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Turmeric and ginger are extensively employed as functional ingredients due to their high content of curcuminoids and gingerols, considered the key bioactive compounds found in these roots. In this study, we present an innovative and fast method for the assay of curcuminoids and gingerols in different foods containing the two spices, with the aim of monitoring the quality of products from a nutraceutical perspective. The proposed approach is based on paper spray tandem mass spectrometry coupled with the use of a labeled internal standard, which has permitted to achieve the best results in terms of specificity and accuracy. All the calculated analytical parameters were satisfactory; accuracy values are around 100% for all spiked samples and the precision data result lower than 15%. The protocol was applied to several real samples, and to demonstrate its robustness and reliability, the results were compared to those arising from the common liquid chromatographic method. [ABSTRACT FROM AUTHOR]

Oleic, linoleic and linolenic acids exert several beneficial effects on human health, some of which are also certified by recent European and U.S. regulations. The goal of the presented work was to develop an innovative methodology to evaluate their content in edible vegetable oils, in order to increase the value of oils from a nutraceutical perspective. The protocol is based on the use of paper spray ionization coupled with tandem mass spectrometry experiments, which allowed the recording of data very quickly and with high specificity. All investigated compounds gained a good linear relation (r2 higher than 0.98). Accuracy values are near 100% for all concentration levels examined, and the repeatability and reproducibility data result lower than 15%, highlighting the consistence of the methodology. The developed approach was successfully applied for the analysis of different real samples, and its robustness was confirmed by comparing the results obtained with those coming from the classical and official methodology. [ABSTRACT FROM AUTHOR]

The B2Π - X2Σ+ electronic spectrum of C4H has been studied by degenerate and double resonance four-wave mixing. The technique identifies vibrational levels in the X2Σ+ ground state. Its sensitivity and unique characteristics permit detection of new levels. The A2Π state lying 222 cm-1 above the X2Σ ground state is also observed, confirming the analysis from anion photoelectron spectroscopy but with improved accuracy. Vibrational level determination in the A2Π electronic manifold up to 700 cm-1 above v = 0 is made. A Renner-Teller analysis is carried out for the two lowest bending modes v6 and v7 in the A2Π state by diagonalization of the effective Hamiltonian matrix. The Renner-Teller parameters ∈ 6, ∈ 7, and ∈ 67, the vibrations ω6 and ω7 and the spin-orbit coupling constant Aso are determined. [ABSTRACT FROM AUTHOR]

A rapid and reliable method to assay the total amount of tyrosol and hydroxytyrosol derivatives in extra virgin olive oil has been developed. The methodology intends to establish the nutritional quality of this edible oil addressing recent international health claim legislations (the European Commission Regulation No. 432/2012) and changing the classification of extra virgin olive oil to the status of nutraceutical. The method is based on the use of high-performance liquid chromatography coupled with tandem mass spectrometry and labeled internal standards preceded by a fast hydrolysis reaction step performed through the aid of microwaves under acid conditions. The overall process is particularly time saving, much shorter than any methodology previously reported. The developed approach represents a mix of rapidity and accuracy whose values have been found near 100% on different fortified vegetable oils, while the RSD% values, calculated from repeatability and reproducibility experiments, are in all cases under 7%.Schematic of the methodology applied to the determination of tyrosol and hydroxytyrosol ester conjugates [ABSTRACT FROM AUTHOR]

We present a simple methodology for the simultaneous identification and determination of biogenic amines in food matrices, based on the use of a stable isotope-coded derivatization and liquid chromatography tandem mass spectrometry. The tagging reagent is N-hydroxysuccinimidyl ester of d0/d4-4-methoxybenzoic acid (d0/d4-4-MBA-OSu) which mainly functionalizes primary amines. The identification and structural characterization of tagged biogenic amines were exploited by matrix-assisted laser desorption/ionization-mass spectrometry (MS) and MS/MS. Multiple-reaction monitoring has been applied in the assay of biogenic amines in different foodstuffs, providing a method whose reliability is confirmed by the values of accuracy (12%) and by the calculated analytical parameters. Copyright © 2014 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Highlights: [•] Direct analysis by paper spray, without sample preparation. [•] In situ derivatization and identification of dialdehydic species. [•] Evaluation of anti-inflammatory active principles. [ABSTRACT FROM AUTHOR]

• A direct determination of the main flavanone- O -glycosides in citrus beverages has been set-up. • The time span of the experiment is within few minutes. • The methodology was tested to fortified and real samples. • The robustness of the proposed approach was evaluated by comparing the results with those obtained by a classic HPLC-UV analysis. A fast and accurate methodology for the quantification of the most abundant flavanone glycosides in citrus beverages has been developed. The approach relies on the use of paper spray mass spectrometry, which allows to record data in few minutes and without sample pre-treatment. The experiments have been carried out in Multiple Reaction Monitoring scan mode, in order to obtain the best specificity and sensitivity. The analytical parameters were all satisfactory. The results coming from the analysis of real samples were compared to the data obtained by the commonly used chromatographic method, proving the robustness of the proposed approach. [ABSTRACT FROM AUTHOR]

Highlights: [•] Gas phase electronic spectrum AgS observed in the 10000–11000cm−1 region and assigned to the transition. [•] Rotationally resolved spectra recorded for the spin–orbit component of the 0–0 and 1–0 vibronic bands. [•] Molecular constants determined for the ground and excited states. [ABSTRACT FROM AUTHOR]

Theoretical quantitative considerations as well as experimental data are presented based on absorption population depletion coupled with cavity ringdown spectroscopy. The absorbing number densities inside the cavity are determined by numerical integration of the coupled rate equations. The number of photons involved in absorption, cavity losses due to mirror reflectivity and stimulated emission are taken into account. The principle is to monitor a first transition by cavity ringdown spectroscopy while a second transition, with a state in common, is resonantly excited by the decaying radiation of different frequency also trapped inside the optical cavity. A numerical example is given for atomic lines of neon and the measurements carried out in a supersonic slit-jet expansion discharge demonstrate the feasibility of the technique. The technique is also proven to work with two resonant transitions of C2. Translational velocity of the jet modifying the rate equations is included in the model. [ABSTRACT FROM PUBLISHER]

Abstract: Hydroxytyrosol and tyrosol, the strong antioxidant present in large amount in virgin olive oil have been assayed by LC–MS/MS under MRM condition and isotope dilution method, using d 2-labelled internal standards obtained by simple synthetic procedures. The assay has been performed under MRM condition monitoring two transitions for each analyte to improve the specificity. This paper deals with a modern approach for assaying the content of this polyphenols in virgin olive oil down to a limit of a few hundreds of parts per billion. Tyrosol and hydroxytyrosol ranged from 10 to 47ppm and from 5 to 25ppm in commercial olive oil, respectively. The accuracy (98–107%) and analytical parameters values confirm the reliability of the proposed approach. The method can be extended to any natural matrices, including mill wastes, after a simple step of sample preparation. [Copyright &y& Elsevier]

5-Dimethylamino-1-sulfonyl naphthalene (DNS, commonly referred as dansyl) is a functionality, bearing well-established properties in directing the fragmentation, by mass spectrometry (MS), of the corresponding ionized sulfonylated derivatives. This property is shared also by its labeled analogs. The use of d0/d6 DNS derivatives is now exploited in the application of the well-established isotope dilution mass spectrometric approach in the assay of complex mixtures. A new method for the quantitation of amino acids (AAs) in beverages is therefore presented, which relies on liquid chromatographic separation of their N-dansylated derivatives followed by comparative electrospray tandem MS/MS of the d0/d6 isobaric mixtures. Labeled and unlabeled DNS derivatives of the selected AAs are readily available by microwave-assisted synthetic protocols. The novelty of the method is represented by the use of heavy and light DNS-isotopologue providing suitable reporter groups. Multiple-reaction monitoring has been applied in the assay of AAs in wine, pineapple juice and bergamot juice with good-to-excellent results as proved by both relative standard deviation, lower than 15%, and by the accuracy values in the range 90-110%. Copyright © 2012 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Abstract: New phenolic compounds from Olea europaea, identified by high performance liquid chromatography/electrospray ionization tandem mass spectrometry, are suitable markers for differentiation between different varieties of olive trees cultivated in the same geographical area (Rende, Italy). Five cultivars (Carolea, Cassanese, Coratina, Nocellara and Leccino) were considered for the discrimination. Samples of Carolea, cultivated in three different geographical zones (Rende, Mirto and Spoleto, Italy), were as well checked to evaluate possible differences. Three supervised pattern recognition procedures, linear discriminant analysis (LDA), soft independent modelling of class analogy (SIMCA) and K-nearest neighbours (KNN) were used to classify samples in five groups corresponding to the five cultivars and in three groups corresponding to the three areas of production. The results show that KNN provides a model unable to predict a proper assignment of the cultivar, at least for those olive trees considered in this work, whereas LDA and SIMCA allow the achievement of good percentage of prediction for the cultivars as well as cultivation zones. [Copyright &y& Elsevier]

Measurement of the transition of C6H+ in the gas phase near 19486 cm−1 is reported. The experiment was carried out with a supersonic slit-jet expansion discharge using cavity ringdown absorption spectroscopy. Partly resolved P lines and observation of band heads permitted a rotational contour fit. Spectroscopic constants in the ground and excited-state were determined. The density of ions being sampled is merely 2 × 108 cm−3. Broadening of the spectral lines indicates the excited-state lifetime to be ≈100 ps. The electronic transition of HC6H2 + at 26402 cm−1 assumed to be in C2v symmetry could not be rotationally resolved. [Copyright &y& Elsevier]

Resveratrol is a phytoalexin found in several plant tissues and present in wines, which is supplied as a nutritional supplement. Different studies have revealed its beneficial effects as anticancer, antiviral, neuroprotective, antiaging, and anti-inflammatory natural active principle. The assaying of resveratrol by mass spectrometry and isotope dilution method, using a stable [2l analogue, has required a full elucidation of its gas-phase H/D isotopomerization. Either selected ion monitoring (SIM) or multiple reaction monitoring (MRM) methods have been used for the evaluation of the amount of resveratrol present in wine and plasma samples in the negative ionization mode. In all instances the acquired accuracy, limit of quantitation (LOQ), and limit of detection (LOD) are fit for the Intended purpose of the assay. [ABSTRACT FROM AUTHOR]

The [image omitted] electronic transition of several isotopologues of the HC4S radical (DC4S, HC434S, DC434S) produced in a pulsed supersonic slit-jet expansion discharge has been measured by cavity ringdown spectroscopy. The sensitivity of the technique and a higher rotational temperature enables observation of weaker features in the spectrum of HC4S not previously detected by laser induced fluorescence. Rotational fits were made on several of these hot bands as well as on the origin bands of the four isotopologues. The high signal-to-noise ratio of the spectra enables precise determination of line positions. Band origin and effective rotational constants were found to be T00 = 19981.441(1), B'eff = 0.04540(1), B''eff = 0.04661(1) cm-1 for HC434S, and T00 = 20035.630(4), B'eff = 0.04318(5), B''eff = 0.04432(4) cm-1 for DC434S. The quartic centrifugal distortion term in the v = 0 of the [image omitted] excited state is 1.50(36) × 10-9 for HC4S and 1.58(43) × 10-9 cm-1 for DC4S. Measurements made at different temperatures combined with theoretical calculations suggest that the spin orbit splitting in the [image omitted] ground state is likely to be close to -270 cm-1 rather than the much smaller value inferred indirectly earlier. [ABSTRACT FROM AUTHOR]

A rapid analytical method for the determination of phenylethanoids content in extra virgin olive oil has been developed. The method intends to address the European regulation EU 432/2012 on health claims, which allows to report on the front label of olive oil, the positive health effects due to the consumption of this food. The innovative method is based on paper spray tandem mass spectrometry using deuterated standards. It relies on a two-step analysis, needed to assess the free form of tyrosol and hydroxytyrosol and their ester conjugates after hydrolysis treatment. Different olive oil samples have been analyzed and the classical analytical parameters such as accuracy, LOQ and LOD were calculated from fortified samples. The good values of the latters show the reliability of the new approach, that limits the time of analysis and sample preparation to few minutes. • A rapid determination of phenylethanoids in olive oil has been set up. • The whole experiment lasts few minutes. • The analysis utilizes labeled standards and paper spray tandem mass spectrometry. • The method was tested to extra virgin olive oil and fortified oil samples. • The proposed method addresses the European regulation 432/2012 on health claims. [ABSTRACT FROM AUTHOR]

Edible insects have the potential to become one of the major future foods. In fact, they can be considered cheap, highly nutritious, and healthy food sources. International agencies, such as the Food and Agriculture Organization (FAO), have focused their attention on the consumption of edible insects, in particular, regarding their nutritional value and possible biological, toxicological, and allergenic risks, wishing the development of analytical methods to verify the authenticity, quality, and safety of insect-based products. Edible insects are rich in proteins, fats, fiber, vitamins, and minerals but also seem to contain large amounts of polyphenols able to have a key role in specific bioactivities. Therefore, this review is an overview of the potential of edible insects as a source of bioactive compounds, such as polyphenols, that can be a function of diet but also related to insect chemical defense. Currently, insect phenolic compounds have mostly been assayed for their antioxidant bioactivity; however, they also exert other activities, such as anti-inflammatory and anticancer activity, antityrosinase, antigenotoxic, and pancreatic lipase inhibitory activities. [ABSTRACT FROM AUTHOR]

A novel approach for the rapid discrimination of bergamot essential oil from other citrus fruits oils is presented. The method was developed using paper spraymass spectrometry (PS-MS) allowing for a rapid molecular profiling coupled with a statistic tool for a precise and reliable discrimination between the bergamot complex matrix and other similar matrices, commonly used for its reconstitution. Ambient mass spectrometry possesses the ability to recordmass spectra of ordinary samples, in their native environment, without sample preparation or pre-separation by creating ions outside the instrument. The present study reports a PS-MS method for the determination of oxygen heterocyclic compounds such as furocoumarins, psoralens and flavonoids present in the non-volatile fraction of citrus fruits essential oils followed by chemometric analysis. The volatile fraction of Bergamot is one of the most known and fashionable natural products, which found applications in flavoring industry as ingredient in beverages and flavored foodstuff. The development of the presented method employed bergamot, sweet orange, orange, cedar, grapefruit and mandarin essential oils. PS-MS measurements were carried out in full scan mode for a total run time of 2 min. The capability of PS-MS profiling to act as marker for the classification of bergamot essential oils was evaluated by using multivariate statistical analysis. Two pattern recognition techniques, linear discriminant analysis and soft independent modeling of class analogy, were applied to MS data. The cross-validation procedure has shown excellent results in terms of the prediction ability because both models have correctly classified all samples for each category. [ABSTRACT FROM AUTHOR]

Highlights: [•] Simultaneous quantification of flavanones in citrus fruit beverages. [•] Derivatization of flavanones using methoxyamine and trideuteromethoxyamine. [•] Use of stable isotope tagged internal standard. [Copyright &y& Elsevier]

A high-throughput mass spectrometric method is presented for the simultaneous detection of Sudan I, II, III, IV and Para-Red azo-dyes in foodstuff. The method is based on the use of paper spray mass spectrometry (MS) and deuterium-labeled internal standards on a triple-quadrupole instrument. A detailed assay of each azo-dye was performed by the isotope dilution method, through the precursor ion scan approach, using deuterium-labeled internal standards. The gas-phase breakdown pattern of each labeled and unlabeled analogue displays the naphthoic moiety as a common fragment. Sudan dyes can be determined above the threshold of 1 ppm. Paper spray allows for a wide range of analytes and samples to be investigated by MS in the open air and without sample preparation and bypassing chromatography. Copyright © 2013 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

The quality of extra virgin olive oil is associated with the presence of microcomponents whose healing effects have been proved in some special cases. The enzymatic hydrolysis of oleuropein and ligstroside, and of their demethylated analogues, affords four different pentanedialdehydes, and for one of which, 2-(4-hydroxyphenyl)ethyl (3S,4E)-4-formyl-3-(2-oxoethyl)hex-4-enoate, also known as oleocanthal, an anti-inflammatory effect was quite recently carefully assessed. Extra virgin olive oil is now worldwide considered as a functional food whose daily intake, as for the Mediterranean diet, helps consumers in keeping a constant level of nonsteroidal anti-inflammatory drug (NSAID) in the blood. The presence of these active principles provides, therefore, olive oil with an important added value. In the framework of the actions of the recently funded Agrifood Regional Center, which should coordinate the scientific research and production worlds, an absolute analytical method was developed for the mass spectrometric detection of the two most abundant NSAIDs, Tyr-OLPD and HTyr-OLPD (oleopentanedialdehydes (OLPDs) conjugated to p-hydroxyphenylethanol and 3,4-dihydroxyphenylethanol, respectively), by UHPLC-ESI-MS/MS. [ABSTRACT FROM AUTHOR]

Abstract: A new device for the preparation of stoned olive oils, called SPIA, has been developed, aiming at fulfilling the targets of: (i) employing a less powered engine, (ii) reducing the size of the machine and (iii) reaching a good efficiency in terms of oil yields. Oleuropein expression was used as a biochemical parameter to distinguish stoned oils from oils produced by conventional milling systems. In vitro experiments performed by exposing oleuropein to pit enzymes, showed an exponential decay of the substrate. [Copyright &y& Elsevier]

Oleuropein (OLP, 1), the active ingredient present (i) in food integrators extracted from olive leaves, (ii) in table olives, and (iii) in extra virgin olive oils is a nutraceutical whose health benefits have been widely documented. A new analytical method for its assay, which is based on the utilization of atmospheric pressure chemical ionization tandem mass spectrometry and on the use of a synthetic labeled analogue, the 4-trideuteriocarboxyoleuropein (2), as an internal standard, is presented. The results obtained with extra virgin olive oils from different cultivars and different Italian regions are discussed. [ABSTRACT FROM AUTHOR]

Food safety represents one of the main issues of national and international agencies appointed to health control. In April 2003, a French agency disclosed that powdered or smashed hot chili pepper imported from India and Pakistan was heavily contaminated with a carcinogenic azo dye known as Sudan I. This paper deals with a modern approach for assaying the content of this colorant in foodstuff down to a limit of a few tens of parts per billion. The isotope dilution method combined with APCI tandem mass spectrometry was used. The internal standard, 1-(d5-phenylazo)-2-naphthalenol, was obtained by simple chemistry, and its structure was determined by 1H NMR spectroscopy. The mass spectrometric method is more sensitive than the HPLC approach by a factor of 20. [ABSTRACT FROM AUTHOR]

A fast methodology for the assay of parabens in drug and cosmetic preparations has been presented. The procedure developed is based on paper spray tandem mass spectrometry and isotope dilution approach. For each investigated paraben, the corresponding labeled standard has been used in order to improve the accuracy and reproducibility of the analyses. The MS experiments have been performed under MRM conditions, monitoring the transitions [M‐H]− → m/z 92 and [M‐H]− → m/z 98, respectively, for each analyte and the corresponding labeled internal standard. The quantitative assay has been performed using a calibration curve built from 2 to 15 mg/L. The method accuracy, in all case near 100%, was evaluated using fortified samples at two concentration levels, which are representative of the lower and the higher portion of calibration curve. The good values of LOQ, LOD, and reproducibility confirm the consistency of the developed approach. [ABSTRACT FROM AUTHOR]

Citrus aurantium is a widespread tree in the Mediterranean area, and it is mainly used as rootstock for other citrus. In the present study, a vacuum infiltration centrifugation procedure, followed by solid phase extraction matrix-assisted laser desorption ionization tandem mass spectrometry (SPE MALDI MS/MS) analysis, was adopted to isolate proteins from leaves. The results of mass spectrometry (MS) profiling, combined with the top-down proteomics approach, allowed the identification of 78 proteins. The bioinformatic databases TargetP, SignalP, ChloroP, WallProtDB, and mGOASVM-Loc were used to predict the subcellular localization of the identified proteins. Among 78 identified proteins, 20 were targeted as secretory pathway proteins and 36 were predicted to be in cellular compartments including cytoplasm, nucleus, and cell membrane. The largest subcellular fraction was the secretory pathway, accounting for 25% of total proteins. Gene Ontology (GO) of Citrus sinensis was used to simplify the functional annotation of the proteins that were identified in the leaves. The Kyoto Encyclopedia of Genes and Genomes (KEGG) showed the enrichment of metabolic pathways including glutathione metabolism and biosynthesis of secondary metabolites, suggesting that the response to a range of environmental factors is the key processes in citrus leaves. Finally, the Lipase GDSL domain-containing protein GDSL esterase/lipase, which is involved in plant development and defense response, was for the first time identified and characterized in Citrus aurantium. [ABSTRACT FROM AUTHOR]

A synthetic strategy for the preparation of two orthogonally protected methyl esters of the non-proteinogenic amino acid 2,3-l-diaminopropanoic acid (l-Dap) was developed. In these structures, the base-labile protecting group 9-fluorenylmethyloxycarbonyl (Fmoc) was paired to the p-toluensulfonyl (tosyl, Ts) or acid-labile tert-butyloxycarbonyl (Boc) moieties. The synthetic approach to protected l-Dap methyl esters uses appropriately masked 2,3-diaminopropanols, which are obtained via reductive amination of an aldehyde prepared from the commercial amino acid Nα-Fmoc-O-tert-butyl-d-serine, used as the starting material. Reductive amination is carried out with primary amines and sulfonamides, and the process is assisted by the Lewis acid Ti(OiPr)4. The required carboxyl group is installed by oxidizing the alcoholic function of 2,3-diaminopropanols bearing the tosyl or benzyl protecting group on the 3-NH2 site. The procedure can easily be applied using the crude product obtained after each step, minimizing the need for chromatographic purifications. Chirality of the carbon atom of the starting d-serine template is preserved throughout all synthetic steps. [ABSTRACT FROM AUTHOR]

• A MALDI-MS/MS quantitative method was developed for saffron authenticity. • The method was sensitive and fast, not requiring chemical manipulation of samples. • Picrocrocin was chosen as the saffron authenticity biomarker. • Percentages of adulteration in commercial saffron were evaluated by using curcumin. We report on a sensitive and fast quantitative MALDI-MS/MS method used to assess saffron authenticity by direct analysis through the determination of picrocrocin as the saffron authenticity marker, and using curcumin as the non-isotopic isobaric internal standard. The internal standard curcumin yielded good linearity (R2 = 0.994), and with confidence intervals at 95% for intercept. The detectable maximum adulteration percentage (99.0%) was estimated interpolating the limit of detection (LOD) for the isobaric internal standard in linear regression. The LOD was 47.63 ppm, and LOQ was 56.53 ppm. Good accuracy and precision were obtained for all concentrations. The capability of the MS approach to monitor analytes in a specific, selective fashion was used to obtain a semi-quantitative adulteration percentage and to establish the adulterant by additional experiments. The detection of gardecin and its derivatives in commercial samples indicated that Gardenia jasminoides Ellis was used as the adulterant. [ABSTRACT FROM AUTHOR]

Extra virgin olive oil provides an important intake of α-tocopherol, which is part of vitamin E complex. A fast analytical method for its quantification, based on paper spray mass spectrometry, has been developed. The methodology possesses the ability to record mass spectra without sample preparation or preseparation steps. The experiments were performed in Multiple Reaction Monitoring scan mode; in particular, the transitions m/z 429 → m/z 163 for α-tocopherol and m/z 435 → m/z 169 for the labeled internal standard were monitored, in order to obtain the greatest specificity and the best sensitivity. The accuracy of the method was tested analyzing spiked samples prepared at concentrations within the dynamic range of the calibration curve, which returned values near 100%. Furthermore, good values of LOQ and LOD were obtained, demonstrating that this approach can be applied for a rapid screening of tocopherols in different vegetable oils. The results were compared with analyses performed by traditional chromatographic methods. [ABSTRACT FROM AUTHOR]

Highlights • Quantitative determination of methylxanthines alkaloids in cocoa products. • Paper Spray mass spectrometry for analytical assay. • Comparison of obtained data with HPLC/UV method. Abstract A fast method for the determination of methylxanthines in cocoa products and drugs based on PS-MS/MS under MRM condition has been developed. Analyte ions were generated by applying a high voltage on a paper substrate drenched of sample extract using a small volume (∼15 μL) of spray solvent. The gas phase chemistry of the molecules under investigation has been elucidated. The accuracy values of the methodology ranged from 95 to 110%, while the analytical parameters LOQ, LOD, recovery and reproducibility, calculated analyzing spiked samples, confirmed the consistency of the proposed method. Furthermore, real samples have been analyzed both by the developed methodology and by using a classical HPLC-UV approach obtaining comparable values. [ABSTRACT FROM AUTHOR]

Abstract: Monacolin K, the active ingredient present in dietary supplement, is a nutraceutical whose health benefits have been widely documented. A fast approach for the assay of lovastatin in both forms, lactone and acid, by mass spectrometry is presented. The quantitative assay is carried out by high‐performance liquid chromatography‐tandem mass spectrometry by using the multiple reaction monitoring mode and simvastatin and pravastatin as internal standards. The accuracy values ranged from 97 to 101%; the analytical parameter values of limit of quantitation, limit of detection, recovery, and reproducibility were calculated by analyzing fortified samples, confirming the reliability of the proposed approach. [ABSTRACT FROM AUTHOR]

A rapid analytical approach for the assay of resveratrol in red wines, based on Paper Spray Mass Spectrometry (PS-MS) and Multiple Reaction Monitoring (MRM) is described. The assay involves the use of the stable isotope dilution method. The analytical parameters calculated analyzing fortified samples confirm the reliability of the proposed approach, with accuracy values about 100%, and LOD and LOQ values calculated at 0.5 and 0.8 μg/mL, respectively. Furthermore, both the recovery, which was quantitative for the analyte, and the reproducibility (RSD%), checked on different days on the same wine, always below 7%, highlighted the consistency of the methodology. [ABSTRACT FROM AUTHOR]

The antioxidant activity and the phenolic and α-tocopherol content of 10 Northern Italian mono- and multi-varietal extra virgin olive oils (EVOOs), after early and late olive harvests, was analyzed. A hierarchical cluster analysis was used to evaluate sample similarity. Secoiridoids (SIDs), lignans and flavonoids were the most abundant phenolic compounds identified. The organic Casaliva (among mono-cultivar) and the organic multi-varietal (among blended oils) EVOOs had the higher total phenol content both in early (263.13 and 326.19 mg/kg, respectively) and late harvest (241.88 and 292.34 mg/kg, respectively) conditions. In comparison to late harvest EVOOs, early harvest EVOOs, in particular the organic mono-cultivar Casaliva, showed both higher antioxidant capacity (up to 1285.97 Oxygen Radicals Absorbance Capacity/ORAC units), probably due to the higher SID fraction (54% vs. 40%), and higher α-tocopherol content (up to 280.67 mg/kg). Overall, these results suggest that SIDs and α-tocopherol mainly contribute to antioxidant properties of the studied EVOOs. In light of this, the authors conclude that early harvest, organic mono-cultivar Casaliva EVOO represents the most interesting candidate to explicate healthy effects ascribed to these functional constituents, particularly regarding oxidative stress-related pathologies. [ABSTRACT FROM AUTHOR]

A simple and fast method based on paper spray mass spectrometry for the determination of caffeine in commercial beverages and drugs has been developed; the analyses were carried out in MRM mode, monitoring the transitions m/z 195 → m/z 138 for caffeine and m/z 198 → m/z 140 for the labeled internal standard. To verify the reliability of the proposed approach, a spiked sample (soda drink and paracetamol tablet) with a known amount of caffeine has been prepared and analyzed by PS-MS, providing accuracy values about 100 %; the LOQ and LOD values were calculated at 1.2 and 1.6 μg/mL, respectively. Both beverages and drugs were also analyzed with the classic analytical method based on LC-UV measurements, showing consistent results between the two approaches, thus confirming the reliability of the developed ambient MS determination. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

A method for the determination and quantification of ketosteroid hormones in meat by mass spectrometry, based on the derivatization of the carbonyl moiety of steroids by O-methylhydroxylamine, is presented. The quantitative assay is performed by means of multiple-reaction-monitoring (MRM) scan mode and using the corresponding labelled species, obtained by reaction with d-methoxylamine, as internal standard. The accuracy of the method was established by evaluating artificially spiked samples, obtaining values in the range 90-110 %. Recovery tests were performed on blank matrix samples spiked with non-natural steroids including trenbolone and melengestrol acetate. The latter experiment revealed that the yield of the extraction processes was approximately 60 %. Good values of LOQ and LOD were achieved, making this method competitive with current hormone assay methods. [ABSTRACT FROM AUTHOR]

Cd(II)-, Pb(II)- and Zn(II)-cystine complexes were investigated by potentiometric and different mass spectrometric (MS) methodologies. Laser desorption mass spectrometry has provided both the composition and structure of metal-cystine complexes according to the speciation models proposed on the basis of the potentiometric data. Detection of neutral complexes was achieved by protonation or electrochemical reduction during mass spectrometric experiments. The redox activity of metal-cystine complexes was confirmed by laser desorption and charge transfer matrix assisted laser assisted MS experiments, which allowed us to observe the formation of complexes with a reduction of cystine. The stoichiometry of Cd(II)-, Pb(II)- and Zn(II)-cystine complexes was defined by observing the isotopic pattern of the investigated compound. The results suggest that interaction occurs through the carboxylate group of the ligand. [ABSTRACT FROM AUTHOR]

The solid phase isobaric mass tagging (SP1MT) approach is presented for simultaneous protein quantitation and identification. The novelty of the SP1MT strategy relies on a CID-based differentiation of regioisomeric species for quantitalion of tagged proteolytic peptides. SPIMFs are unlabeled mass-tagging reagents, which consist of a reporter group, a mass balance group, and a spacer with a amine-specific reactive group, able to be linked to any N-terminal peptide. Therefore SPIIWF-llnked peptides from a two-plex set appear as a single unresolved precursor ion in MS, whereas the reporter groups lead to quantitation signals of m/z 168.2 and 182.2 Da upon tandem mass specUvimetiy (MS/MS) analysis with matrixassisted laser desorption time-of-flight/time-of-flight (MAh Dl TOF/TOF). This strategy allows ease protein identification by direct submission of MS and MS/MS data to the MASCOT database. SPIMf approach showed an excellent quantitation linearity, detecting any relative concentration differences of peptides in two solutions over a 5-fold concentration range without losing sequencing informadon. Therefore, SPIMT's are an attractive, simple, and low cost alternative for two-plex quantitation of proteins and offer possibilities of tuning the two-plex signal mass window by replacing the spacer. [ABSTRACT FROM AUTHOR]