Aim of this study was to provide an up-to-date assessment of the antibiotics contaminating the aqueous environment in Italy, for a better understanding of risks for the ecosystem and human health. ...Antibiotics were first listed in order of their theoretical environmental loads, then were measured in wastewater of some sewage treatment plants (STPs) and in rivers in Italy. Macrolides, particularly clarithromycin and spiramycin, and quinolones, particularly ciprofloxacin and
l-floxacin/ofloxacin, were the most abundant antibiotics in untreated wastewater. Several of them were not removed in STPs and still remained in the treated wastewater, and a total estimate of 7–14
tons of active principles were discharged annually into the aqueous environment in Italy through this route. Results of the analysis of rivers in northern Italy agreed with these figures, with an average load of 5
kg/day, or about 1.8
tons/year, of antibiotics flowing in the River Po, at sampling sites covering a basin comprising about one-fifth of the Italian population. In conclusion, antibiotics, particularly macrolides and quinolones, are widespread environmental contaminants, and urban STPs are confirmed a major source of the contamination.
Spent coffee ground (SCG) is the remaining residue produced after extraction of coffee, and it is considered a source of unextracted bioactive compounds. For this, in the latest years, the attention ...has been focused to innovative reuses that can exploit the potentiality of SCG. Unfortunately, the content of bioactive compounds has not been thoroughly studied yet, and the major of publication has investigated the caffeine and chlorogenic acids levels, total polyphenol contents, and total flavonoid content. Hence, these approaches have determined only an estimation of flavonoids and polyphenols content and lack on single polyphenols investigation. Therefore, the objective of the current work was to provide a deep characterization of bioactive compounds in SCG. For this purpose, a new analytical method for the quantification of 30 molecules, including caffeine, chlorogenic acids, phenolic acids, flavonoids, and secoiridoids, has been developed using high‐performance liquid chromatography tandem mass spectrometry. Moreover, several extraction procedures, that is, liquid–solid extraction assisted and not by ultrasounds, testing diverse solvents, were evaluated. Liquid–solid extraction assisted by sonication, with water/ethanol (30/70, v/v), resulted the best in terms of total bioactive compounds, and, once validated, the new analytical method was applied to five different espresso SCG samples. Data showed that caffeine (means: 1193.886 ± 57.307 mg kg−1) and chlorogenic acids (means of total CQAs: 1705.656 ± 88.694 mg kg−1) were the most abundant compounds in all SCG samples followed by phenolic acids such as caffeic, ferulic, gallic, p‐coumaric, syringic, trans‐cinnamic, and vanillic acid. Moreover, some flavonoids, that is, rutin, cyanidin 3‐glucoside, and quercetin, occurred in almost all samples. This work provided a deepened characterization of bioactive compounds in SCG and can contribute to develop new strategies of reuses.
Oxytetracycline (OTC) is a widely used broad-spectrum antibiotic, whose presence in water and sediments was reported in various regions of the world. The effects of OTC and other tetracyclines on the ...environment have been intensively studied although many of their transformation products (TPs) formed in the environment and their impact have not been yet fully characterized. Abiotic and biotic degradation tests under aerobic conditions at two pH values were carried out using OTC in artificial water/sediment systems to assess the effect of these variables on the environmental fate of the pollutant. HPLC-MSn was employed to detect and identify the main degradation products and pathways. Several transformations involved in the process were identified including alcohol oxidation, decarbonylation and hydroxylation. Differences in TPs and kinetics were found among degradation conditions, remarking a faster degradation of both OTC and TPs in the presence of microorganisms and at lower pH values. In summary, a total of 44 TPs were detected and structures were proposed for 20 of them, none of them having been previously reported. Furthermore, OTC degradation generated 24 TPs which remained in either solution or sediment, although none of them displayed higher algae toxicity than OTC. These results might be useful for planning future remediation and monitoring strategies.
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•OTC remains more in artificial sediment at the higher pH tested for all conditions•Transformation products of OTC were dependent on both the pH and biotic conditions•More than 50% of the transformation products were still in solution after 55 days•Chemical structures were proposed for 20 of the 44 transformation products detected
Nitrate commands genome‐wide gene expression changes that impact metabolism, physiology, plant growth, and development. In an effort to identify new components involved in nitrate responses in ...plants, we analyze the Arabidopsis thaliana root phosphoproteome in response to nitrate treatments via liquid chromatography coupled to tandem mass spectrometry. 176 phosphoproteins show significant changes at 5 or 20 min after nitrate treatments. Proteins identified by 5 min include signaling components such as kinases or transcription factors. In contrast, by 20 min, proteins identified were associated with transporter activity or hormone metabolism functions, among others. The phosphorylation profile of NITRATE TRANSPORTER 1.1 (NRT1.1) mutant plants was significantly altered as compared to wild‐type plants, confirming its key role in nitrate signaling pathways that involves phosphorylation changes. Integrative bioinformatics analysis highlights auxin transport as an important mechanism modulated by nitrate signaling at the post‐translational level. We validated a new phosphorylation site in PIN2 and provide evidence that it functions in primary and lateral root growth responses to nitrate.
Synopsis
Phosphoproteomic analysis in response to nitrate treatment reveals early nitrate‐induced changes in Arabidopsis thaliana root phosphoproteins associated to signaling while late changes are associated to transport and hormone metabolism. Moreover, nitrate promotes the dephosphorylation of PIN2, impacting PIN2 subcellular localization and root development.
Several nitrate‐regulated phosphoproteins involved in signaling, metabolism and other functions were identified.
NRT1.1 is required for normal phosphoproteome responses to nitrate treatments.
Nitrate regulates root system architecture by modulating PIN2 phosphorylation status.
Phosphoproteomic analysis in response to nitrate treatment reveals early nitrate‐induced changes in Arabidopsis thaliana root phosphoproteins associated to signaling while late changes are associated to transport and hormone metabolism. Moreover, nitrate promotes the dephosphorylation of PIN2, impacting PIN2 subcellular localization and root development.
•A fast method for the simultaneous determination of 11 additives.•HPLC coupled with DAD and MS/MS methods are used.•Good recoveries in the range of 75.2–113.8%.•Suitable for the routine monitoring ...analysis of 11 additives.
In this study, an efficient, fast and sensitive method for the simultaneous determination of eleven synthetic color additives (Allura red, Amaranth, Azo rubine, Brilliant blue, Erythrosine, Indigotine, Ponceau 4R, New red, Sunset yellow, Quinoline yellow and Tartrazine) in flour and meat foodstuffs is developed and validated using HPLC coupled with DAD and MS/MS. The color additives were extracted with ammonia–methanol and was further purified with SPE procedure using Strata-AW column in order to reduce matrix interference. This HPLC–DAD method is intended for a comprehensive survey of color additives in foods. HPLC–MS/MS method was used as the further confirmation and identification. Validation data showed the good recoveries in the range of 75.2–113.8%, with relative standard deviations less than 15%. These methods are suitable for the routine monitoring analysis of eleven synthetic color additives due to its sensitivity, reasonable time and cost.
Ferula species have occupied great value in traditional medicine in various countries. The aim of the present paper was to assess for the first time to the phytochemical profile of Ferula tunetana ...Pomel ex Batt. (F. tunetana) seed and leaf extracts using HPLC-MS/MS, as well as to evaluate their antioxidant and anti-α-amylase activities. Therefore, total phenolic and flavonoid amounts of the studied extracts were determined and 38 compounds were detected and quantified (phenolic acids, flavonoids, non-phenolic acid and stilbenes). In addition of their antioxidant potential against 1,1-diphenyl-2-picrylhydrazyl (DPPH) and Ferric Reducing Antioxidant Power (FRAP) assays, in vitro and in silico studies were adopted to evaluate α-amylase inhibitory properties of F. tunetana extracts. Ethyl acetate (EtOAc) seed extract showed the highest total phenolic content, antioxidant potential (IC50 = 19.00 ± 0.37 μg/mL) in terms of free radical scavenging, also for α-amylase inhibition activity with IC50 values of 17.39 ± 0.92 μg/mL. The molecular docking analysis and the drug-likeness prediction of the major selected compounds explained the significant anti-α-amylase activity of the studied extracts. The obtained analysis and results suggest that F. tunetana extracts could be promising candidates to develop a new generation of efficient and especially safe antidiabetic treatments.
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•38 phytochemicals were quantified in Ferula tunetana extracts by HPLC-MS/MS method.•Total phenolic and flavonoid contents in seed and leaf extracts were estimated.•The studied extracts exhibited good anti-α-amylase and antioxidant activities.•The molecular docking of main components validated the strong antidiabetic effects.•The drug-likeness proprieties of the major compounds were predicted.
► Development of HPLC–MS/MS method for simultaneous quantification of 12 nitro-aromatics. ► Validation of the method for analysis of atmospheric particulate matter. ► Detailed investigation of matrix ...effects. ► Significantly higher concentrations of nitrocatechols in winter samples. ► Correlation analysis between nitro-aromatics and anhydrosugars.
Nitrogen-containing organic compounds in the atmosphere have drawn attention owing to their impact on aerosol chemistry and physics and their potential adverse effects on the biosphere. Among them, nitrocatechols and their homologs have recently been associated with biomass burning. In the present study, nitrocatechols, nitrophenols, nitroguaiacols and nitrosalicylic acids (NSAs) were simultaneously quantified for the first time by using a new analytical method based on liquid chromatography/tandem mass spectrometry, which was systematically optimized and validated. Several analyte specific issues regarding the sample preparation and chromatographic analysis were addressed in order to ensure method sensitivity, precision, and accuracy. Sample matrix effects were thoroughly investigated in order to ensure method specificity. The method was found to be sensitive with limits of detection ranging from 0.1 to 1.0μgL−1, and with accuracy generally between 90 and 104%. The relative standard deviations for repeatability and intermediate precision were better than 4% and 9%, respectively. The method was applied to the analysis of winter and summer PM10 samples from the city of Ljubljana, Slovenia. Aerosol concentrations as high as 152 and 134ngm−3 were obtained for the major aerosol nitro-aromatics: 4-nitrocatechol (4NC) and methyl-nitrocatechols (MNCs), respectively. Up to 500-times higher concentrations of 4NC and MNCs were found in winter compared to summer aerosols. The correlation analysis for winter samples showed that 4NC, MNCs, and NSAs are strongly inter-correlated (R2=0.84–0.96). Significant correlations between these analytes and anhydrosugars support their proposed origin from biomass burning. The studied nitro-aromatics were found to constitute a non-negligible fraction (around 1%) of the organic carbon.
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•Two tandem MS techniques were applied to structural speciation of CGAs in Ferrovia Italian sweet cherry.•Some methylcoumaroyl and caffeoylquinates were found in cherries for the ...first time.•trans-3-O-Coumaroylquinic and chlorogenic acids were the main CGAs quantified.
This paper deals with an extensive analytical approach, which uses two complementary tandem mass spectrometry techniques, to characterize the chlorogenic acids (CGAs) present in a typical Italian sweet cherry variety (cv Ferrovia). Sixteen monoacyl-quinic acids and esters, five diacyl-quinic acids, three caffeoyl-quinic acids glycosides, and two caffeic acid hexoses were detected by HPLC-MSn analyses (MSn up to MS4), among which four methyl coumaroyl quinate and three methyl caffeoyl quinate isomers were tentatively identified in sweet cherries for the first time. HPLC-MS/MS analyses through multiple reaction monitoring (MRM) experiments showed that trans-3-O-caffeoylquinic acid, cis-3-O-coumaroylquinic acid, trans-3-O-coumaroylquinic acid, trans-5-O-caffeoylquinic acid, and methyl-3-O-caffeoyl quinate were the main CGAs in the mature berries of cv Ferrovia. Considering that CGAs can have several health benefits depending on their amount but also on their structural features, the results of this study provide new insight into the knowledge of the quali-quantitative profile of these phytochemicals in a widespread fruit such as sweet cherry.
Growing scientific evidence indicates that
is a valuable source of active ingredients with potential cosmetic applications. However, the data on its composition and pharmacological properties are ...still insufficient. This study aims to optimize the extraction procedure of the plant material, evaluate its phytochemical composition, and compare anti-tyrosinase potential of
extracts obtained by various methods. In order to identify compounds responsible for the tyrosinase inhibitory activity of
, the most active anti-tyrosinase extract was fractionated by column chromatography. The fractions were examined for their skin lightening potential by mushroom and murine tyrosinase inhibitory assays and melanin release assay. HPLC-ESI-Q-TOF-MS/MS analysis of the total extract revealed the presence of several phenolic acids, flavonoids, flavonoid glucosides, and carboxylic acid. Among them, fraxetin-8-
-glucoside, quercetin-
-glucopyranose, schaftoside/isoschaftoside, gmelinin B, 1,3-dicaffeoylquinic acid (1,3-DCQA), and ferulic acid were found in the fractions with the highest skin lightening potential. Based on obtained qualitative and quantitative analysis of the fractions, it was assumed that the caffeoylquinic acid derivatives and dicaffeoylquinic acid derivatives are more likely responsible for mushroom tyrosinase inhibitory activity of
extracts and fractions. Ferulic acid was proposed as the most active murine tyrosinase inhibitor, responsible also for the reduced melanin release from B16F10 murine melanoma cells.
A multiresidue method for the quantification of 13 sulfonamides in animal feed is described. It involves the application of a modified QuEChERS procedure followed by HPLC–MS/MS (high performance ...liquid chromatography coupled to tandem mass spectrometry) analysis. The best conditions for the extraction solution and PSA (primary secondary amine) mass were determined. After optimization, the method was validated according to the European Commission Decision 2002/657/EC. The validation levels employed were 25, 50 and 75 μg kg−1. Acceptable values were obtained for the following parameters: linearity (0.9864 < r2 < 0.9993), decision limit (50.4 μg kg−1 < CCα < 55.8 μg kg−1), detection capability (50.7 μg kg−1<CCβ < 55.8 μg kg−1), limit of quantification (0.9 μg kg−1 < LOQ < 7.1 μg kg−1), accuracy (86.0 < recovery rates < 106.8), precision (3.6 < repeatability < 19.5), (5.5 < intermediate precision < 21.6), measurement uncertainty (MU) (4.1 < MU < 32.6) and selectivity. These findings met the Codex requirements, which allow for the routine use of the method by the laboratories linked to the Ministry of Agriculture, Livestock and Food Supply of Brazil. Finally, the method was applied to real samples and only one of them showed positive for sulfamethazine, however, with a concentration below the LOQ of the method.
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