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Food quality has recently received considerable attention from governments, researchers, and consumers due to the increasing demand for healthier and more nutritious food products. Traditionally, food quality is determined using a range of destructive and time-consuming approaches with modest analytical performance, underscoring the urgent need to develop novel analytical techniques. The Fourth Industrial Revolution (called Industry 4.0) is progressing exponentially, driven by the advent of a range of digital technologies and other innovative technological advances. “Food Quality 4.0” is a new concept referring to the use of Industry 4.0 technologies in food analysis to achieve rapid, reliable, and objective assessment of food quality. In this review, we will first discuss the fundamentals and principles of Food Industry 4.0 technologies and their connections with the Food Quality 4.0 concept. Then, the most common techniques used to determine food quality will briefly be reviewed before highlighting the advancements made in analytical techniques to assess food quality in the era of Industry 4.0. Food Quality 4.0 is characterized by growing digitalization and automation of food analysis using the most advanced technologies in the food industry. Key aspects of Food Quality 4.0, including, among others, non-destructive fingerprinting techniques, omics technologies and bioinformatics tools, Artificial Intelligence and Big Data, have great potential to revolutionize food quality. Although most of these technologies are still under development, it is anticipated that future research will overcome current limitations for large-scale applications.

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.

Mallow blue (Malva sylvestris L.), hibiscus (Hibiscus rosa-sinensis L.) and nasturtium (Tropaeolum majus L.), are common edible flowers rich in bioactive secondary metabolites (BASMs) whose use in sophisticated gastronomy present currently as increasing trend. In this study the BASMs profile of these edible flowers was established using an emerging green extraction technique, μQuEChERS followed by ultra-high performance liquid chromatography coupled to a photodiode array detection system (UHPLC-PDA). After validation the μQuEChERS/UHPLC-PDA methodology allow to identify that apigenin and epigallocatechin gallate are the most abundant BASMs in mallow blue flowers, while catechin and dicaffeoylquinic acid are predominant in hibiscus flowers, and myricitrin and dicaffeoylquinic acid in nasturtium flowers. Total polyphenol content is the highest in the extract of hibiscus. Nasturtium shows the greatest radical scavenging activity. The results revealed that these flowers constitute a potential source of BASMs with different bioactive properties suggesting its use in design of new functional foods.

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.

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.

Plant cell cultures from cloudberry (CL), lingonberry (LI), stone berry (ST), arctic bramble (AB), and strawberry (SB) were studied in terms of their polyphenol and carotenoid composition, antioxidant activity, antihemolytic activity and cytotoxicity effects on cancerous cells. High-resolution mass spectrometry data showed that LI, presented the highest antioxidant activity, contained the highest contents of flavones, phenolic acids, lignans, and total carotenoids, while CL, ST and SB presented the opposite behavior. AB and SB presented the lowest FRAP and CUPRAC values, while AB and CL presented the lowest reducing power. SB presented the lowest antioxidant activity measured by single electron transfer assays and the lowest content of lignans, phenolic acids, and flavones. CL and LI decreased the viability of in vitro mammary gland adenocarcinoma while only LI decreased the viability of in vitro lung carcinoma and showed protective effects of human erythrocytes against mechanical hemolysis.

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.

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.

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

In this study, the health-promoting benefits of different fruits grown in Madeira Island, namely lemon (Citrus limon var. eureka), tangerine (Citrus reticulata var. setubalense), pitanga (Eugenia uniflora var. red), tomato (Solanum lycopersicum var. gordal) and uva-da-serra, an endemic blueberry (Vaccinium padifolium Sm.), were investigated. The phenolic composition (total phenolics and total flavonoids content) and antioxidant capacity (assessed through ABTS and DPPH assays) were measured revealing a high phenolic potential for all fruits, except tomato, while uva-da-serra is particularly rich in flavonoids. In relation to the antioxidant capacity, the highest values were obtained for pitanga and uva-da-serra extracts. The bioactive potential was also assessed through the ability of the extracts to inhibit digestive enzymes linked to diabetes (α-amylase, α- and β-glucosidases) and hypertension (angiotensin-converting enzyme, ACE). The results obtained point to a very high bioactive potential with the selected samples exhibiting very important ACE anti-enzymatic capacities. A statistical analysis of the obtained data reveals a very strong correlation between ABTS and TPC, and a strong contribution of the fruit polyphenols for enzyme inhibition, and thus, presenting high antihypertensive and antidiabetic capacities. Overall, the results obtained clearly show a high bioactive potential of the selected fruits that should be further studied, in terms of specific phenolic composition. Moreover, these results strongly support the valorisation of pitanga seeds usually discarded as a waste, and uva-da-serra, an endemic and wild bush, as potential bioresources of bioactive compounds with impact in human diet.

Phthalates are a group of chemicals used in a multitude of important industrial products (e.g., medical devices, children’s toys, and food packages), mainly as plasticizers to improve mechanical properties such as flexibility, transparency, durability, and longevity of polyvinyl chloride (PVC). The wide occurrence of phthalates in many consumer products, including foods (e.g., bottled water, soft drinks, wine, milk, and meat) brings that most people are exposed to phthalates every day, which raises some concerns. Adverse health outcomes from phthalates exposure have been associated with endocrine disruption, deformities in the human reproductive system, increased risk of preterm birth, carcinogen exposure, among others. Apprehension related to the health risks and ubiquitous incidence of phthalates in foods inspires the development of reliable analytical approaches that allow their detection and quantification at trace levels. The purpose of the current review is to provide information related to the presence of phthalates in the food chain, highlighting the health risks associated with their exposure. Moreover, an overview of emerging extraction procedures and high-resolution analytical approaches for a comprehensive quantification of phthalates is presented.

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.

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.

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 from 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. M1420-01-0145-FEDER-000005 M1420-01-0145-FEDER-000008 info:eu-repo/semantics/publishedVersion

Food deterioration caused by microbial agents often involve the formation of biogenic amines (BAs), which can have harmful effects on human health. In this study a set of BAs - tryptamine, cadaverine, putrescine, spermine, histamine, tyramine, and spermidine, were simultaneously analysed to monitor their occurrence in different types of tuna samples. An improved extraction approach involving ultrasound-assisted microextraction (USAμET) followed by derivatization with dansyl chloride (DnsCl) and analysis by ultrahigh performance liquid chromatography (UHPLC) with fluorescence detection was validated for BAs quantification. The performance of the USAμET/UHPLC-FLD was assessed by studying the limits of detection (LOD) and quantification (LOQ), linear dynamic range (LDR), precision (intra and inter-day) and matrix effect (ME). Good linearity (r2 > 0.98), LODs (from 0.98 to 8.57 mg kg−1) and LOQs (3.20–25.6 mg kg−1) were achieved for all BAs analysed. Recoveries ranged from 76% to 106%, with relative standard deviations (RSD) lower than 5.0%. ME was determined from 7.52 to 50% and the intra and inter-day precisions ranged from 4.7 to 11.6% and 5.5–14.2%, respectively. BAs levels varied significantly from 4.09 ± 0.8 mg kg−1 of putrescine in olive oil canned samples to 577.9 ± 5.9 mg kg−1 of cadaverine in natural canned samples. Tryptamine and tyramine were not detected in any of the samples analysed, while spermine and spermidine were found in 85.7% of the assayed tuna samples. Cadaverine was the most dominant BA with concentrations ranging from 54.3 ± 2.5 mg kg−1, in olive oil canned tuna, to 577.9 ± 5.9 mg kg−1, in natural canned samples, whereas putrescine had the lowest concentration (average 6.9 ± 2.5 mg kg−1). The validated methodology revealed important improvements in terms of simplification of the experimental layout, expressed in the low sample and reagent amounts, in addition to less time-consuming and labour-intensive requirements that did not compromise the analytical performance.

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 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.