation, substituting organic solvents and further improving the current microextraction approaches.

It is known that many bacteria are susceptible to low pH, but it is less clear how the acid nature influences this susceptibility. The objective of this work was to evaluate the susceptibility of selected bacteria to different low pH conditions and to understand if their tolerance is affected by the type of acid (organic vs inorganic) in the media acidification. Strains of different species of human pathogenic bacteria were cultivated at different acidic conditions, using organic or inorganic acids. Overall, we verified that tolerance to acidic conditions is dependent on the type of acid used to acidify the growing medium, organic or inorganic. The strains analysed, although having different tolerance to low pH, were shown to be more susceptible to organic than inorganic acids. This result shows that beyond the pH of the media, the nature of the acid affects bacterial growth. Such a result has consequences in the evaluation of the efficiency of an antibacterial extract, which should take into consideration the differential susceptibility of bacteria to low pHs obtained using organic or inorganic acids.

In the upcoming years, the world will face societal challenges arising, in particular, from the impact of climate change and the inefficient use of natural resources, in addition to an exponential growth of the world population, which according to the United Nations (UN) estimations will be 9.8 billion in 2050. This increasing trend requires optimized management of natural resources with the use of value-added waste and a significant reduction in food loss and food waste. Moreover, the recent pandemic situation, COVID-19, has contributed indisputably. Along with the agri-food supply chain, several amounts of waste or by-products are generated. In most cases, these biomass wastes cause serious environmental concerns and high costs to enterprises. The valorisation of the agri-food loss and food industry wastes emerged as a useful strategy to produce certain value-added compounds with several potential applications, namely in the food, health, pharmaceutical, cosmetic, and environmental fields. Therefore, in this review, some of the crucial sustainable challenges with impacts on the valorisation of agri-food loss/wastes and by-products are discussed and identified, in addition to several opportunities, trends and innovations. Potential applications and usages of the most important compounds found in food loss/waste will be highlighted, with a focus on the food industry, pharmaceutical industry, and the environment.

Finger lime is receiving growing attention as an ingredient of gastronomic preparations of haute cuisine for its delicious flavor and fragrance and for its appealing aspect. Volatile compounds play a crucial role in determining the organoleptic characteristics of the fruit and its pleasantness for consumers. The aim of the present study was to investigate the volatile profiles by headspace solid phase micro-extraction (HS-SPME) coupled to gas chromatography–mass spectrometry (GC–MS) in the peel and, for the first time, in the pulp of three Australian finger lime cultivars grown in Sicily (southern Italy): Pink Pearl, Sanguinea, and Faustrime, allowing to overall identify 84 volatile organic compounds (VOCs). The analytical data showed that the three cultivars were characterized by distinct volatile chemotypes: limonene/sabinene/bicyclogermacrene in the Pink Pearl, limonene/γ-terpinene/bicyclogermacrene in the Sanguinea, and limonene/β-phellandrene/γ-terpinene in the Faustrime. Moreover, some volatiles, found exclusively in one cultivar, could be considered potential markers of the individual cultivar. PCA allowed us to clearly discriminate the samples into three clusters: the first related to the Sanguinea peel, the second to the Faustrime peel, and a third group associated with the Pink Pearl peel along with the pulp of the three cultivars. Accordingly, the VOCs that mostly contributed to the differentiation of the three finger lime cultivars were also identified. Among them, D-limonene, sabinene γ-terpinene, α-pinene, α-phellandrene, β-myrcene, p-cymene, linalool, δ-elemene, ledene, bicyclogermacrene β-citronellol, α-bergamotene, α-caryophillene, and β-bisabolene, have been previously reported to exhibit important biological activities, suggesting that these cultivars, in addition to possessing unique volatile profiles, can show promise for several applications in pharmaceutical and food industry, namely for development of functional foods.

Coffee is one of the world’s most popular beverages, and its consumption generates copious amounts of waste. The most relevant by-product of the coffee industry is the spent coffee grounds, with 6 million tons being produced worldwide per year. Although generally treated as waste, spent coffee grounds are a rich source of several bioactive compounds with applications in diverse industrial fields. The present work aimed at the analysis of spent coffee grounds from different geographical origins (Guatemala, Colombia, Brazil, Timor, and Ethiopia) for the identification of bioactive compounds with industrial interest. For this purpose, the identification and quantification of the bioactive compounds responsible for the antioxidant activity attributed to the spent coffee grounds were attempted using miniaturized solid-phase extraction (µ-SPEed), combined with ultrahigh-performance liquid chromatography with photodiode array detection (UHPLC-PDA). After validation of the µ-SPEed/UHPLC-PDA method, this allowed us to conclude that caffeine and 5-caffeoylquinic acid (5-CQA) are the most abundant bioactive compounds in all samples studied. The total phenolic content (TPC) and antioxidant activity are highest in Brazilian samples. The results obtained show that spent coffee grounds are a rich source of bioactive compounds, supporting its bioprospection based on the circular economy concept closing the loop of the coffee value chain, toward the valorization of coffee by-products.

Many harmful and potentially harmful constituents are present in tobacco products. Cigarette smoke is known to cause different forms of cancer and trigger the development of chronic diseases. In the last decade, electronic cigarettes have emerged as a healthier alternative associated to less harmful effects in comparison to traditional tobacco. However, the lack of standardization of electronic cigarettes products makes it difficult to establish and compare the real effects on health of products from different manufacturers. To better understand the impact of smoking and vaping, the volatomic composition of urine samples from traditional tobacco smokers and electronic cigarette users was established and compared with nonsmokers (control group), using headspace solid-phase microextraction combined with gas chromatography-mass spectrometry. A total of 45 urinary volatile organic metabolites belonging to different chemical families were identified in the urine of the studied groups. Benzene derivatives, terpenes, and aromatics were the chemical families that contributed the most to the urinary profile of smokers. The vapers urinary volatomic pattern was also dominated by terpenes and aromatics, in addition to alcohols. The orthogonal partial least squares-discriminant analysis of the data obtained indicated that the urinary profile of vapers is more closely related to the control group, reinforcing the hypothesis of the lowest harmfulness of electronic cigarettes. Further studies recruiting a higher number of subjects are therefore necessary to consolidate the data obtained.

Funding: This work was supported by FCT-Fundação para a Ciência e a Tecnologia through the CQM Base Fund—UIDB/00674/2020, and Programmatic Fund -UIDP/00674/2020, and by Madeira 14–20 Program, project PROEQUIPRAM—Reforço do Investimento em Equipamentos e Infraestruturas Científicas na RAM (M1420-01-0145-FEDER-000008), by ARDITI—Agência Regional para o Desenvolvimento da Investigação Tecnologia e Inovação, through the projects M1420-01-0145-FEDER-000005—Centro de Química da Madeira—CQM+ (Madeira 14–20 Program), Project M1420-09-5369-FSE-000001—Madeira Oceanic Observatory project. André Lopes was supported by a grant under the project ISLANDAP “R+D+i Towards Aquaponic Development in the UP islands and the Circular Economy (ISLANDAP, MAC/1. 1ª/207)” founded by the FEDER under the INTERREG MAC 2014-2020 program. Worldwide, the food industry generates a large number of by-products from a wide variety of sources. These by-products represent an interesting and economical source of added value components with potential functionalities and/or bioactivities, which might be explored for industrial purposes, encouraging and promoting the circular economy concept. In this context, the current work aimed to evaluate the fatty acids (FAs) profile using gas chromatography–flame ionization detector (GC–FID) and Fourier Transform Infrared (FTIR), as well as the determination of related health lipid indices (e.g., atherogenic (AI) and thrombogenic (TI)) as a powerful strategy to investigate the potential applications of different agri-food by-products for human nutrition and animal feeding. This work results showed that polyunsaturated fatty acids (PUFAs) are the predominant group in grape pomace (72.7%), grape bunches (54.3%), and brewer’s spent grain (BSG, 59.0%), whereas carrot peels are dominated by monounsaturated fatty acids (MUFAs, 47.3%), and grape stems (46.2%), lees (from 50.8 to 74.1%), and potato peels (77.2%) by saturated fatty acids (SFAs). These findings represent a scientific basis for exploring the nutritional properties of agri-food by-products. Special attention should be given to grape pomace, grape bunches, and BSG since they have a high content of PUFAs (from 54.3 to 72.7%) and lower AI (from 0.11 to 0.38) and TI (from 0.30 to 0.56) indexes, suggesting their potential to provide a variety of health benefits against cardiovascular diseases including well-established hypotriglyceridemia and anti-inflammatory effects, products to which they are added. info:eu-repo/semantics/publishedVersion

Sugarcane honey (SCH) is a syrup produced on Madeira Island and recognized by its unique aroma, a complex attribute of quality with an important influence on the final consumer’s acceptance of the product, and determined by a complex mixture of a large number of volatile organic compounds (VOCs) generated during its traditional making process and storage. Therefore, the purpose of this study was to establish the volatile profile of genuine SCH produced by a regional certified producer for seven years and compare it with syrups from non-certified regional producers and with producers from different geographical regions (Spain, Egypt, Brazil and Australia), as a powerful strategy to define the volatomic fingerprint of SCH. Different volatile profiles were recognized for all samples, with 166 VOCs being identified belonging to different chemical classes, including furans, ketones, carboxylic acids, aldehydes and alcohols. Chemometric analysis allowed (i) the differentiation between all syrups, being more pronounced between SCH and other syrups, and (ii) the identification of 32 VOCs as potential markers for the traceability and authenticity of SCH on the global market.

The Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method is a simple and straightforward extraction technique involving an initial partitioning followed by an extract clean-up using dispersive solid-phase extraction (d-SPE). Originally, the QuEChERS approach was developed for recovering pesticide residues from fruits and vegetables, but rapidly gained popularity in the comprehensive isolation of analytes from different matrices. According to PubMed, since its development in 2003 up to November 2018, about 1360 papers have been published reporting QuEChERS as extraction method. Several papers have reported different improvements and modifications to the original QuEChERS protocol to ensure more efficient extractions of pH-dependent analytes and to minimize the degradation of labile analytes. This analytical approach shows several advantages over traditional extraction techniques, requiring low sample and solvent volumes, as well as less time for sample preparation. Furthermore, most of the published studies show that the QuEChERS protocol provides higher recovery rate and a better analytical performance than conventional extraction procedures. This review proposes an updated overview of the most recent developments and applications of QuEChERS beyond its original application to pesticides, mycotoxins, veterinary drugs and pharmaceuticals, forensic analysis, drugs of abuse and environmental contaminants. Their pros and cons will be discussed, considering the factors influencing the extraction efficiency. Whenever possible, the performance of the QuEChERS is compared to other extraction approaches. In addition to the evolution of this technique, changes and improvements to the original method are discussed.

Synthetic cathinones (SCat) are amphetamine-like psychostimulants that emerged onto drug markets as "legal" alternatives to illicit drugs such as ecstasy, cocaine, and amphetamines. Usually they are sold as "bath salts," "plant food," or "research chemicals," and rapidly gained popularity amongst drugs users due to their potency, low cost, and availability. In addition, internet drug sales have been replacing the old way of supplying drugs of abuse, contributing to their rapid spread. Despite the legislative efforts to control SCat, new derivatives continue to emerge on the recreational drugs market and their abuse still represents a serious public health issue. To date, about 150 SCat have been identified on the clandestine drugs market, which are one of the largest groups of new psychoactive substances (NPS) monitored by the United Nations Office on Drugs and Crime and the European Monitoring Center for Drugs and Drug Addiction. Similar to the classical stimulants, SCat affect the levels of catecholamines in the central nervous system, which results in their psychological, behavioral and toxic effects. Generally, the effects of SCat greatly differ from drug to drug and relatively little information is available about their pharmacology. The present work provides a review on the development of SCat as substances of abuse, current patterns of abuse and their legal status, chemical classification, known mechanisms of action, and their toxicological effects.

The volatomic fingerprint of ciders produced in different geographical regions from Madeira Island was established using headspace solid phase microextraction combined with gas chromatography mass spectrometry (HS-SPME/GC–MS) in order to explore the effects of geographical region on the volatile pattern ciders in addition to identify potential molecular geographic markers. A total of 107 volatile organic compounds (VOCs) belonging to different chemical families were identified from which 50 VOCs are common to all ciders analysed. Significant differences in the relative content of VOCs from ciders of different geographical regions were observed. The potential of the identified VOCs for ciders discrimination according to region was assessed through chemometric tools, such as principal components analysis (PCA) and partial least squares-discriminant analysis (PLS-DA). The PCA showed significant differences among ciders from different island geographical regions. Fifteen VOCs responsible for ciders discrimination were identified by PLS-DA. Fifteen VOCs, namely five terpenoids, four alcohols, three acids and three esters, present variable importance in projection (VIP) values higher than one. Our findings provide relevant information related to volatile signature of ciders produced in Madeira Island, which may be a useful tool to cider-making process contributing to improve the quality of the final product. In addition, the geographical discrimination recognizes the unique and distinctive characteristics that will allow in the future to protect the quality and typicity of products originating in certain geographical regions.

In recent years, food frauds and adulterations have increased significantly. This practice is motivated by fast economical gains and has an enormous impact on public health, representing an important issue in food science. In this context, this review has been designed to be a useful guide of potential biomarkers of food authenticity and safety. In terms of food authenticity, we focused our attention on biomarkers reported to specify different botanical or geographical origins, genetic diversity or production systems, while at the food safety level, molecular evidences of food adulteration or spoilage will be highlighted. This report is the first to combine results from recent studies in a format that allows a ready overview of metabolites (

Background Food frauds and counterfeit products produced to obtain economic advantages have become a growing concern over the last decade. The assessment of food safety and authenticity constitute a powerful tool to mitigate this problem and protect public health. Nevertheless, the growing sophistication of fraudulent practices requires a continuous update and improvement of the analytical methodologies. Scope and approach In this context, the advances and novel techniques and chemometric approaches reported since 2016 are discussed regarding their potential use in food authentication. This review details the main analytical techniques applied in the extraction, detection and identification of metabolites to obtain food fingerprints, emphasizing the advantages and drawbacks of each approach with practical examples. Additionally, the current legislation on food authentication has also been revised. Key findings and conclusions GC-MS, LC- q-TOF-MS and NMR followed by PCA and PLS-DA are the most often reported analytical methodologies to discriminate between authentic and non-authentic foodstuffs using chemical fingerprints. More recently, novel and promising statistical methods with high classification power (DD-SIMCA, OO-SIMCA, BPR, k-NN, among others) are being already applied. Overall, the development of non-destructive, on-site and real-time analytical procedures able to deliver fast and unambiguous food authentication results will continue to be the goal driving food research.

Liquid phase-based microextraction techniques (LPµETs) have attracted great attention from the scientific community since their invention and implementation mainly due to their high efficiency, low solvent and sample amount, enhanced selectivity and precision, and good reproducibility for a wide range of analytes. This review explores the different possibilities and applications of LPμETs including dispersive liquid–liquid microextraction (DLLME) and single-drop microextraction (SDME), highlighting its two main approaches, direct immersion-SDME and headspace-SDME, hollow-fiber liquid-phase microextraction (HF-LPME) in its two- and three-phase device modes using the donor–acceptor interactions, and electro membrane extraction (EME). Currently, these LPμETs are used in very different areas of interest, from the environment to food and beverages, pharmaceutical, clinical, and forensic analysis. Several important potential applications of each technique will be reported, highlighting its advantages and drawbacks. Moreover, the use of alternative and efficient “green” extraction solvents including nanostructured supramolecular solvents (SUPRASs, deep eutectic solvents (DES), and ionic liquids (ILs)) will be discussed.

Coffee is one of the most popular beverages worldwide, whose production and consumption result in large amounts of waste, namely spent coffee grounds, constituting an important source of compounds for several industrial applications. This work focused on the establishment of the volatile fingerprint of five spent coffee grounds from different geographical origins using headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry (HS-SPME/GC-MS), as a strategy to identify volatile organic metabolites (VOMs) with potential application in the food industry as antioxidant, anti-inflammatory, and antiproliferative agents. One hundred eleven VOMs belonging to different chemical families were identified, of which 60 were found in all spent coffee grounds analyzed. Furanic compounds (34%), nitrogen compounds (30%), and esters (19%) contributed significant to the total volatile fingerprint. The data obtained suggest that spent coffee grounds have great potential to be used as raw material for different approaches in the food industry towards the development of new food ingredients or products for human consumption, in addition to pharmaceutical and cosmetic applications, namely as antioxidant (e.g., limonene, carvacrol), antimicrobial (e.g., pyrrole-2-carboxaldehyde, β-myrcene) and anti-inflammatory (e.g., furfural, 2-furanmethanol) agents, promoting their integral valorization within the circular bioeconomy concept.

Green extraction techniques (GreETs) emerged in the last decade as greener and sustainable alternatives to classical sample preparation procedures aiming to improve the selectivity and sensitivity of analytical methods, simultaneously reducing the deleterious side effects of classical extraction techniques (CETs) for both the operator and the environment. The implementation of improved processes that overcome the main constraints of classical methods in terms of efficiency and ability to minimize or eliminate the use and generation of harmful substances will promote more efficient use of energy and resources in close association with the principles supporting the concept of green chemistry. The current review aims to update the state of the art of some cutting-edge GreETs developed and implemented in recent years focusing on the improvement of the main analytical features, practical aspects, and relevant applications in the biological, food, and environmental fields. Approaches to improve and accelerate the extraction efficiency and to lower solvent consumption, including sorbent-based techniques, such as solid-phase microextraction (SPME) and fabric-phase sorbent extraction (FPSE), and solvent-based techniques (μQuEChERS; micro quick, easy, cheap, effective, rugged, and safe), ultrasound-assisted extraction (UAE), and microwave-assisted extraction (MAE), in addition to supercritical fluid extraction (SFE) and pressurized solvent extraction (PSE), are highlighted., This research was funded by FCT (Fundação para a Ciência e a Tecnologia) through the CQM Base Fund, UIDB/00674/2020, Programmatic Fund, UIDP/00674/2020, and CEB—Centre of Biological Engineering, and by ARDITI (Agência Regional para o Desenvolvimento da Investigação Tecnologia e Inovação) through the project M1420-01-0145-FEDER-000005, Centro de Química da Madeira (CQM+; Madeira 14-20 Program). The authors also acknowledge FCT and the Madeira 14–20 Program to the Portuguese Mass Spectrometry Network (RNEM) through the PROEQUIPRAM program, M14-20 M1420-01-0145-FEDER-000008). ARDITI is also acknowledged for the postdoctoral fellowship granted to J.A.M.P. (Project M1420-09-5369-FSE-000001)., info:eu-repo/semantics/publishedVersion

A wormhole-like mesostructured silica was synthesized and modified with octadecylsilane (C18) groups. The resulting hybrid material (HMS-C18) was characterized and evaluated as sorbent for simultaneous extraction of 20 polyphenols from mixed fruit-vegetable juices and smoothies by dispersive solid-phase extraction (dSPE). The samples were first subjected to solvent extraction followed by dSPE procedure. The extraction step was optimized and combined with a reversed-phase ultra-high-performance liquid chromatography method coupled to ion-trap tandem mass spectrometry (UHPLC-IT-MS/MS), which was also optimized. HMS-C18 showed high potential to extract and purify the target analytes, being more effective than commercial C18 amorphous silica. The proposed method was validated for both samples, obtaining average recoveries from 57% to 99% with relative standard deviations lower than 9%. Its applicability in the analysis of commercial mixed fruit-vegetable juices and smoothies revealed mainly contents of rutin, 4-hydroxybenzoic acid, chlorogenic acid, epicatechin, caffeic acid, and naringin in the samples analyzed.

Sugarcane honey (SCH) is a syrup from Madeira Island recognized by its unique and excellent aroma, associated to volatile organic compounds (VOCs) generated during the well-defined five stages of its traditional making process. The establishment of volatile profile throughout all SCH-making stages during four years, allowed the evaluation of the influence of each stage in the typical characterisitcs of SCH. One hundred eighthy seven VOCs were identified, being associated to several origins and formation pathways. VOCs formed during stage 1 and 2 were originate from raw material, and its oxidation (i.e. enzymatic browning) and thermal degradation (i.e. lipid oxidation, Maillard reactions, Strecker degradation). In stage 3 and 4, the caramelization and melanoidin degradation also occurred, while in stage 5, the thermal degradation continues, followed by microbial activity. Chemometric analysis allowed to identify 35 VOCs as potential markers for processing control by the producers and as guarantee of the typicality and authenticity of SCH. Based on the obtained results, we propose for the first time an innovative schematic diagram explaining the potential reactions and pathways for VOCs formation during the different steps of the SCH production.

Sugarcane (SC) is a perennial grass widely cultivated in tropical and subtropical regions. However, its cultivation in Europe is residual, where Madeira Island, Portugal, is the only region where SC continues to be extensively cultivated. For the first time, the volatile profiles of regional cultivars were established by solid-phase microextraction combined with gas chromatography-mass spectrometry. Different volatile profiles for each cultivar were recognized, identifying 260 volatile organic compounds belonging to 15 chemical classes, such as aldehydes, alcohols, ketones, hydrocarbons, esters, and terpenes. Chemometric analysis procedure, namely, one-way ANOVA with Tukey's test, principal component analysis, partial least-square analysis, linear discriminant analysis, and hierarchical clustering analysis, allowed the differentiation between all regional cultivars. This study represents an important contribution for the maintenance of biodiversity and subsistence of the SC industry in Europe. Furthermore, it is also a valuable contribution to establish the typicality of traditional SC-based products, such as SC honey.

The innovation of the new psychoactive substances (NPS) market requires the rapid identification of new substances that can be a risk to public health, in order to reduce the damage due to their use. Twelve seized products suspected to contain illicit substances were analyzed by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), gas chromatography coupled to mass spectrometry (GC-MS), and nuclear magnetic resonance spectroscopy (NMR). Synthetic cathinones (SCat) were found in all products, either as a single component or in mixtures. Infrared spectra of all products were consistent with the molecular structure of SCat, showing an intense absorption band at 1700–1674 cm‐1, corresponding to the carbonyl stretching, a medium/strong peak at 1605-1580 cm-1, indicating stretching vibrations in the aromatic ring (C=C) and bands with relative low intensity at frequencies near 2700–2400 cm-1, corresponding to an amine salt. It was possible to identify a total of eight cathinone derivatives by GC-MS and NMR analysis: 4’-methyl-α-pyrrolidinohexanophenone (MPHP), α-pyrrolidinohexanophenone (α-PHP), 3-fluoromethcathinone (3-FMC), methedrone, methylone, buphedrone, N-ethylcathinone, and pentedrone. Among the adulterants found in these samples, caffeine was the most frequently detected substance, followed by ethylphenidate. These results highlight the prevalence of SCat in seized materials of the Portuguese market. Reference standards are usually required for confirmation, but when reference materials are not available, the combination of complementary techniques is fundamental for a rapid and an unequivocal identification of such substances.

Globally, breast cancer (BC) is leading at the top of women's diseases and, as a multifactorial disease, there is the need for the development of new approaches to aid clinicians on monitoring BC treatments. In this sense, metabolomic studies have become an essential tool allowing the establishment of interdependency among metabolites in biological samples. The combination of nuclear magnetic resonance (NMR) and gas chromatography–quadrupole mass spectrometry (GC–qMS) based metabolomic analyses of urine and breast tissue samples from BC patients and cancer-free individuals was used. Multivariate statistical tools were used in order to obtain a panel of metabolites that could discriminate malignant from healthy status assisting in the diagnostic field. Urine samples (n = 30), cancer tissues (n = 30) were collected from BC patients, cancer-free tissues were resected outside the tumor margin from the same donors (n = 30) while cancer-free urine samples (n = 40) where obtained from healthy subjects and analysed by NMR and GC–qMS methodologies. The orthogonal partial least square discriminant analysis model showed a clear separation between BC patients and cancer-free subjects for both classes of samples. Specifically, for urine samples, the goodness of fit (R2Y) and predictive ability (Q2) was 0.946 and 0.910, respectively, whereas for tissue was 0.888 and 0.813, revealing a good predictable accuracy. The discrimination efficiency and accuracy of tissue and urine metabolites was ascertained by receiver operating characteristic curve analysis that allowed the identification of metabolites with high sensitivity and specificity. The metabolomic pathway analysis identified several dysregulated pathways in BC, including those related with lactate, valine, aspartate and glutamine metabolism. Additionally, correlations between urine and tissue metabolites were investigated and five metabolites (e.g. acetone, 3-hexanone, 4-heptanone, 2-methyl-5-(methylthio)-furan and acetate) were found to be significant using a dual platform approach. Overall, this study suggests that an improved metabolic profile combining NMR and GC–qMS may be useful to achieve more insights regarding the mechanisms underlying cancer.

Food supply disruption and shortage verified during the current pandemic events are a scenario that many anticipate for the near future. The impact of climate changes on food production, the continuous decrease in arable land, and the exponential growth of the human population are important drivers for this problem. In this context, adding value to food waste is an obvious strategy to mitigate food shortages, but there is a long way to go in this field. Globally, it is estimated that one-third of all food produced is lost. This is certainly due to many different factors, but the lack of awareness of the consumer about the nutritional value of certain foods parts, namely peels and seeds, is certainly among them. In this review, we will unveil the nutritional and bioactive value of the waste discarded from the most important fresh fruit and vegetables consumed worldwide as a strategy to decrease food waste. This will span the characterization of the bioactive composition of selected waste from fruits and vegetables, particularly their seeds and peels, and their possible uses, whether in our diet or recycled to other ends.

Food fraud is still a recurrent practice throughout food supply chains. In the case of seafood, misidentification of species and products repackaging constitute the most common frauds. Therefore, the development of appropriate analytical approaches to be used against food fraud is necessary. The present study goal is to explore for the first time, the possibility to differentiate between Sparus aurata from two different mariculture farms located in Madeira Island (Caniçal and Ribeira Brava), using the mass fingerprint of fish mucus obtained from MALDI-TOF MS and analyzed using Mass-UP software for multivariate statistical analysis and biomarker identification. It was possible to establish, from the mucus protein fraction, a set of potential biomarkers for each location in a total of 35 peaks, being 17 peaks specific to Caniçal located farm and 18 to Ribeira Brava. The proposed analytical approach revealed a useful strategy providing accurate and fast results for fish geographical origin discrimination.

The popularity of new psychoactive substances among drug users has become a public health concern worldwide. Among them, synthetic cannabinoids (SCs) represent the largest, most diversified and fastest growing group. Commonly known as 'synthetic marijuana' as an alternative to cannabis, these synthetic compounds are easily accessible via the internet and are sold as 'herbal incenses' under different brand names with no information about the chemical composition. In the present work, we aim to integrate gas chromatography-tandem mass spectrometry (GC-MS) and nuclear magnetic resonance (NMR) data as useful strategy for the identification and confirmation of synthetic cannabinoids present in nine seized herbal incenses. The analysis of all samples allowed the initial identification of 9 SCs, namely 5 napthoylindoles (JWH-018, JWH-073, JWH-122, JWH-210, MAM-2201), APINACA, XLR-11 and CP47,497-C8 and its enantiomer. JWH-018 was the most frequently detected synthetic compound (8 of 9 samples), while APINACA and XLR-11 were only identified in one herbal product. Other non-cannabinoid drugs, including oleamide, vitamin E and vitamin E acetate, have also been detected. Oleamide and vitamin E are two adulterants, frequently added to herbal products to mask the active ingredients or added as preservatives. However, to our knowledge, no analytical data about vitamin E acetate was reported in herbal products, being the first time that this compound is identified on this type of samples. The integration data obtained from the used analytical technologies proved to be useful, allowing the preliminary identification of the different SCs in the mixture. Furthermore, the examination of mass spectral fragment ions, as well as the results of both 1D and 2D NMR experiments, enabled the identification and confirmation of the molecular structure of SCs.

The word "cannabinoid" refers to every chemical substance, regardless of structure or origin, that joins the cannabinoid receptors of the body and brain and that have similar effects to those produced by the Cannabis plant and based on their source of production, cannabinoids can be classified into endocannabinoids, phytocannabinoids and synthetic cannabinoids. Synthetic cannabinoids represent the largest class of drugs detected through the EU Early Warning System with a total of 190 substances notified from 2008 to 2018 and about 280 have been reported worldwide to the United Nations Office on Drugs and Crime. Sprayed on natural herb mixtures with the aim to mimic the euphoria effect of cannabis and sold as "herbal smoking blends" or "herbal incense" under brand names like "Spice" or "K2", synthetic cannabinoids are available from websites for the combination with herbal materials or more recently, for the use in e-cigarettes. Currently labeled as "not for human consumption" to circumvent legislation, their legal status varies by country with many government institutions currently pushing for their control. However, due to the emergence of new substances, it requires a constant update of the list of controlled drugs. Little is known about how these substances work and their toxic effects in humans and the same product could vary not only in the amount and in the type of substance added. In the last years, synthetic cannabinoids have been associated with deaths and acute intoxications in Europe and, despite a range of new measures introduced in this area, continue to represent a challenge to current drug policy models. These synthetic substances are much more potent than natural cannabis, as well as displayed greater efficacy, acting as full agonists at the cannabinoid receptors. It is possible that, along with being highly potent, some may also have long half-lives, potentially leading to a prolonged psychoactive effect. The present work provides a review on existing literature about the development of synthetic cannabinoids as substances of abuse, current patterns of abuse and their legal status, chemical classification, and some pharmacological and toxicological properties.

Uveira-da-serra (Vaccinium padifolium Sm) is a native blueberry from Madeira Island (Portugal). In this study, the free low-molecular weight phenolic composition of Vaccinium padifolium berries (uva-da-serra - UdS), was established using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) strategy combined with liquid chromatography electrospray ionization tandem mass spectroscopy (LC-ESI-MSMS). Total phenolic content (TPC), total flavonoid content (TFC), 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS) radical-scavenging activities and oxygen radical absorbance capacity (ORAC) were also evaluated. Twenty-six phenolic compounds were identified in the UdS, being chlorogenic acid (17.4 mg/g DW), epigallocatechin (2.33 mg/g DW), caffeic acid (0.66 mg/g DW), quercetin-3-glucoside (0.38 mg/g DW) and myricetin (0.33 mg/g DW) the predominant compounds. As far we are aware, this is the first time that the free low molecular weight phenolic composition of Vaccinium padifolium Sm is characterized, also unveiling (-)epigallocatechin gallate, o-coumaric acid and m-coumaric acids presence in a Vaccinium specie. TPC (3021.8 mg GAE/100 g DW), TFC (2645.2 mg QE/100 g DW), DPPH (20509.0 µmol TE/g DW), ORAC (18510.0 µmol TE/g DW) and ABTS (19338.0 µmol TE/g DW) suggest a high antioxidant potential which is to health benefits including on cardiovascular and neurodegenerative disease prevention, making UdS a useful biosource with potential applications in food, pharmaceutical and cosmetic industries.

Electronic cigarettes (e-cigarettes) have become popular alternatives to traditional tobacco. Despite this, a comprehensive evaluation of their long-term effects and safety for the consumers and the environment is missing. To contribute to filling this gap, headspace solid-phase microextraction combined with gas chromatography-mass spectrometry (HS-SPME/GC–MS) was employed to establish and compare the volatile fingerprints of traditional tobacco and e-cigarettes. The analysis of traditional tobacco included two popular brands and different parts of the cigarette (solid tobacco, cigarette smoke, cigarette paper and filter). Regarding the e-cigarettes, two e-liquids, with and without nicotine, their main constituents (e-bases) and corresponding vapours, obtained under default vaping (power) conditions, were analysed. A total of 80 volatile organic compounds (VOCs) were identified in traditional tobacco, of which 14 carbonyl compounds, 9 benzene derivatives, 9 ethyl esters and 9 hydrocarbons. Slight differences in the volatile profile of cigarette paper and filter between the two brands were also detected, showing that exogenous components of tobacco influence the flavour and harmfulness perceived by the smokers. In turn, 92 VOCs were identified in e-cigarettes, including 31 ethyl esters, 18 alcohols and 10 hydrocarbons. No VOCs with potentially toxic or harmful effects were identified in the vapour of Do It Yourself (DIY) liquids and Premium samples. Therefore, taking into consideration the volatile compositions obtained for smoking and vaping procedures under normal conditions of operation and using certified e-liquid mixtures, the e-cigarettes analysed seemed to constitute a valid and less harmful alternative to traditional tobacco for smokers, second-hand smokers and the environment.