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1.
J Mass Spectrom ; 58(10): e4952, 2023 Oct.
Article En | MEDLINE | ID: mdl-37401097

An analytical method based on ultrasound assisted extraction (UAE) and liquid chromatography coupled to electrospray tandem mass spectrometry (LC-ESI/MS/MS) was validated and applied for determining L-dopa in four ecotypes of Fagioli di Sarconi beans (Phaseolus vulgaris L.), marked with the European label PGI (Protected Geographical Indication). The selectivity of the proposed method was ensured by the specific fragmentation of the analyte. Simple isocratic chromatographic conditions and mass spectrometric detection in multiple reaction monitoring (MRM) acquisition mode were used for sensitive quantification. The LC-ESI/MS/MS method was validated within a linear range of 0.001-5.000 µg/mL. Values of 0.4 and 1.1 ng/mL were obtained for the limits of detection and quantification, respectively. The repeatability, inter-day precision, and recovery values ranges were 0.6%-4.5%, 5.4%-9.9%, and 83%-93%, respectively. Fresh and dried beans, as well as pods, cultivated exclusively with organic methods avoiding any synthetic fertilizers and pesticides were analyzed showing an L-dopa content ranging from 0.020 ± 0.005 to 2.34 ± 0.05 µg/g dry weight.


Pesticides , Phaseolus , Chromatography, Liquid/methods , Tandem Mass Spectrometry/methods , Phaseolus/chemistry , Levodopa , Chromatography, High Pressure Liquid
2.
Food Chem ; 429: 136906, 2023 Dec 15.
Article En | MEDLINE | ID: mdl-37480776

Reinforced films were fabricated by impregnating paper in ethyl cellulose solutions. After solvent evaporation, the infused ethyl cellulose acted as binder of the paper microfibres and occupied the pores and cavities, thus improving the mechanical and barrier properties. To prepare active films, avocado by-products from guacamole industrial production were extracted in ethyl acetate. Then, the extract (optimized to be rich in phenolic compounds and flavonoids and mainly composed by lipids) was incorporated to the paper reinforced with the highest content of ethyl cellulose. In general, the addition of the avocado by-products extract decreased the water uptake and permeability, improved the wettability, and increased the biodegradability in seawater and the antioxidant capacity. In addition, these films acted as barriers and retainers for Escherichia coli and Bacillus cereus. The potentiality of these materials for food packaging was demonstrated by low overall migrations and a similar food preservation to common low-density polyethylene.


Persea , Food Packaging , Antioxidants , Escherichia coli , Plant Extracts
3.
Molecules ; 28(13)2023 Jul 06.
Article En | MEDLINE | ID: mdl-37446900

L-Dopa, a bioactive compound naturally occurring in some Leguminosae plants, is the most effective symptomatic drug treatment for Parkinson's disease. During disease progression, fluctuations in L-DOPA plasma levels occur, causing motor complications. Sensing devices capable of rapidly monitoring drug levels would allow adjusting L-Dopa dosing, improving therapeutic outcomes. A novel amperometric biosensor for L-Dopa detection is described, based on tyrosinase co-crosslinked onto a graphene oxide layer produced through electrodeposition. Careful optimization of the enzyme immobilization procedure permitted to improve the long-term stability while substantially shortening and simplifying the biosensor fabrication. The effectiveness of the immobilization protocol combined with the enhanced performances of electrodeposited graphene oxide allowed to achieve high sensitivity, wide linear range, and a detection limit of 0.84 µM, suitable for L-Dopa detection within its therapeutic window. Interference from endogenous compounds, tested at concentrations levels typically found in drug-treated patients, was not significant. Ascorbic acid exhibited a tyrosinase inhibitory behavior and was therefore rejected from the enzymatic layer by casting an outer Nafion membrane. The proposed device was applied for L-Dopa detection in human plasma, showing good recoveries.


Biosensing Techniques , Graphite , Humans , Levodopa , Monophenol Monooxygenase , Biosensing Techniques/methods , Electrochemical Techniques
4.
Mass Spectrom Rev ; 42(5): 1557-1588, 2023.
Article En | MEDLINE | ID: mdl-34570373

Surfactants are surface-active agents widely used in numerous applications in our daily lives as personal care products, domestic, and industrial detergents. To determine complex mixtures of surfactants and their degradation products, unselective and rather insensitive methods, based on colorimetric and complexometric analyses are no longer employable. Analytical methodologies able to determine low concentration levels of surfactants and closely related compounds in complex matrices are required. The recent introduction of robust, sensitive, and selective mass spectrometry (MS) techniques has led to the rapid expansion of the surfactant research field including complex mixtures of isomers, oligomers, and homologues of surfactants as well as their chemically and biodegradation products at trace levels. In this review, emphasis is given to the state-of-the-art MS-based analysis of surfactants and their degradation products with an overview of the current research landscape from traditional methods involving hyphenate techniques (gas chromatography-MS and liquid chromatography-MS) to the most innovative approaches, based on high-resolution MS. Finally, we outline a detailed explanation on the utilization of MS for mechanistic purposes, such as the study of micelle formation in different solvents.

5.
Molecules ; 27(21)2022 Nov 02.
Article En | MEDLINE | ID: mdl-36364292

L-Dopa (LD), a substance used medically in the treatment of Parkinson's disease, is found in several natural products, such as Vicia faba L., also known as broad beans. Due to its low chemical stability, LD analysis in plant matrices requires an appropriate optimization of the chosen analytical method to obtain reliable results. This work proposes an HPLC-UV method, validated according to EURACHEM guidelines as regards linearity, limits of detection and quantification, precision, accuracy, and matrix effect. The LD extraction was studied by evaluating its aqueous stability over 3 months. The best chromatographic conditions were found by systematically testing several C18 stationary phases and acidic mobile phases. In addition, the assessment of the best storage treatment of Vicia faba L. broad beans able to preserve a high LD content was performed. The best LD determination conditions include sun-drying storage, extraction in HCl 0.1 M, chromatographic separation with a Discovery C18 column, 250 × 4.6 mm, 5 µm particle size, and 99% formic acid 0.2% v/v and 1% methanol as the mobile phase. The optimized method proposed here overcomes the problems linked to LD stability and separation, thus contributing to the improvement of its analytical determination.


Vicia faba , Chromatography, High Pressure Liquid/methods , Vicia faba/chemistry , Levodopa , Methanol
6.
J Am Soc Mass Spectrom ; 33(11): 2108-2119, 2022 Nov 02.
Article En | MEDLINE | ID: mdl-36264209

An analytical approach based on reversed-phase liquid chromatography coupled to electrospray ionization Fourier-transform mass spectrometry in negative ion mode (RPLC-ESI-(-)-FTMS) was developed for the untargeted characterization of glucosinolates (GSL) in the polar extracts of four Brassica microgreen crops, namely, garden cress, rapeseed, kale, and broccoli raab. Specifically, the all ion fragmentation (AIF) operation mode enabled by a quadrupole-Orbitrap mass spectrometer, i.e., the systematic fragmentation of all ions generated in the electrospray source, followed by the acquisition of an FTMS spectrum, was exploited. First, the best qualifying product ions for GSL were recognized from higher-energy collisional dissociation (HCD)-FTMS2 spectra of representative standard GSL. Extracted ion chromatograms (EIC) were subsequently obtained for those ions from RPLC-ESI(-)-AIF-FTMS data referred to microgreen extracts, by plotting the intensity of their signals as a function of retention time. The alignment of peaks detected in the EIC traces was finally exploited for the recognition of peaks potentially related to GSL, with the EIC obtained for the sulfate radical anion [SO4]•- (exact m/z 95.9523) providing the highest selectivity. Each putative GSL was subsequently characterized by HCD-FTMS2 analyses and by collisionally induced dissociation (CID) multistage MSn (n = 2, 3) acquisitions based on a linear ion trap mass spectrometer. As a result, up to 27 different GSLs were identified in the four Brassica microgreens. The general method described in this work appears as a promising approach for the study of GSL, known and novel, in plant extracts.


Brassica , Glucosinolates , Glucosinolates/analysis , Glucosinolates/chemistry , Chromatography, Liquid/methods , Spectrometry, Mass, Electrospray Ionization/methods , Ions/chemistry , Plant Extracts
7.
Anal Bioanal Chem ; 414(27): 7805-7812, 2022 Nov.
Article En | MEDLINE | ID: mdl-36121471

The chemical composition of wine samples comprises numerous bioactive compounds responsible for unique flavor and health-promoting properties. Thus, it's important to have a complete overview of the metabolic profile of new wine products in order to obtain peculiar information in terms of their phytochemical composition, quality, and traceability. To achieve this aim, in this work, a mass spectrometry-based phytochemical screening was performed on seven new wine products from Villa D'Agri in the Basilicata region (Italy), i.e., Aglianico Bianco, Plavina, Guisana, Giosana, Malvasia ad acino piccolo, Colata Murro and Santa Sofia. Ultra-high-resolution mass spectrometry data were processed into absorption mode FT-ICR mass spectra, in order to remove artifacts and achieve a higher resolution and lower levels of noise. Accurate mass-to-charge ratio (m/z) values were converted into putative elemental formulas. Therefore, 2D van Krevelen diagrams were used as a tool to obtain molecular formula maps useful to perform a rapid and more comprehensive analysis of the wine sample metabolome. The presence of important metabolite classes, i.e., fatty acid derivatives, amino acids and peptides, carbohydrates and phenolic derivatives, was assessed. Moreover, the comparison of obtained metabolomic maps revealed some differences among profiles, suggesting their employment as metabolic fingerprints. This study shed some light on the metabolic composition of seven new Italian wine varieties, improving their value in terms of related bioactive compound content. Moreover, different metabolomic fingerprints were obtained for each of them, suggesting the use of molecular maps as innovative tool to ascertain their unique metabolic profile.


Wine , Amino Acids/analysis , Carbohydrates/analysis , Fatty Acids/analysis , Mass Spectrometry , Metabolomics/methods , Peptides/analysis , Wine/analysis
8.
Antioxidants (Basel) ; 10(11)2021 Oct 25.
Article En | MEDLINE | ID: mdl-34829554

The peppers of the Capsicum species are exploited in many fields, as flavoring agents in food industry, or as decorative and therapeutic plants. Peppers show a diversified phytochemical content responsible for different biological activities. Synergic activity exerted by high levels of antioxidant compounds is responsible for their important anti-inflammatory property. A methanolic extract was obtained from a new pepper genotype and tested for anti-inflammatory activity. The extract was incorporated into phospholipid vesicles to increase the bioavailability of its bioactive components. Two types of phospholipid vesicles were produced, conventional liposomes and Penetration Enhancer containing Vesicles (PEVs). They were tested in human monoblastic leukemia U937 cell line, showing no cytotoxic effect. The intracellular reactive oxygen species (ROS) and nitric oxide (NO) levels were measured to value the in vitro efficacy of the vesicles in regulating inflammatory responses. Liposomal incorporation significantly reduced ROS levels in extract-treated LPS-activated cells. Furthermore, LC-MS/MS analyses demonstrated that liposomes facilitated the transport of the extract components across the cell membrane and their accumulation into the cytoplasm.

9.
J Mass Spectrom ; 56(5): e4722, 2021 May.
Article En | MEDLINE | ID: mdl-33813760

Chronic wounds result from the failure of the normal wound healing process. Any delay during the tissue repair process could be defined as chronic wound healing, potentially having a highly detrimental impact on human health. To face this problem, in the last years, the use of different technologies alternative to therapeutic agents is gaining more attention. The Helix aspersa snail slime-based products are increasingly being used for skin injury, thanks to their ability to make tissue repair processes faster. To date, a comprehensive overview of pure snail slime metabolome is not available. Besides, Au nanoparticles (AuNPs) technology is spreading rapidly in the medical environment, and the search for AuNPs "green" synthetic routes that involve natural products as precursor agents is demanded, alongside with a deep comprehension of the kind of species that actively take part in synthesis and product stabilization. The aim of this work is to characterize the metabolic profile of a pure snail slime sample, by an untargeted high-resolution mass spectrometry-based analysis. In addition, insights on AuNPs synthesis and stabilization by the main components of pure snail slime used to induce the synthesis were obtained. The untargeted analysis provided a large list of important classes of metabolites, that is, fatty acid derivatives, amino acids and peptides, carbohydrates and polyphenolic compounds that could be appreciated in both samples of slime, with and without AuNPs. Moreover, a direct comparison of the obtained results suggests that mostly nitrogen and sulfur-bearing metabolites take part in the synthesis and stabilization of AuNPs.


Anti-Infective Agents/chemistry , Gold/chemistry , Metal Nanoparticles/chemistry , Mucus/chemistry , Wound Healing/drug effects , Amino Acids/chemistry , Amino Acids/metabolism , Animals , Anti-Infective Agents/pharmacology , Carbohydrates/chemistry , Fatty Acids/chemistry , Fatty Acids/metabolism , Green Chemistry Technology , Humans , Metabolome , Peptides/chemistry , Peptides/metabolism , Polyphenols/chemistry , Polyphenols/metabolism , Skin , Snails , Tandem Mass Spectrometry/methods
10.
Polymers (Basel) ; 13(1)2021 Jan 04.
Article En | MEDLINE | ID: mdl-33406618

Conventional petroleum-derived plastics represent a serious problem for global pollution because, when discarded in the environment, are believed to remain for hundreds of years. In order to reduce dependence on fossil resources, bioplastic materials are being proposed as safer alternatives. Bioplastics are bio-based and/or biodegradable materials, typically derived from renewable sources. Food waste as feedstock represents one of the recent applications in the research field of bioplastics production. To date, several food wastes have been used as raw materials for the production of bioplastics, including mostly fruit and vegetable wastes. The conversion of fruit and vegetable wastes into biomaterials could occur through simple or more complex processes. In some cases, biopolymers extracted from raw biomass are directly manufactured; on the other hand, the extracted biopolymers could be reinforced or used as reinforcing agents and/or natural fillers in order to obtain biocomposites. The present review covers available results on the application of methods used in the last 10 years for the design of biomaterials obtained from formulations made up with both fruits and vegetables by-products. Particular attention will be addressed to the waste pre-treatment, to the bioplastic formulation and to its processing, as well as to the mechanical and physical properties of the obtained materials.

11.
Talanta ; 224: 121862, 2021 Mar 01.
Article En | MEDLINE | ID: mdl-33379073

Since coronavirus disease 2019 (COVID-19) started as a fast-spreading pandemic, causing a huge number of deaths worldwide, several therapeutic options have been tested to counteract or reduce the clinical symptoms of patients infected with the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Currently, no specific drugs for COVID-19 are available, but many antiviral agents have been authorised by several national agencies. Most of them are under investigation in both preclinical and clinical trials; however, pharmacokinetic and metabolism studies are needed to identify the most suitable dose to achieve the desired effect on SARS-CoV-2. Therefore, the efforts of the scientific community have focused on the screening of therapies able to counteract the most severe effects of the infection, as well as on the search of sensitive and selective analytical methods for drug detection in biological matrices, both fluids and tissues. In the last decade, many analytical methods have been proposed for the detection and quantification of antiviral compounds currently being tested for COVID-19 treatment. In this review, a critical discussion on the overall analytical procedure is provided, i.e (a) sample pre-treatment and extraction methods such as protein precipitation (PP), solid-phase extraction (SPE), liquid-liquid extraction (LLE), ultrasound-assisted extraction (UAE) and QuEChERS (quick, easy, cheap, effective, rugged and safe), (b) detection and quantification methods such as potentiometry, spectrofluorimetry and mass spectrometry (MS) as well as (c) methods including a preliminary separation step, such as high performance liquid chromatography (HPLC) and capillary electrophoresis (CE) coupled to UV-Vis or MS detection. Further current trends, advantages and disadvantages and prospects of these methods have been discussed, to help the analytical advances in reducing the harm caused by the SARS-CoV-2 virus.


Antiviral Agents/analysis , Animals , Antiviral Agents/chemistry , Antiviral Agents/isolation & purification , COVID-19/epidemiology , Chemical Fractionation , Chromatography, High Pressure Liquid , Humans , Pandemics , SARS-CoV-2/drug effects , Tandem Mass Spectrometry , COVID-19 Drug Treatment
12.
Oxid Med Cell Longev ; 2020: 4264815, 2020.
Article En | MEDLINE | ID: mdl-33204395

Pistacia lentiscus shows a long range of biological activities, and it has been used in traditional medicine for treatment of various kinds of diseases. Moreover, related essential oil keeps important health-promoting properties. However, less is known about P. lentiscus hydrosol, a main by-product of essential oil production, usually used for steam distillation itself or discarded. In this work, by using ultra-high-resolution ESI(+)-FT-ICR mass spectrometry, a direct identification of four main classes of metabolites of P. lentiscus hydrosol (i.e., terpenes, amino acids, peptides, and condensed heterocycles) was obtained. Remarkably, P. lentiscus hydrosol exhibited an anti-inflammatory activity by suppressing the secretion of IL-1ß, IL-6, and TNF-α proinflammatory cytokines in lipopolysaccharide- (LPS-) activated primary human monocytes. In LPS-triggered U937 cells, it inhibited NF-κB, a key transcription factor in inflammatory cascade, regulating the expression of both the mitochondrial citrate carrier and the ATP citrate lyase genes. These two main components of the citrate pathway were downregulated by P. lentiscus hydrosol. Therefore, the levels of ROS, NO, and PGE2, the inflammatory mediators downstream the citrate pathway, were reduced. Results shed light on metabolic profile and anti-inflammatory properties of P. lentiscus hydrosol, suggesting its potential as a therapeutic agent.


Anti-Inflammatory Agents/pharmacology , Citric Acid/metabolism , Inflammation/drug therapy , Monocytes/drug effects , NF-kappa B/metabolism , Pistacia/chemistry , Plant Extracts/pharmacology , Apoptosis/drug effects , Cell Proliferation/drug effects , Humans , Inflammation/immunology , Inflammation/metabolism , Inflammation/pathology , Inflammation Mediators/metabolism , Metabolome/drug effects , Monocytes/immunology , Monocytes/metabolism , Monocytes/pathology , U937 Cells
13.
Soft Matter ; 16(48): 10876-10888, 2020 Dec 28.
Article En | MEDLINE | ID: mdl-33225330

In this work, for the first time, snail slime from garden snails "Helix Aspersa Müller", has been used to induce the formation of eco-friendly gold nanoparticles (AuNPs-SS) suitable for biomedical applications. An AuNPs-SS comprehensive investigation was performed and AuNPs with an average particle size of 14 ± 6 nm were observed, stabilized by a slime snail-based organic layer. Indeed, as recognized in high-resolution MALDI-MS analyses, and corroborated by FESEM, UV-Vis, ATR-FTIR, and XPS results, it was possible to assess the main presence of peptides and amino acids as the main components of the slime, that, combined with the AuNPs confers on them interesting properties. More specifically, we tested, in vitro, the AuNPs-SS safety in human keratinocytes and their potential effect on wound healing as well as their anti-inflammatory properties in murine macrophages. Moreover, the AuNPs-SS treatment resulted in a significant increase of the urokinase-type plasminogen activator receptor (uPAR), essential for keratinocyte adhesion, spreading, and migration, together with the reduction of LPS-induced IL1-ß and IL-6 cytokine levels, and completely abrogated the synthesis of inducible nitric oxide synthase (iNOS).


Gold , Metal Nanoparticles , Animals , Anti-Inflammatory Agents/pharmacology , Humans , Mice , Mucus , Snails , Wound Healing
14.
Biosensors (Basel) ; 10(10)2020 Oct 17.
Article En | MEDLINE | ID: mdl-33080859

The present study describes the kinetics of L-lysine-α-oxidase (LO) from Trichoderma viride immobilised by co-crosslinking onto the surface of a Pt electrode. The resulting amperometric biosensor was able to analyse L-lysine, thus permitting a simple but thorough study of the kinetics of the immobilised enzyme. The kinetic study evidenced that LO behaves in an allosteric fashion and that cooperativity is strongly pH-dependent. Not less important, experimental evidence shows that cooperativity is also dependent on substrate concentration at high pH and behaves as predicted by the Monod-Wyman-Changeux model for allosteric enzymes. According to this model, the existence of two different conformational states of the enzyme was postulated, which differ in Lys species landing on LO to form the enzyme-substrate complex. Considerations about the influence of the peculiar LO kinetics on biosensor operations and extracorporeal reactor devices will be discussed as well. Not less important, the present study also shows the effectiveness of using immobilised enzymes and amperometric biosensors not only for substrate analysis, but also as a convenient tool for enzyme kinetic studies.


Amino Acid Oxidoreductases/analysis , Biosensing Techniques , Hypocreales , Electrodes , Enzymes, Immobilized , Hydrogen-Ion Concentration , Kinetics , Lysine
15.
Foods ; 9(9)2020 Sep 04.
Article En | MEDLINE | ID: mdl-32899742

Nitrate and nitrite as sodium or potassium salts are usually added to meat products to develop the characteristic flavor, to inhibit the growth of microorganisms (particularly Clostridium botulinum), and effectively control rancidity by inhibiting lipid oxidation. However, both nitrate and nitrite ions need to be monitored for ensuring the quality and safety of cured meats. In this work, for the first time the content of nitrite and nitrate ions in homogenized meat samples of baby foods was determined by a validated method based on ion chromatography (IC) coupled with conductivity detection. Recoveries of nitrate and nitrite ions in meat samples were not lower than 84 ± 6%. The detection limits of nitrate and nitrite were 0.08 mg L-1 and 0.13 mg L-1, respectively. Five commercial samples of homogenized meat, namely lamb, rabbit, chicken, veal, and beef, for infant feeding were investigated; while nitrite content was below the detection limit, nitrate ranged from 10.7 to 21.0 mg kg-1. The results indicated that nitrate contents were below the European (EU) fixed value of 200 mg kg-1, and an acceptable daily intake of 3.7 mg kg-1 was estimated.

16.
J Am Soc Mass Spectrom ; 31(9): 1994-2005, 2020 Sep 02.
Article En | MEDLINE | ID: mdl-32840368

1,2-Diacyl-sn-glycero-3-phospho-N-acyl-ethanolamines (NAPE) are low abundance phospholipids but important constituents of intracellular membranes of plant tissues, responsible for generating bioactive N-acylethanolamine (NAE), which participates in several physiological processes such as regulation of seed germination and protection against pathogenic attacks. From an analytical point of view, the critical aspect of these bioactive lipids lies in the determination of fatty acyl chains located in sn-1/sn-2 position on the glycerol backbone (O-linked), along with the amide-bound (N-linked) fatty acyl chain. Here, the identity and occurrence of NAPE in lipid extracts of lupin seeds (Lupinus luteus L.) was assessed by electrospray ionization in negative ion mode upon reversed-phase liquid chromatography (RPLC-ESI) coupled to mass spectrometry (MS) either at high- (i.e., Orbitrap FTMS) or low- (linear ion trap, LIT) resolution/accuracy. Collisional induced dissociation (CID)-tandem MS and MS3 acquisitions of chemically prepared NAPE allowed to unequivocally recognize the N-linked fatty acyl chain and to establish the diagnostic product ions that were successfully applied to identify NAPE in lipid extracts of yellow lupin seeds. The most abundant NAPE species were those containing N-acyl groups C18:1, C18:2; a minor prevalence was found for C16:0, C18:0, and C18:3, and almost the same acyl chains O-linked on the glycerol backbone in several sn-1/sn-2 combinations were observed. The positional isomers of NAPE species were identified as deprotonated molecules ([M-H]-) at m/z 978.7541 (three isomers 52:3), m/z 980.7694 (two isomers 52:2), m/z 1002.7535 (four isomers 54:5), m/z 1004.7686 (two isomers 54:4), m/z 1006.7837 (two isomers 54:3), and m/z 1008.8026 (single isomer 54:2). The total amount of NAPE in lupin seeds ranged in the interval of 2.00 ± 0.13 mg/g dw, in agreement with other edible legumes. We anticipate our approach to be a robust assessment method potentially applicable to biological extracts containing NAPE species and can provide comprehensive profiles and contents.


Chromatography, High Pressure Liquid/methods , Lupinus/chemistry , Phosphatidylethanolamines , Seeds/chemistry , Spectrometry, Mass, Electrospray Ionization/methods , Chromatography, Reverse-Phase , Phosphatidylethanolamines/analysis , Phosphatidylethanolamines/chemistry , Stereoisomerism , Tandem Mass Spectrometry/methods
17.
Rapid Commun Mass Spectrom ; 34(20): e8884, 2020 Oct 30.
Article En | MEDLINE | ID: mdl-32648966

RATIONALE: The anionic surfactants, among which are alkyl ether sulfates (AESs), are the most used class of surfactants in cleansing applications. The negatively charged head group of AESs is a sulfate moiety linked with a variable number of ethylene oxide units, i.e. a polyethylene glycol chain. The hydrophobic part of an AES is constituted by a linear alkyl chain of carbon atoms, generally obtained from natural fatty acids. Coconut oil fatty acids, including the sodium salts of coceth sulfate (CES) with chemical formula Cx Hy (OCH2 CH2 )n OSO3 Na, are widely used as feedstock for AESs synthesis. CES is added to many cleaning products and detergents defined as non-aggressive. Currently, no detailed structural information concerning the alkyl chain length x and, more importantly, the degree of ethoxylation n has been reported. METHODS: A commercial standard solution of CES was characterized by tandem mass spectrometry, employing direct injection into the electrospray ionization (ESI) source of a a linear quadrupole ion trap mass spectrometer. RESULTS: Two series of oligomeric species, characterized by a C12 and C14 alkyl chains, i.e. [C12 H25 (OCH2 CH2 )nOSO3 ]- and [C14 H29 (OCH2 CH2 )n OSO3 ]- with n ranging from 0 to 7, were successfully identified. The interpretation of these data was very useful for CES identification in three commercial dishwasher cleaning products. CONCLUSIONS: Direct injection MS/MS analysis of CES revealed a well-defined molecular weight distribution and allowed the alkyl chain composition and the number of ethylene oxide units to be to identified.

18.
Anal Bioanal Chem ; 412(12): 3005-3015, 2020 May.
Article En | MEDLINE | ID: mdl-32215688

Interest in targeted profiling of quercetin glycoconjugates occurring in edible foodstuffs continues to expand because of their recognized beneficial health effects. Quercetin derivatives encompass several thousands of chemically distinguishable compounds, among which there are several compounds with different glycosylations and acylations. Since reference standards and dedicated databases are not available, the mass spectrometric identification of quercetin glycoconjugates is challenging. A targeted liquid chromatography (LC) coupled with tandem mass spectrometry (MS/MS) was applied for screening quercetin glycoconjugates in edible peperoni di Senise peppers (Capsicum annuum L.), protected by the European Union with the mark PGI (i.e., Protected Geographical Indication), and cultivated in Basilicata (Southern Italy). Chromatographic separation was accomplished by reversed-phase liquid chromatography (RPLC) using water/acetonitrile as the mobile phase and detection was performed on a linear ion trap mass spectrometer fitted with an electrospray ionization (ESI) source operating in negative ion mode. A correlation between experimental RP chromatographic retention time and those predicted by partition coefficients (log P) along with MS/MS data and an in-house developed database (named QUEdb) provided deep coverage for sixteen quercetin glycoconjugates. Among them, eleven quercetin glycoconjugates were already described in the literature and five were reported for the first time. These last acyl glycosidic quercetin derivatives were tentatively identified as quercetin-(galloyl-rhamnoside)-hexoside, [C34H33O20]- at m/z 761.1; quercetin-(sinapoyl-hexoside)-rhamnoside, [C38H39O20]- at m/z 815.4; quercetin-(galloyl-caffeoyl-hexoside)-rhamnoside, [C43H39O23]- at m/z 923.0; quercetin-(feruloyl-hexoside)-rhamnoside, [C37H37O19]- at m/z 785.1; and quercetin-(succinyl-rhamnoside)-rhamnoside, [C31H33O18]- at m/z 693.1. Graphical abstract.


Capsicum/chemistry , Chromatography, Liquid/methods , Chromatography, Reverse-Phase/methods , Glycosides/analysis , Quercetin/analysis , Spectrometry, Mass, Electrospray Ionization/methods , Tandem Mass Spectrometry/methods , Acylation
19.
J Agric Food Chem ; 68(10): 3171-3183, 2020 Mar 11.
Article En | MEDLINE | ID: mdl-32052628

Reversed-phase liquid chromatography with electrospray ionization-high-resolution/accuracy Fourier transform mass spectrometry (RPC-ESI-FTMS) and chemometrics were exploited to evaluate the influence of horizontal centrifugation by two- or three-phase decanters on the content of major phenolic secoiridoids in extravirgin olive oils (EVOOs). Despite the occurrence of other potential sources of variability typical of commercial olive oils, horizontal centrifugation was found to play a primary role, with a general increase of secoiridoid content occurring when two-phase decanters were used. As emphasized by principal component analysis (PCA), the increase involved preferentially oleacin and oleocanthal, when oxidative deterioration was purposely minimized during and/or after production, and oleuropein and ligstroside aglycones, when no vertical centrifugation was performed at the end of the productive cycle. The influence of the type of horizontal centrifugation was also emphasized by the elaboration of RPC-ESI-FTMS data based on hierarchical cluster analysis (HCA) and linear discriminant analysis (LDA).


Centrifugation/methods , Food Handling/methods , Iridoids/chemistry , Olive Oil/chemistry , Phenols/chemistry , Chromatography, Reverse-Phase , Fruit/chemistry , Olea/chemistry , Oxidation-Reduction , Spectrometry, Mass, Electrospray Ionization
20.
Microorganisms ; 9(1)2020 Dec 29.
Article En | MEDLINE | ID: mdl-33383704

Lactic acid bacteria (LAB) potential in the food industry and in the biotechnological sector is a well-established interest. LAB potential in counteracting especially food-borne infections has received growing attention, but despite being a road full of promises is yet poorly explored. Furthermore, the ability of LAB to produce antimicrobial compounds, both by ribosomal synthesis and by decrypting them from proteins, is of high value when considering the growing impact of multidrug resistant strains. The antimicrobial potential of 14 food-derived lactic acid bacteria strains has been investigated in this study. Among them, four strains were able to counteract Listeria monocytogenes growth: Lactococcus lactis SN12 and L. lactis SN17 by high lactic acid production, whereas L. lactis 41FLL3 and Lactobacillus sakei I151 by Nisin Z and Sakacin P production, respectively. Strains Lactococcus lactis MG1363, Lactobacillus rhamnosus 17D10 and Lactobacillus helveticus 4D5 were tested and selected for their potential attitude to hydrolyze caseins. All the strains were able to release bioactive peptides with already known antimicrobial, antihypertensive and opioid activities. These features render these strains or their bioactive molecules suitable for use in food as biocontrol agents, or as nutraceutical supplements to treat mild disorders such as moderate hypertension and children insomnia. These results highlight once again that LAB potential in ensuring food safety, food nutraceutical value and ultimately in favoring human health is still underexplored and underexploited.

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