Maria Careri

Università degli studi di Parma, Parma, Emilia-Romagna, Italy

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Publications (180)517.32 Total impact

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    ABSTRACT: The capabilities of desorption electrospray ionization-high resolution mass spectrometry (DESI-HRMS) were tested for screening the presence of some paralytic shellfish toxins in clams. A quick, easy, cheap, effective, rugged, and safe (QuEChERS) approach is proposed for sample clean-up. QuEChERS extraction was optimized by using a full factorial design followed by the multicriteria method of the desirability functions. Quantitation limits in the microgram per kilogram range proved reliability of the method for the detection of the investigated toxins in accordance to the rules laid down by European legislation. The optimized QuEChERS-DESI-HRMS based-method allowed for a rapid reliable screening of the investigated compounds at levels of interest, thus being useful for high-throughput analyses.
    No preview · Article · Jan 2016 · Talanta
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    ABSTRACT: A tetraquinoxaline cavitand functionalized with methylenoxy bridges at the upper rim is proposed as selective solid-phase microextraction (SPME) coating for the determination of BTEX at trace levels in air. The SPME fibers were characterized in terms of film thickness, morphology, thermal stability and extraction capabilities. An average coating thickness of 35 (±4) μm, a thermal stability up to 350 °C and a good fiber-to-fiber and batch-to-batch repeatability with RSD lower than 15% were obtained. Excellent enrichment factors ranging from 360-700 × 103 were obtained for the investigated compounds. Finally, method validation proved the capabilities of the developed coating for the selective sampling of BTEX, achieving LOD values in the 0.4-1.2 ng m-3 range.
    No preview · Article · Dec 2015 · Analytica Chimica Acta
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    ABSTRACT: Celiac patients should feel confident in the safety of foods labelled or expected to be gluten-free. In this context, a targeted proteomic approach based on liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) technique was proposed to assess the presence of celiotoxic cereals, namely wheat, oats, barley and rye, in raw and processed food products. To this aim, unique marker peptides were properly selected in order to distinguish between the different cereal types. A revised cocktail solution based on reducing and denaturing agents was exploited for prolamin extraction from raw and processed food; in addition, defatting with hexane was carried out for sample clean-up, allowing to largely reduce problems related to matrix effect. Method validation on fortified rice flour showed good analytical performance in terms of sensitivity (limits of detection in the 2-18 mg kg(-1) range). However, poor trueness was calculated for self-made incurred bread (between 3 and 30% depending on the peptide), probably due to baking processes, which reduce gluten extractability. Thus, it is evident that in the case of processed foods further insights into sample treatment efficiency and reference materials for protein calibration are required to obtain accurate gluten determination. Finally, the developed method was applied for the analysis of market food products, offering the possibility to discriminate among cereals, with good agreement with labelled ingredients for gluten-containing foodstuffs.
    No preview · Article · Oct 2015 · Analytica chimica acta
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    ABSTRACT: A rapid and simple QuEChERS sample treatment was proposed for the development of a selective hydrophilic interaction liquid chromatography-ESI-MS2-based method for the determination of saxitoxins (STXs) in mussel samples. Among different sorbents, ABS Elut-NEXUS phase, composed of polystyrene cross-linked with 50% divinyl benzene and poly(methyl methacrylate), provided the best results. The effects of experimental parameters, including sorbent amount, vortexing time and centrifugation time were investigated and optimized by experimental design. In particular, regression models and desirability functions were applied to find the experimental conditions providing the highest global extraction response. The method was validated under the optimized conditions; detection and quantification limits in the 3-159 μg/kg and 7-436 μg/kg ranges respectively were obtained, except for C2 for which highest values were calculated due to its low ESI ionization efficiency. Finally, the analysis of twenty-eight mussel samples permitted to detect and quantify some of the investigated STXs, proving the applicability of the devised method.
    No preview · Article · Jul 2015 · Food Control
  • Monica Mattarozzi · Maria Careri

    No preview · Article · Jun 2015
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    ABSTRACT: Environmental scanning electron microscopy (ESEM) permits to analyze samples in their native-hydrated state, allowing a broad spectrum of biological applications. In this study, ESEM equipped with energy dispersive X-ray spectrometer (EDS) was used as a fast method to analyze tissue morphology and to investigate metal distribution in the Ni hyperaccumulator Noccaea caerulescens, an established model to study the adaptation of plants to metalliferous soils. The low vacuum and wet mode operative conditions required the proper choice of experimental parameters both for morphological and compositional characterization of plant tissues. The calibration strategy for semi-quantitative analysis involved the use of Ni fortified agar as standard and signal normalization respect to endogenous carbon, chosen as internal standard. The obtained results are in accordance with present literature, showing a preferential Ni distribution in the epidermal cells respect to near the stomata for leaves and in the cotyledon epidermidis respect to cotyledon parenchyma area for seeds. Thanks to the absence of any time consuming sample treatment steps, ESEM-EDS technique can be proposed as valid strategy for in vivo high-throughput analysis of plant tissues and for a rapid screening and identification of other hyperaccumulator plants in a selected contaminated area. Copyright © 2015 Elsevier Ltd. All rights reserved.
    Full-text · Article · May 2015 · Micron
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    ABSTRACT: Since it was proposed for the first time, desorption electrospray ionization-mass spectrometry (DESI-MS) has been evaluated for applicability in numerous areas. Elucidations of the ionization mechanisms and the subsequent formation of isolated gas-phase ions have been proposed so far. In this context, the role of both surface and pneumatic effects on ion-formation yield has recently been investigated. Nevertheless, the effect of the surface chemistry has not yet been completely understood. Functionalized glass surfaces have been prepared, in order to tailor surface performance for ion formation. Three substrates were functionalized by depositing three different silanes [3-mercaptopropyltriethoxysilane (MTES), octyltriethoxysilane (OTES), and 1H,1H,2H,2H-perfluorooctyltriethoxy-silane (FOTES)] from toluene solution onto standard glass slides. Surface characterization was carried out by contact-angle measurements, tapping-mode atomic force microscopy, and X-ray photoelectron spectroscopy. Morphologically homogeneous and thickness-controlled films in the nm range were obtained, with surface free energies lying between 15 and 70 mJ/m2. These results are discussed, together with those of DESI-MS on low-molecular-weight compounds such as melamine, tetracycline, and lincomycin, also taking into account the effects of the sprayer potential and its correlation with surface wettability. The results demonstrate that ion-formation efficiency is affected by surface wettability, and this was demonstrated operating above and below the onset of the electrospray. Graphical Abstract ᅟ
    No preview · Article · Apr 2015 · Journal of the American Society for Mass Spectrometry
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    ABSTRACT: Platelet-derived MPs (PMPs) are a heterogeneous population of microvesicles released from platelets upon activation and apoptosis. Different platelet activations may affect PMP protein profiles and roles in intercellular communication. Here, we performed a quantitative proteomics study to characterize the protein content of PMPs generated by four differentially activated platelet samples. We selected known physiological agonists for platelet activation such as ADP, thrombin and collagen. Thrombin, which is mostly used to generate PMPs in vitro, was set as control. Platelets were activated by following a known agonist strength scale in which ADP was the weakest activation and thrombin and collagen stimulations were the strongest ones. Our proteomics analysis allowed the quantification of 3383 proteins, of which 428 membrane and 131 soluble proteins were found as significantly different in at least one of the analyzed conditions. Activation with stronger agonists led to the enrichment of proteins related to platelet activation in PMPs. In addition, proteins involved in platelet degranulation and proteins from the electron transport chain were less abundant in PMPs when stronger activation was used. Collectively, our data describe the most detailed characterization of PMPs after platelet physiological activation. Furthermore, we show that PMP protein content is highly dependent on the type of physiological agonist involved in platelet stimulation. Copyright © 2015. Published by Elsevier B.V.
    No preview · Article · Mar 2015 · Journal of proteomics
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    ABSTRACT: A new amperometric immunosensor based on the covalent immobilization of tissue transglutaminase enzyme in its open conformation (open-tTG) was developed and optimized for determination of anti-tissue transglutaminase antibodies (anti-tTG) in human serum. Experimental design allowed us to find the optimal conditions for quantification of both IgA and IgG isotypes of anti-tTG in order to assess suitability of the device for diagnostic purposes. The glassy carbon electrodic substrate was electrochemically functionalized with gold nanoparticles and subsequently derivatized with a self-assembled monolayer of 11-mercaptoundecanoic acid for the covalent anchoring of the enzyme. This step was performed under carefully controlled conditions in order to keep the open conformation of the tTG. The immunosensor showed good analytical performance with limit of detection levels (1.7 AU mL−1 for IgA and 2.7 AU mL−1 for IgG) below the diagnostic threshold value (3.0 AU mL−1) and inter-sensor reproducibility giving RSD lower than 10%. The developed sensor was validated in serum samples from pediatric patients for clinical applications, using two ELISA kits specific for the determination of anti-tTG IgA and IgG antibodies as reference methods; good recovery rates ranging from 74% to 117% were calculated.
    No preview · Article · Dec 2014 · Biosensors & Bioelectronics
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    ABSTRACT: A selective cavitand-based solid-phase microextraction coating was synthesized for the determination of nitroaromatic explosives and explosive taggants at trace levels in air and soil. A quinoxaline cavitand functionalized with a carboxylic group at the upper rim was used to enhance selectivity towards analytes containing nitro groups. The fibers were characterized in terms of film thickness, morphology, thermal stability and pH resistance. An average coating thickness of 50 (±4) µm, a thermal stability until 400°C and an excellent fiber-to-fiber and batch to batch repeatability with RSD lower than 4% were obtained. The capabilities of the developed coating for the selective sampling of nitroaromatic explosives were proved achieving LOD values in the low ppbv and ng kg-1 range, respectively for air and soil samples.
    Full-text · Article · Oct 2014 · Analytical Chemistry
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    ABSTRACT: Home-made micro-solid-phase extraction (SPE) cartridges using different adsorbent materials were tested for the desorption electrospray ionization–high-resolution mass spectrometry (DESI-HRMS) determination of explosives like 2,4,6-trinitrotoluene, cyclotrimethylene-trinitramine, cyclotetramethylene-tetranitramine, pentaerythritol tetranitrate, and trinitrophenylmethylnitramine in soil samples. Quantitation limits in the low nanogram per kilogram range proved the reliability of the method for the detection of explosives at ultra-trace levels. The reduced sample preparation allowed for low costs and high-throughput analyses. Finally, the superior extraction capability of the method was proved by obtaining DESI-HRMS responses at least five times higher than those achieved by performing DESI-HRMS analyses of solid–liquid extracts spotted onto commercial polytetrafluoroethylene slides. Graphical Abstract DESI-HRMS analysis of explosives from soil samples
    No preview · Article · Oct 2014 · Analytical and Bioanalytical Chemistry
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    ABSTRACT: A piezoelectric immunosensor was developed for the first time for direct detection of anti-tissue transglutaminase antibodies (anti-tTG), very specific biomarkers for reliable and early diagnosis of celiac disease. Since the inflammation processes associated to the pathology's occurrence involve tTG structural changes from closed to open conformation as well the extended structure has been demonstrated to have higher diagnostic accuracy if compared with closed conformation, the new strategy undertaken in this study was based on the immobilization of tTG enzyme in its open conformation as receptor on immunosensor surface. Ten nm-sized gold nanoparticles conjugated with secondary antibodies were exploited for signal amplification. Liquid phase detection conditions using a laminar flow cell were properly selected in order to have a good signal stability both in dynamic and in static modes. Optimization of the operating conditions, by experimental design on mouse anti-tTG antibodies in serum, allowed us to obtain a model for the realization of a reliable piezoelectric immunosensor with high potential as diagnostic device for the determination of human autoantibodies of celiac patients.
    No preview · Article · Oct 2014 · Sensors and Actuators B Chemical
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    ABSTRACT: Primary aromatic amines (PAAs) can migrate from packaging into food from different sources such as polyurethanic adhesives used for the manufacture of multilayer films, which may contain residual aromatic isocyanates, or recycled paperboard, because of the presence of azo dyes in the printed paper massively used in the recycling process. In the present work, a reliable analytical method, exploiting a conventional high-performance liquid chromatography-(selected ion monitoring)-mass spectrometry system, for PAAs compliance assessment in food contact materials was developed as an effective alternative to the current standard spectrophotometric one, moving in this way from the screening to the accurate and selective quantitation perspective for the analysis of PAAs both in aqueous and acidic food simulants. The main validation parameters were verified achieving very satisfactory results in terms of linearity range, limit of detection (ranging from 0.1 to 1.0 µg kg−1) and quantitation (ranging from 0.1 to 3.6 µg kg−1), repeatability and accuracy. Suitability of the method was demonstrated for a wide range of commercial samples, chosen among different producers of the most common used food packaging plastic and paperboard categories and then analyzed to assess the risk related to PAAs migration. Finally, the method was also successfully exploited to monitor the evolution of potential PAAs migration during the industrial curing process of multilayer plastic laminates, prior to their release for delivery to the food industry end user. Copyright © 2014 John Wiley & Sons, Ltd.
    No preview · Article · Sep 2014 · Journal of Mass Spectrometry
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    ABSTRACT: Different sample treatment protocols for the liquid chromatography–electrospray-tandem mass spectrometry (LC–ESI-MS/MS) analysis of potential residuals of ovalbumin and caseins added to red wines were developed. In particular, attention was paid to the simultaneous detection and quantitation of fining agent residues, i.e. ovalbumin, α- and β-casein, in wine samples. The different sample treatment methods were compared in terms of protein recovery. The use of denaturing agents combined with size exclusion concentration and purification allowed to obtain a reproducible (RDS < 20%) analytical protocol with good recoveries (73(±2) – 109(±4)% range) for digested proteins from 12.5 mL of wine sample. Matrix-matched calibration from LC–ESI-MS/MS analysis indicated that the devised method allowed detection of target peptides in the 0.01–0.8 μg/mL range. Finally, method applicability and selectivity was demonstrated by using fining agents commonly exploited in winery industry and by analyzing 20 commercial red wine samples.
    No preview · Article · Apr 2014 · Food Control
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    ABSTRACT: Wearable solid phase microextraction (SPME) devices consisting in necklaces and pins were developed for the environmental monitoring of ketamine in recreational places using ionic liquid as coating. SPME fibers obtained using both monocationic and dicationic polymeric ionic liquids were characterized in terms of morphology, film thickness, thermal stability and pH resistance. An average thickness of 30±5μm, an excellent thermal stability until 350°C and a very good fiber-to-fiber and batch-to-batch repeatability with RSD lower than 4% were some of the features of the developed coatings. A quantitation limit (LOQ) of 0.05mg/m(3) with a sampling time of 1min proved the feasibility of the developed method for the quantitation of ketamine in air at low concentration levels. Finally, the capabilities of the fibers for the rapid SPME sampling of ketamine in recreational places were proved obtaining extraction efficiencies at least two-fold higher than those obtained using commercial devices and extraction recoveries ranging from 84.2±3.3% to 93.6±2.6% (n=3).
    No preview · Article · Jan 2014 · Journal of Chromatography A
  • Marco Giannetto · Eleonora Umiltà · Maria Careri
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    ABSTRACT: A new voltammetric competitive immunosensor selective for atrazine, based on the immobilization of a conjugate atrazine-bovine serum albumine on a nanostructured gold substrate previously functionalized with poliamidoaminic dendrimers, was realized, characterized, and validated in different real samples of environmental and food concern. Response of the sensor was reliable, highly selective and suitable for the detection and quantification of atrazine at trace levels in complex matrices such as territorial waters, corn-cultivated soils, corn-containing poultry and bovine feeds and corn flakes for human use. Selectivity studies were focused on desethylatrazine, the principal metabolite generated by long-term microbiological degradation of atrazine, terbutylazine-2-hydroxy and simazine as potential interferents. The response of the developed immunosensor for atrazine was explored over the 10(-2)-10(3)ngmL(-1) range. Good sensitivity was proved, as limit of detection and limit of quantitation of 1.2 and 5ngmL(-1), respectively, were estimated for atrazine. RSD values <5% over the entire explored range attested a good precision of the device.
    No preview · Article · Jan 2014 · Analytica chimica acta
  • Federica Bianchi · Marco Giannetto · Maria Careri
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    ABSTRACT: Biomarkers are cellular or molecular mediators or responders that can serve as indicators of normal biological processes, pathologic processes, or responses to specific pharmacologic treatment. Identification of new biomarkers for specific diseases and the development of novel strategies for prognosis, diagnosis, and treatment designed to take advantage of diagnostic and prognostic indicators is of paramount importance not only for clinical chemistry but also for other types of medicine, for example internal medicine and, obviously, for patients. On the basis of these considerations, the development of easy, non-invasive, and reliable methods for early detection of malignant tumors is a matter of great concern; a specific interest nowadays is the search for biomarkers enabling early identification and distinction between indolent tumors and more aggressive forms of cancer capable of spreading and leading to metastasis. Autoimmune diseases (ADs) arise from an overactive immune response of the body against substances and tissues normally present in the body.
    No preview · Article · Nov 2013 · Analytical and Bioanalytical Chemistry
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    ABSTRACT: European Union legislation has established that plastic food contact materials shall not release primary aromatic amines (PAAs), which are toxic compounds and suspected human carcinogens. As valid alternative to existing methods for PAA determination, which are based on spectrophotometric test or targeted liquid chromatography-tandem mass spectrometry (LC-MS/MS) approaches, in this study a LC-Orbitrap-full scan-high resolution mass spectrometry (HRMS) method was devised and validated for the determination of migration levels of 22 PAAs from food contact materials, thus exploiting the specificity of accurate mass measurement. Direct injection of the simulant (acetic acid 3%, w/v) into the LC-MS system after migration, without any pre-treatment step, makes the developed method of great value for rapid screening analysis of a large number of amines. A very fast and efficient separation (<11min) of PAAs was achieved. Detection limits in the 0.06-0.7μgkg(-1) range were calculated for 17 out of 22 of the investigated PAAs, however obtaining values within 5.3μgkg(-1) for the other 5 amines. Good dynamic linear ranges from two to four orders of magnitude (r(2)≥0.990) were obtained and satisfying results were achieved in terms of intra-day (RSDs<10%) and inter-day repeatability (RSDs<17%). Trueness values in the 70±1-131±5% range proved reliability of the developed method for PAAs quantification also at very low concentration levels. Finally, the method was successfully applied to a range of different real plastic multilayer food packaging materials, noticing in all cases levels below the established limits of detection.
    No preview · Article · Oct 2013 · Journal of Chromatography A
  • Maria Careri

    No preview · Article · Jul 2013 · Analytical and Bioanalytical Chemistry
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    ABSTRACT: Migration of melamine into foods from melamine tableware has been object of recent Rapid Alert System for Food and Feed (RASFF) notifications. In this context, a rapid and sensitive desorption electrospray ionization-high resolution mass spectrometry (DESI-HRMS) method was developed and validated for the determination of melamine migration from plastic materials. The migration test was performed using acetic acid 3% (w/v) as food simulant. Evaluation of DESI parameters in terms of choice of support, motion profile, geometrical configuration and operating conditions coupled to the use of an orbitrap mass analyzer allowed to achieve significant improvements in terms of selectivity and accuracy obtaining detection and quantitation limits at low microgram per kilogram level. A LC-ESI-MS method was also developed for confirmatory purposes. Both methods were applied to 44 melamine tableware samples available on Italian market in order to assess their compliance with the law. Different concentration levels ranging from 0.00773±0.0006 to 3.0±0.1mg/kg were found after the third exposure to the simulant in new and used tableware with two samples out of 44 being characterized by a melamine release higher than the legal limit, i.e. 2.5mg/kg. A two tailed t-test allowed to assess the good agreement between the quantitative results obtained applying the DESI-MS method with those provided by LC-ESI-MS, thus proving reliability of DESI-HRMS as rapid technique for the study of melamine release from plastic materials.
    No preview · Article · Nov 2012 · Talanta