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Irinotecan (CPT-11) is a water-soluble anticancer drug widely used to treat several types of cancer. Even if the metabolites of CPT-11 are well-known and investigated, only limited information is available in the literature about the formation of photo-degradation products that can naturally originate from sunlight irradiation when the drug is released in aqueous systems. CTP-11 solutions at 10.0 mg L-1 were irradiated by simulated sunlight. The intensity of the drug decreased by 90% after 7.5 days of irradiation and no significant reduction of absorbance values was observed after 13 days. A sensitive UHPLC-MS/MS method was developed employing a hybrid triple quadrupole/linear ion trap mass spectrometer, that is able to work in data-dependent acquisition mode and to obtain information about the compounds formed during the photoirradiation. Moreover, a selected reaction monitoring method was built using the MS/MS fragmentation pattern of the compounds previously investigated. The method was validated considering LOD, LOQ, linearity, precision, selectivity, recovery and matrix effect. LOD and LOQ values were 0.02 and 0.05 ng mL-1, respectively, whereas MDL and MQL values in real water samples (river water, groundwater, well water, and wastewater) were lower than 0.05 and 0.2 ng mL-1, respectively. Eight photodegradation products were identified, among which five for the first time. Based on the MS and MS/MS fragmentation, the chemical structures of the degradation products were proposed. Hydrolysis experiments were carried out on the same solutions preserved in the dark, but no formation of other species was highlighted. The method was applied to several real samples: CPT-11 was detected and quantified only in a hospital effluent sample at the concentration of 0.41 ± 0.2 ng mL-1 together with the occurrence of PDP3. The outcomes of this study may be useful for updating the pollutant screening in water samples

Irinotecan (CPT-11) is a water-soluble anticancer drug widely used to treat several types of cancer. Even if the metabolites of CPT-11 are well-known and investigated, only limited information is available in the literature about the formation of photo-degradation products that can naturally originate from sunlight irradiation when the drug is released in aqueous systems. CTP-11 solutions at 10.0 mg L-1 were irradiated by simulated sunlight. The intensity of the drug decreased by 90% after 7.5 days of irradiation and no significant reduction of absorbance values was observed after 13 days. A sensitive UHPLC-MS/MS method was developed employing a hybrid triple quadrupole/linear ion trap mass spectrometer, that is able to work in data-dependent acquisition mode and to obtain information about the compounds formed during the photoirradiation. Moreover, a selected reaction monitoring method was built using the MS/MS fragmentation pattern of the compounds previously investigated. The method was validated considering LOD, LOQ, linearity, precision, selectivity, recovery and matrix effect. LOD and LOQ values were 0.02 and 0.05 ng mL-1, respectively, whereas MDL and MQL values in real water samples (river water, groundwater, well water, and wastewater) were lower than 0.05 and 0.2 ng mL-1, respectively. Eight photodegradation products were identified, among which five for the first time. Based on the MS and MS/MS fragmentation, the chemical structures of the degradation products were proposed. Hydrolysis experiments were carried out on the same solutions preserved in the dark, but no formation of other species was highlighted. The method was applied to several real samples: CPT-11 was detected and quantified only in a hospital effluent sample at the concentration of 0.41 ± 0.2 ng mL-1 together with the occurrence of PDP3. The outcomes of this study may be useful for updating the pollutant screening in water samples

Background: Based on the medical history and laboratory analytical tests, a patient presenting symptoms compatible with Chronic Fatigue Syndrome was suspected of metal intoxication; therefore, a chelating therapy was attempted. In parallel, the profile of elemental excretion in urine was determined. Methods: Chelation therapy by CaNa2EDTA was administered every two weeks and urine samples were routinely collected for 17 months. The samples were mineralized with HNO3 69 % and analyzed by Inductively-Coupled Plasma – Mass Spectrometry. Data were processed by multivariate statistical methods. Results: Most of the toxic elements showed a peak of excretion in 12−24 h after EDTA administration, which returned to basal level by 24−36 h after the treatment. Yet, the excretion of some trace elements persisted in the urine collected 26 h after the treatment. Conclusions: The analysis of excreted metals following the CaNa2EDTA infusion allowed to monitor dynamically the chelation therapy. The chelation therapy was effective in mobilizing and eliminating the principal heavy metals present from the body. However, since such clearance almost vanished 24 h after the treatment, a protocol with more frequent and low-dose administrations is advisable to improve the metal excretion.

Rice cultivation requires a large use of pesticides and nutrients to control weed proliferation and improve production. The water quality of four neighboring rice fields located in the Lomellina area (Italian Padana plain) was monitored in this study along with the cultivation period (before, during, and after the period of planting), for two successive agricultural seasons (2015 and 2016). Two paddy fields were traditionally cultivated with wet-seeding and the other fields with dry-seeding. Eighteen sampling points were considered: eight points for surface water, two points for underground water, and eight points for porous cups with two different depths. In order to evaluate the goodness of the paddy field system to maintain unchanged the quality of the inflow with respect to the outflow water, three of the most used herbicides in Italian rice cultivation (imazamox, oxadiazon, and profoxydim) and other physical–chemical parameters were determined, namely biological oxygen demand after 5 days; chemical oxygen demand; total suspended solids; anionic surfactants; total hardness; total amount of phosphorus, nitrogen, and potassium; and heavy metal concentrations. In general, all the collected data confirmed that paddy fields did not contribute to worsen the environmental pollution. The different flooding techniques adopted in the fields did not highlight significant differences in concentrations of pesticides or metals. The pesticides reached their maximum concentration (of the magnitude order of few ng mL−1) on the day after the administration and on the day after the application in the adjacent field. A slight reduction of total As in grain was obtained adopting a dry period from steam elongation up to booting. From the collected data, it was possible to identify a general water flow direction in the paddy fields from north–west to south–east: this prevailing flow direction was useful to understand not only the diffusion of the pesticides and their degradation produ

Purpose: The present research reports the study the of plasma proteome profile of stable coronary artery disease (CAD) patients characterized by different levels of total Apolipoprotein-CIII (Apo C-III), a prognostic marker for cardiovascular risk. Experimental design: Two subgroups of CAD patients (n = 52) with divergent concentrations of total circulating Apo C-III (≤ and ≥10 mg dL−1) are examined using a shotgun proteomic approach. Validation experiments are also performed with immunochemistry methods including both the patients affected by CAD (n = 119) and the subjects without CAD (CAD-free; n = 58). Results are analyzed by bioinformatics tools and multivariate statistics. Results: A total of 188 proteins are quantified among the patients. The fold change analysis and the partial least square discriminant analysis show a clear separation of the two groups. Lipoproteins (Apo C-II and Apo E), retinol-binding protein 4, and vitronectin are upregulated in patients with high Apo C-III, while alpha-1 antitrypsin is downregulated. Conclusions and clinical relevance: In this pilot study, the differential expression of plasma proteins related to different concentrations of Apo C-III is defined, suggesting possible new players involved in the Apo C-III-associated process of arterial damage. Data are available via ProteomeXchange with identifier PXD005973

Arbuscular mycorrhizal fungi (AMF) colonize the roots of most terrestrial plant species, improving plant growth, nutrient uptake and biotic/abiotic stress resistance and tolerance. Similarly, plant growth promoting bacteria (PGPB) enhance plant fitness and production. In this study, three different AMF (Funneliformis mosseae, Septoglomus viscosum, and Rhizophagus irregularis) were used in combination with three different strains of Pseudomonas sp. (19Fv1t, 5Vm1K and Pf4) to inoculate plantlets of Fragaria x ananassa var. Eliana F1. The effects of the different fungus/bacterium combinations were assessed on plant growth parameters, fruit production and quality, including health-promoting compounds. Inoculated and uninoculated plants were maintained in a greenhouse for 4 months and irrigated with a nutrient solution at two different phosphate levels. The number of flowers and fruits were recorded weekly. At harvest, fresh and dry weights of roots and shoots, mycorrhizal colonization and concentration of leaf photosynthetic pigments were measured in each plant. The following fruit parameters were recorded: pH, titratable acids, concentration of organic acids, soluble sugars, ascorbic acids, and anthocyanidins; volatile and elemental composition were also evaluated. Data were statistically analyzed by ANOVA and PCA/PCA-DA. Mycorrhizal colonization was higher in plants inoculated with R. irregularis, followed by F mosseae and S. viscosum. In general, AMF mostly affected the parameters associated with the vegetative portion of the plant, while PGPB were especially relevant for fruit yield and quality. The plant physiological status was differentially affected by inoculations, resulting in enhanced root and shoot biomass. Inoculation with Pf4 bacterial strain increased flower and fruit production per plant and malic acid content in fruits, while decreased the pH value, regardless of the used fungus. Inoculations affected fruit nutritional quality, increasing sugar and anth

The characterization of 72 Italian honey samples from 8 botanical varieties was carried out by a comprehensive approach exploiting data fusion of IR, NIR and Raman spectroscopies, Proton Transfer Reaction – Time of Flight – Mass Spectrometry (PTR-MS) and electronic nose. High-, mid- and low-level data fusion approaches were tested to verify if the combination of several analytical sources can improve the classification ability of honeys from different botanical origins. Classification was performed on the fused data by Partial Least Squares – Discriminant Analysis; a strict validation protocol was used to estimate the predictive performances of the models. The best results were obtained with high-level data fusion combining Raman and NIR spectroscopy and PTR-MS, with classification performances better than those obtained on single analytical sources (accuracy of 99% and 100% on test and training samples respectively). The combination of just three analytical sources assures a limited time of analysis.

Arbuscular mycorrhizal fungi (AMF) colonize the roots of most terrestrial plant species, improving plant growth, nutrient uptake and biotic/abiotic stress resistance and tolerance. Similarly, plant growth promoting bacteria (PGPB) enhance plant fitness and production. In this study, three different AMF (Funneliformis mosseae, Septoglomus viscosum, and Rhizophagus irregularis) were used in combination with three different strains of Pseudomonas sp. (19Fv1t, 5Vm1K and Pf4) to inoculate plantlets of Fragaria x ananassa var. Eliana F1. The effects of the different fungus/bacterium combinations were assessed on plant growth parameters, fruit production and quality, including health-promoting compounds. Inoculated and uninoculated plants were maintained in a greenhouse for 4 months and irrigated with a nutrient solution at two different phosphate levels. The number of flowers and fruits were recorded weekly. At harvest, fresh and dry weights of roots and shoots, mycorrhizal colonization and concentration of leaf photosynthetic pigments were measured in each plant. The following fruit parameters were recorded: pH, titratable acids, concentration of organic acids, soluble sugars, ascorbic acids, and anthocyanidins; volatile and elemental composition were also evaluated. Data were statistically analyzed by ANOVA and PCA/PCA-DA. Mycorrhizal colonization was higher in plants inoculated with R. irregularis, followed by F mosseae and S. viscosum. In general, AMF mostly affected the parameters associated with the vegetative portion of the plant, while PGPB were especially relevant for fruit yield and quality. The plant physiological status was differentially affected by inoculations, resulting in enhanced root and shoot biomass. Inoculation with Pf4 bacterial strain increased flower and fruit production per plant and malic acid content in fruits, while decreased the pH value, regardless of the used fungus. Inoculations affected fruit nutritional quality, increasing sugar and anth

The characterization of 72 Italian honey samples from 8 botanical varieties was carried out by a comprehensive approach exploiting data fusion of IR, NIR and Raman spectroscopies, Proton Transfer Reaction – Time of Flight – Mass Spectrometry (PTR-MS) and electronic nose. High-, mid- and low-level data fusion approaches were tested to verify if the combination of several analytical sources can improve the classification ability of honeys from different botanical origins. Classification was performed on the fused data by Partial Least Squares – Discriminant Analysis; a strict validation protocol was used to estimate the predictive performances of the models. The best results were obtained with high-level data fusion combining Raman and NIR spectroscopy and PTR-MS, with classification performances better than those obtained on single analytical sources (accuracy of 99% and 100% on test and training samples respectively). The combination of just three analytical sources assures a limited time of analysis.

Natural and Artificial Flavoring Agents and Dyes, Volume 7 in the Handbook of Food Bioengineering series, examines the use of natural vs. artificial food dyes and flavors, highlighting some of the newest production and purification methods. This solid resource explores the most recent trends and benefits of using natural agents over artificial in the production of foods and beverages. Using the newest technologies and evidence-based research methods, the book demonstrates how natural flavoring agents and dyes can be produced by plants, microorganisms and animals to produce higher quality foods that are more economical and safe to the consumer

Alpha-cypermethrin is a broad-spectrum insecticide widely used in the treatment of rice crops, mainly commercialized as a CONTEST® formulation. The photodegradation of alpha-cypermethrin and of the commercial formulation has not yet been systematically investigated in paddy water under natural conditions. Here, paddy water solutions of alpha-cypermethrin and CONTEST® formulation at 5.0 mg L−1 were irradiated under simulated sunlight for 10 days. Hydrolysis experiments were carried out on the same solutions preserved in the dark. Analysis by ultra-high-performance liquid chromatography–tandem mass spectrometry was developed for the identification of photodegradation products. Results show that degradation of pure alpha-cypermethrin and the formulation counterpart produces both common and different photodegradation products. Five out eleven photodegradation products were identified for the first time, in particular three in the alpha-cypermethrin paddy water solution and four in the formulation. Our findings underline the importance of carrying out photodegradation experiments directly on the commercial formulation, since degradation products could be different from the pure insecticide

The paper deals with the development of an online UHPLC-MS/MS method for the identification and determination of 25 Endocrine Disrupting Chemicals (EDCs) belonging to different chemical classes (perfluorochemicals, bisphenols, alkylphenols, phthalates, and parabens). The study regards the possible EDC migration from different medical devices of diverse materials used in the routine hospitals for blood sampling or for the parenteral nutrition therapies. In order to evaluate the release of EDCs, the equipment used for blood sampling (syringes, butterfly, cannula-needle, microcapillary tube) was put in contact with a physiological solution at a prefixed time. As regards the migration tests carried out on the medical devices used in the parenteral nutrition therapy (infusion tubes, venous catheters), the catheters were undergone to internal contact with parenteral solution and external contact with physiological one, whereas the infusion tubes were subjected only to internal migration test with parenteral solution. The results demonstrated the released of some ECDs (such as parabens at the concentration of few pg mL −1 , diethylphthalate and dibutylphthlate at ng mL −1 level), when using physiological solution as the leaching agent. In addition, the presence of a PFOS structural isomer was found at 29.0 ng mL -1 : this compound was released in part from the infusion tubes and mostly from the venous catheters, particularly from silicone ones. Using a more lipophilic solution, such as parenteral preparations, a greater amount of EDCs was released, among which also the diethylhexylphthalate that was quantified in all the investigated devices (without highlighting particular trends or migration from PVC devices), but its concentration remained always lower than imposed maximum threshold limit on medical device of 0.1% w/w. The releases from the infusion tubes of the same materials (polyethylene) from different manufacturers are very comparable, whereas the catheter of silic

We conducted a proteomics study in order to detect the proteomic method which provides the most complete characterization of the proteins of rice milk. In particular, we compared the results obtained from LC-MS/MS after protein precipitation with acetone or TCA, as well as the results obtained from LC-MS/MS after protein prefractionation based on SDS-PAGE (GeLC-MS/MS) or ProteoMinerTM technology (ProteoMiner-LC-MS/MS), and after peptide prefractionation based on IEF (pIEF-LC-MS/MS). A total of 158 protein species have been detect in rice milk. The physical-chemical analysis and classification of the identified proteins were also reported. In particular, we showed that pIEF-LC-MS/MS method led to a significant increase in the proteome coverage, allowing the identification of a total of 96 proteins of milk rice. This study demonstrates the utility of a prefractionation step based on pIEF before the shotgun proteomic analysis and offers an in-depth insight into the rice milk proteome.

Head space (HS) solid phase microextraction (SPME) followed by gas chromatography with mass spectrometry detection (GC-MS) is the most widespread technique to study the volatile profile of honey samples. In this paper, the experimental SPME conditions were optimized by a multivariate strategy. Both sensitivity and repeatability were optimized by experimental design techniques considering three factors: extraction temperature (from 50°C to 70°C), time of exposition of the fiber (from 20 min to 60 min), and amount of salt added (from 0 to 27.50%). Each experiment was evaluated by Principal Component Analysis (PCA) that allows to take into consideration all the analytes at the same time, preserving the information about their different characteristics. Optimal extraction conditions were identified independently for signal intensity (extraction temperature: 70°C; extraction time: 60 min; salt percentage: 27.50% w/w) and repeatability (extraction temperature: 50°C; extraction time: 60 min; salt percentage: 27.50% w/w) and a final global compromise (extraction temperature: 70°C; extraction time: 60 min; salt percentage: 27.50% w/w) was also reached. Considerations about the choice of the best internal standards were also drawn. The whole optimized procedure was than applied to the analysis of a multiflower honey sample and more than 100 compounds were identified.

Proteins and small molecules from ancient objects and cultural heritage can provide key information and contribute to study the context of objects and artists. However, all present-day protocols and strategies for the analysis of ancient samples are often invasive and require microsampling. Here, we present a new method for the noninvasive analysis of proteins and small molecules: the technique uses a special ethyl-vinyl acetate film functionalized with strong cation/anion exchange and C8 resins, for interacting with both proteins and small molecules present on the surface of the objects, followed by LC-MS/MS analysis. The new method was fully validated for the determination of both proteins and small molecules on several types of supports, showing excellent analytical performances such as, for example, R2 of the calibration curve of 0.98 and 0.99 for proteins and small molecules, low but very repeatable recoveries, particularly adequate for investigations on precious ancient samples that must not be altered by the analytical procedure. ESEM images and LED multispectral imaging confirmed that no damages or alterations occurred onto the support surfaces and no residues were left from the extractive film. Finally, the new method was applied for the characterization of the binders of a historical fresco of the XVI century from the Flemish painter Paul Brill and of a recently discovered fresco from Isidoro Bianchi (XVII century). Moreover the method was employed for the identification of the colorant used by Pietro Gallo (XIV century) on a wood panel. The method here reported can be easily applied to any other research on ancient precious objects and cultural heritage, since it does not require microsampling and the proteins/small molecules extraction can be performed directly in situ, leaving the object unchanged and intact. (Figure Presented)

The industrial processes of starch cationization are widely used and the workers must protect their health from the potential presence of toxic species, such as 2,3-epoxypropyltrimethylammonium chloride (ETA or Quab 151®) or 3-chloro-2-hydroxypropyltrimethylammonium chloride (CTA or Quab 188®) used during the industrial processes. In this study, a sensitive and fast chromatographic method for the identification and determination of these toxic species in samples placed in fixed air sampling positions near to the reactor of starch processing has been developed and fully validated. The method is based on hydrophilic interaction liquid chromatography coupled to tandem mass spectrometry detection. The limits of detection are 3.0 ng mL-1 and 1.0 ng mL-1 for ETA and CTA, respectively, and the RSD% of the intraday (n = 5) and the interday (n = 35) precision of concentration determination are lower than 3.4% and 6.1%, respectively. The solid-liquid extraction procedure employed here is very simple (sonication) and fast (5 min) and allows obtaining reliable recovery values greater than 91.0%. No evidence of statistically significant matrix effects (at a 95% of confidence level) during the mass spectrometry analysis has been found. The method has been successfully applied to filter samples used in routine controls for the safety of workers involved in these type of industrial processes.

Background: In the last decades particular attention has been devoted to packaging materials to obtain the best conditions to store food and to preserve the organoleptic properties. Methods: In the present study samples of tomato sauce collected in different Italian markets and preserved in different packaging materials (glass, tin and multilayer plastic containers) were chemically characterized considering the content of anions (6 species), carotenoids (lycopene, sum of alpha-and beta-carotene), flavonoids (epicatechin and quercetin), metals (41 species), total polyphenols, vitamins (C and Bgroup), and volatile profile. Different analytical techniques were employed like GC and LC with different detectors (MS and DAD), ICP-MS and ICP-OES. All developed methods were validated and applied to different commercial products collected from local markets. Results: Multivariate statistical tools (Principal Components Analysis – Discriminant Analysis, PCA – DA, Ranking PCA and Partial Least Square – Discriminant Analysis, PLS – DA) were then applied to evaluate the effect played by the different packaging on the chemical profile of the samples. The multivariate strategy adopted allowed to identify markers able to discriminate samples stored in glass, tin or multilayer plastic containers. Conclusion: In both cases, the differences identified between the classes of samples can be ascribed to a double effect: 1) products stored in glass preserve their content in vitamins and other important nutrients or 2) storage in glass could force manufacturers to provide a product of better quality since the product is visible to the final consumer.