RESUMO
Rapid evaporative ionization mass spectrometry (REIMS) is a relatively recent MS technique explored in many application fields, demonstrating high versatility in the detection of a wide range of chemicals, from small molecules (phenols, amino acids, di- and tripeptides, organic acids, and sugars) to larger biomolecules, that is, phospholipids and triacylglycerols. Different sampling devices were used depending on the analyzed matrix (liquid or solid), resulting in distinct performances in terms of automation, reproducibility, and sensitivity. The absence of laborious and time-consuming sample preparation procedures and chromatographic separations was highlighted as a major advantage compared to chromatographic methods. REIMS was successfully used to achieve a comprehensive sample profiling according to a metabolomics untargeted analysis. Moreover, when a multitude of samples were available, the combination with chemometrics allowed rapid sample differentiation and the identification of discriminant features. The present review aims to provide a survey of literature reports based on the use of such analytical technology, highlighting its mode of operation in different application areas, ranging from clinical research, mostly focused on cancer diagnosis for the accurate identification of tumor margins, to the agri-food sector aiming at the safeguard of food quality and security.
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Espectrometria de Massas , Espectrometria de Massas/métodos , Humanos , Metabolômica , Análise de Alimentos/métodosRESUMO
BACKGROUND: Following our previous research on the differentiation of Italian extra virgin olive oils (EVOOs) by rapid evaporative ionization mass spectrometry coupled to a tandem high resolution mass analyser, the present study deals with the evaluation of another direct mass spectrometry (direct-MS) approach for the rapid and automatic discrimination of EVOOs. In particular, direct analysis in real time (DART-MS) was explored as an ambient MS (AMS) source for the building of a top-quality Italian EVOOs database and fast identification of unknown samples. A single quadrupole detector (QDa) was coupled with DART, taking advantage of a cost-saving, user-friendly and less sophisticated instrumental setup. Particularly, quickstrip cards, located on a moving rail holder, were employed, allowing for the direct analysis of 12 EVOO spots in a total analysis time of 6 min. The aim was to develop a reliable statistical model by applying principal component and linear discriminant analyses to clusterize and classify EVOOs according to geographical origin and cultivar, as main factors determining their nutritional and sensory profiles. RESULTS: Satisfactory results were achieved in terms of identification reliability of unknown EVOOs, as well as false positive risk, thus confirming that the use of AMS combined with chemometrics is a powerful tool against fraudulent activities, without the need for mass accuracy data, which would increase the analysis cost. CONCLUSION: A DART ionization source with a compact and reliable QDa MS analyser allowed for rapid fingerprinting analysis. Furthermore, MS spectra provided quali-quantitative information successfully related to EVOO differentiation. © 2023 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.
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Azeite de Oliva , Azeite de Oliva/química , Reprodutibilidade dos Testes , Espectrometria de Massas , Análise Discriminante , ItáliaRESUMO
The present work proposes the use of a fast analytical platform for the mass spectrometric (MS) profiling of canine mammary tissues in their native form for the building of a predictive statistical model. The latter could be used as a novel diagnostic tool for the real-time identification of different cellular alterations in order to improve tissue resection during veterinary surgery, as previously validated in human oncology. Specifically, Rapid Evaporative Ionization Mass Spectrometry (REIMS) coupled with surgical electrocautery (intelligent knife-iKnife) was used to collect MS data from histologically processed mammary samples, classified into healthy, hyperplastic/dysplastic, mastitis and tumors. Differences in the lipid composition enabled tissue discrimination with an accuracy greater than 90%. The recognition capability of REIMS was tested on unknown mammary samples, and all of them were correctly identified with a correctness score of 98-100%. Triglyceride identification was increased in healthy mammary tissues, while the abundance of phospholipids was observed in altered tissues, reflecting morpho-functional changes in cell membranes, and oxidized species were also tentatively identified as discriminant features. The obtained lipidomic profiles represented unique fingerprints of the samples, suggesting that the iKnife technique is capable of differentiating mammary tissues following chemical changes in cellular metabolism.
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Mama , Lipidômica , Animais , Cães , Feminino , Humanos , Espectrometria de Massas/métodos , Fosfolipídeos/química , TriglicerídeosRESUMO
The present work aims to a promising re-utilization of the massive waste derived from the tuna fishing industry, for which by-products can represent more than 50% of the original material. Due to the considerable content in polyunsaturated fatty acids and noble proteins, such wastes can be used as primary source of functional ingredients in the production of nutraceuticals. The composition of the lipid and protein tuna fractions was investigated by means of gas chromatography-mass spectrometry and high-performance liquid chromatography-tandem mass spectrometry methods (in wastes and edible parts), and a preliminary characterization of potential bioactive peptides was achieved. Automated sample preparation allowed speeding up the analytical workflow, while allowing for highly sensitive and selective lipid characterization. The ω3 fatty acid content was found higher in waste products compared to the muscle, in terms of fatty acids as well as complex lipids. As for peptides, extraction by isoelectric solubilization/precipitation was performed, followed by enzymatic digestion and high-performance liquid chromatography-tandem mass spectrometry analysis. Furthermore, the use of bioinformatics tools highlighted the presence of potential antimicrobial peptides in the samples investigated.
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Automação , Lipídeos/análise , Proteínas/análise , Resíduos/análise , Animais , Cromatografia Gasosa , Cromatografia Líquida de Alta Pressão , Pesqueiros , Indústrias , AtumRESUMO
In a previous article, Rigano et al. established a new linear retention index system for the identification of triacylglycerols by liquid chromatography methods only on the basis of the retention behavior and independently from many experimental parameters. In that work, a database of 209 compounds was built, but only 54 of them, typical of vegetable oils, were confirmed by mass spectrometry. The aim of the present research is to extend the applicability of the novel approach to more complex samples, such as fish lipid extracts, and assess the complementarity between mass spectromtery and retention information to achieve univocal identification. With this purpose, a new software was implemented to make the identification process easy and automatic as in gas chromatography-mass spectrometry where the retention index filter is added in the spectral search to discriminate between compounds with similar mass spectrometry spectra. A total of 69 species were identified and, thanks to their baseline separation obtained by an ultra high performance liquid chromatography method, a semiquantification was also performed. The species under investigation were Dicentrarchus labrax, coming from aquaculture and the wild. Some differences in their native lipid composition were observed, probably related to a different diet. A major number of samples would be necessary to confirm such a preliminary finding.
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Lipídeos/análise , Animais , Bass , Cromatografia Líquida , Bases de Dados Factuais , Espectrometria de Massas , SoftwareRESUMO
Rapid evaporative-ionization mass spectrometry (REIMS) coupled with an electroknife as a sampling device was recently employed in many application fields to obtain a rapid characterization of different samples without any need for extraction or cleanup procedures. In the present research, REIMS was used to obtain a metabolic profiling of the Kigelia africana fruit, thus extending the applicability of such a technique to the investigation of phytochemical constituents. In particular, the advantages of REIMS linked to a typical electrosurgical handpiece were applied for a comprehensive screening of this botanical species, by exploiting the mass accuracy and tandem MS capabilities of a quadrupole-time of flight analyzer. Then, 78 biomolecules were positively identified, including phenols, fatty acids and phospholipids. In the last decade, Kigelia africana (Lam.) Benth. fruit has attracted special interest for its drug-like properties, e.g., its use for infertility treatments and as anti-tumor agent, as well as against fungal and bacterial infections, diabetes, and inflammatory processes. Many of these properties are currently correlated to the presence of phenolic compounds, also detected in the present study, while the native lipid composition is here reported for the first time and could open new directions in the evaluation of therapeutic activity.
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Antibacterianos/análise , Anti-Inflamatórios/análise , Antineoplásicos Fitogênicos/análise , Bignoniaceae/química , Frutas/química , Hipoglicemiantes/análise , Espectrometria de MassasRESUMO
Scarce information about the phenolic composition of Scabiosa atropurpurea L. is available, and no carotenoid compounds have been reported thus far. In this study the phenolic and carotenoid composition of this plant was both investigated and associated bioactivities were evaluated. Aiming to obtain extracts and volatile fractions of known medicinal plants to valorize them in the pharmaceutical or food industries, two techniques of extraction and five solvents were used to determine the biologically active compounds. Gas chromatography coupled to flame ionization and mass spectrometry and liquid chromatography coupled to photodiode array and atmospheric pressure chemical ionization/electrospray ionization mass spectrometry highlighted the presence of 15 volatiles, 19 phenolic, and 24 natural pigments in Scabiosa atropurpurea L. stem samples; among them, the most abundant were 1,8-cineole, chlorogenic acid, cynaroside, and lutein. Bioactivity was assessed by a set of in vitro tests checking for antioxidant, antibacterial, antifungal, and allelopathic (against Brassica oleracea L. and Lens culinaris Medik) effects. Scabiosa atropurpurea L. stem extracts presented a considerable antioxidant, antibacterial, and allelopathic potential, with less antifungal effectiveness. These results indicate that the volatile fractions and extracts from S. atropurpurea L. stem could be considered as a good source of bioactive agents, with possible applications in food-related, agriculture, and pharmaceutical fields. Genetic investigations showed 97% of similarity with Scabiosa tschiliensis, also called Japanese Scabiosa.
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Antibacterianos , Antifúngicos , Antioxidantes , Dipsacaceae/química , Extratos Vegetais/química , Caules de Planta/química , Antibacterianos/química , Antibacterianos/farmacologia , Antifúngicos/química , Antifúngicos/farmacologia , Antioxidantes/química , Antioxidantes/farmacologia , Cromatografia Líquida de Alta Pressão , Dipsacaceae/crescimento & desenvolvimento , Cromatografia Gasosa-Espectrometria de Massas , Caules de Planta/crescimento & desenvolvimento , TunísiaRESUMO
The topic of food analysis and safety has attracted increasing interest in recent decades owing to recent scandals concerning fraudulent activities (mislabeling, sophistication, adulteration, etc.) that can undermine human health. Among them, seafood fraud has probably the strongest relationship with food safety, an activity that goes beyond economic interests. This article explores the capabilities of an innovative instrumental setup, called the "iKnife," as a powerful tool in this specific research area, where until now genomics and proteomics have been the workhorses in analytical approaches. iKnife, which means "intelligent knife," is the name of a recent technology based on rapid evaporative ionization mass spectrometry (REIMS). REIMS is an emerging technique able to characterize different samples rapidly, affording a comprehensive profile usable as a fingerprint, without the need for preliminary extraction or cleanup procedures. In detail, a REIMS source is coupled to a high-resolution tandem mass spectrometer; such coupling allows one to maximize the amount of information (discriminant features) collected for a single analysis, as well as to focus on target analytes to achieve enhanced sensitivity and selectivity. A database was created from 18 marine species typical of the Mediterranean Sea, all caught in the very small area of the Strait of Messina, and reliable identification was achieved for each species with confidence higher than 99%. One big model and three submodels were built by principal component analysis and linear discriminant analysis for unambiguous key variable identification within each class (e.g., Cephalopoda), order (e.g., Perciformes), or family (e.g., Carangidae). Graphical abstract.
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Peixes , Espectrometria de Massas/instrumentação , Alimentos Marinhos/análise , Animais , Análise Discriminante , Desenho de Equipamento , Peixes/classificação , Análise de Alimentos/instrumentação , Mar Mediterrâneo , Análise de Componente Principal , Alimentos Marinhos/classificaçãoRESUMO
Pistachio (Pistacia vera L.) belongs to the Anacardiaceae family and it is a small tree species. It is native of the Middle East and Central Asia, but currently, it is cultivated also in California and in some Mediterranean countries, such as Greece and Italy. The most important pistachio producers are Iran, the USA, and Turkey. Besides being a delicious nut, pistachio, due to its wholesome nutritional properties, could be considered as a functional food. According to the results of several studies, pistachios have been proven to have various groups of valuable phytochemicals such as anthocyanins, flavan-3-ols, proanthocyanidins, flavonols, isoflavones, flavanones, stilbenes, and phenolic acids, possessing excellent biological activities. The most common analytical technique employed for their analysis is represented by liquid chromatography coupled to photodiode array and mass spectrometry detection. However, conventional LC can present some limits especially in terms of resolving power. In this contribution, as a powerful alternative, comprehensive two-dimensional liquid chromatography (LC×LC) was applied to the determination of the polyphenolic fraction of pistachio kernels from different geographical origins. A 150-mm micro-bore cyano column (2.7 µm dp) and 50-mm superficially porous C18 silica column (2.7 µm dp) in the first (1D) and second (2D) dimensions were employed, respectively. For boosting orthogonality, a shift 2D gradient was investigated leading to an increase in the overall peak capacity. The newly developed LC×LC method showed satisfactory linearity, sensitivity, precision and accuracy, which was then applied to sample quantitative analysis. A total of 51 different polyphenolic compounds were determined in the four samples investigated and 18 out of them are hereby reported for the first time.
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Cromatografia Líquida/métodos , Espectrometria de Massas/métodos , Pistacia/química , Extratos Vegetais/química , Polifenóis/análiseRESUMO
This study aimed to investigate the potential of four sea water microalgae, isolated and cultivated at M'diq Bay in Morocco, as a new source of natural antioxidants. These microalgae belong to different classes, including Phaedactylium tricornitum (Bacillariophyceae), Nannochloropsis gaditana (Eustigmatophyceae), Nannochloris sp (Trebouxiophyceae), and Tetraselmis suecica (Chlorodendrophycea). The antioxidant properties were screened by the use of in vitro assays, namely 2,2-difenil-1-picrylhydrazyl, Ferric reducing antioxidant power, and Ferrous ions chelating activity, and compoundidentification was carried out in methanol and acetone extracts of both dried and fresh microalgae biomass by HPLC-PDA-MS analysis. Among the investigated microalgae, Phaedactylium tricornutum was the richest one regarding its carotenoid (especially all-E-fucoxanthin) and phenolic (especially protocatechuic acid) contents, as well as antioxidant activity (65.5%), followed by Nannochloris sp, Tetraselmis suicica, and Nannochloropsis gaditana, with antioxidant activity of 56.8%, 54.9%, and 51.1%, respectively.
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Antioxidantes , Carotenoides , Diatomáceas/química , Microalgas/química , Fenóis , Carotenoides/química , Carotenoides/isolamento & purificação , Flavonoides/química , Flavonoides/isolamento & purificação , Marrocos , Fenóis/química , Fenóis/isolamento & purificaçãoRESUMO
Shikimic acid is a intermediate of aromatic amino acid biosynthesis and the preferred starting material for production of the most commonly prescribed anti-influenza drug, Tamiflu. Its six-membered carbocyclic ring is adorned with several chiral centers and various functionalities, making shikimic acid a valuable chiral synthon. When microbially-produced, in addition to shikimic acid, numerous other metabolites are exported out of the cytoplasm and accumulate in the culture medium. This extracellular matrix of metabolites is referred to as the microbosphere. Due to the high sample complexity, in this study, the microbosphere of shikimate-producing Escherichia coli SP1.1/pKD15.071 was analyzed by liquid chromatography and comprehensive two-dimensional liquid chromatography coupled to photodiode array and mass spectrometry detection. GC analysis of the trimethylsilyl derivatives was also carried out in order to support the elucidation of the selected metabolites in the microbosphere. The elucidation of the metabolic fraction of this bacterial strain might be of valid aid for improving, through genetic changes, the concentration and yield of shikimic acid synthesized from glucose. Graphical abstract.
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Cromatografia Líquida/métodos , Escherichia coli/metabolismo , Ácido Chiquímico/metabolismo , Escherichia coli/química , Escherichia coli/genética , Fermentação , Cromatografia Gasosa-Espectrometria de Massas , Engenharia Genética , Microbiologia Industrial , Redes e Vias Metabólicas , Ácido Chiquímico/análiseRESUMO
The present work focuses on the phytochemical characterization and evaluation of antianginal activity of the bark of Sterculia setigera. It was collected and authenticated in the African region of Mali, where the local population largely employs this plant for the treatment of several diseases. In the context of traditional or folk medicine and recent progresses in alternative medicine practices, it is essential to expand the knowledge about the chemical composition of such medicinal plants. In this research, a direct-Mass Spectrometry (MS) technique, known as Rapid Evaporative Ionization Mass Spectrometry (REIMS) was used for the identification of the main constituents of the Sterculia setigera bark. The REIMS source is here coupled with an electroknife as sampling device, so that the dried and pulverized bark was directly cut through the electroknife to generate a vapor, which was online transferred to the source via a Venture tube. In this way, an ambient MS approach was realized, which avoids any sample preparation procedure or pretreatment; the sample was analyzed in its native state according to a time-saving analytical process. A quadrupole-time of flight MS/MS analyzer was exploited for the identification process, based on mass accuracy data and MS/MS experiments for structure elucidation purposes. Lipids, including triterpenes, fatty acids, γ-sitosterol and α-tocopherol, and phenolic compounds were identified, some of them reported for the first time in a plant of the Sterculia genus and further confirmed through a gas chromatography-mass spectrometry analysis. The obtained metabolomic profile was successfully correlated to the antianginal activity of this plant.
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Angina Pectoris , Fármacos Cardiovasculares , Casca de Planta , Extratos Vegetais , Casca de Planta/química , Mali , Angina Pectoris/tratamento farmacológico , Extratos Vegetais/farmacologia , Extratos Vegetais/uso terapêutico , Fármacos Cardiovasculares/farmacologia , Fármacos Cardiovasculares/uso terapêuticoRESUMO
The present study aimed to identify the content of astaxanthin and its esterified forms using high-performance liquid chromatography coupled with diode array and atmospheric pressure chemical ionisation mass spectrometry detection in three samples of shrimp waste. The analyses revealed twenty-one astaxanthin derivatives, including astaxanthin in free form, across all three extracts with the highest number of derivatives observed in the head extract. The shell extract had a lower content of astaxanthin and its esterified forms, with monoesterified astaxanthins being the major components, with contents ranging from 0.5-1 mg g-1. On the other hand, in both global waste and head extracts, astaxanthin diesters were found to be the dominant bioactive compounds, with contents ranging from 0.7-5.2 mg g-1 and 10.2-18.2 mg g-1, respectively. Notably, the astaxanthin content extracted from head was significantly higher compared to other extracts, indicating its potential as a valuable source of bioactive compounds.
RESUMO
Punica granatum L., commonly known as pomegranate, is an ancient fruit widely consumed all over the world as fresh fruit or juice. In addition, it is extensively used in therapeutic formulas, cosmetics and food seasonings. The fruit is native to Afghanistan, Iran, China and the Indian sub-continent. The pomegranate market has steadily grown, presumably due to the increasing demand of health-conscious consumers for products with potential beneficial effects on human health, due to the synergistic presence of a unique and complex phytochemical composition that enclose anthocyanins, phenolic acids and hydrolysable tannins. Conventionally, for their analysis liquid chromatography is employed even though it can present some drawbacks in terms of resolving power. In this contribution, as a valuable alternative, comprehensive two-dimensional liquid chromatography with "shifted gradients" in the second dimension, was applied for the characterization of three pomegranate samples, leading to the identification of 37 different polyphenolic compounds.
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Cromatografia Líquida/métodos , Espectrometria de Massas/métodos , Polifenóis/análise , Punica granatum/química , Antocianinas/análise , Frutas/química , Humanos , Taninos Hidrolisáveis/análise , Lythraceae , Compostos Fitoquímicos/análise , Extratos Vegetais/químicaRESUMO
Isolation and identification of novel microalgae strains with high lipid productivity is one of the most important research topics to have emerged recently. However, practical production processes will probably require the use of local strains adapted to commanding climatic conditions. The present manuscript describes the isolation of 96 microalgae strains from seawater located in Bay M'diq, Morocco. Four strains were identified using the 18S rDNA and morphological identification through microscopic examination. The biomass and lipid productivity were compared and showed good results for Nannochloris sp., (15.93 mg/L/day). The lipid content in the four species, namely Nannochloropsis gaditana, Nannochloris sp., Phaedactylum tricornutum and Tetraselmis suecica, was carried out by high performance liquid chromatography coupled to mass spectrometry (HPLC-MS )highlighting the identification of up to 77 compounds.
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Apart from its essential oil, Prunus armeniaca L. kernel extract has received only scarce attention. The present study aimed to describe the lipid and polyphenolic composition of the dichloromethane, chloroform, ethyl acetate, and ethanol extracts on the basis of hot extraction, performing analysis by gas chromatography and high-performance liquid chromatography coupled with mass spectrometry. A total of 6 diacylglycerols (DAGs) and 18 triacylglycerols (TAGs) were detected as being present in all extracts, with the predominance of OLL (dilinoleyl-olein), OOL (dioleoyl-linolein), and OOO (triolein), with percentages ranging from 19.0-32.8%, 20.3-23.6%, and 12.1-20.1%, respectively. In further detail, the extraction with ethyl acetate (medium polarity solvent) gave the highest signal for all peaks, followed by chloroform and dichloromethane (more apolar solvent), while the extraction with ethanol (polar solvent) was the least efficient. Ethanol showed very poor signal for the most saturated TAGs, while dichloromethane showed the lowest percentages of DAGs. Accordingly, the screening of the total fatty acid composition revealed the lowest percentage of linoleic acid (C18:2n6) in the dichloromethane extract, which instead contained the highest amount (greater than 60%) of oleic acid (C18:1n9). Polyphenolic compounds with pharmacological effects (anti-tumor, anti-coagulant, and inflammatory), such as coumarin derivative and amygdalin, occurred at a higher amount in ethyl acetate and ethanol extracts.
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The proanthocyanidins and carotenoids composition of peel and pulp from persimmon "Seedless Pollination Variant Non-Astringent" cultivar during ripening was evaluated. Phloroglucinolysis method, combined with HPLC separation, confirmed three terminal units, the flavonol myricetin, in addition to the typical flavan-3-ols catechin and epicatechin. The extender units were epicatechin, epigallocatechin, epigallocatechin-3-O-gallate, epicatechin-3-O-gallate, and catechin. Proanthocyanidins were characterized by a considerable level of 3-O-galloylation (34-60%), showing a high prodelphinidin content (29-46%) and a mean degree of polymerization between 55 and 10. A carotenoid increase was observed during fruit ripening both in the peel and the pulp, with the highest contents respectively, for the peel and the pulp of 42.11â¯mg/Kg and 13.32â¯mg/Kg, determined at the almost fully mature stage.