Recently, the high analytical power provided by the new HRMS instruments (working in the MS or MS/MS mode, stand alone or hyphenated with separation techniques) is making more feasible the ...characterization of plant secondary metabolites. In this regard, HRMS-based techniques are becoming the technique of choice, since they are capable of answering many questions regarding the analytical characterization of secondary metabolites, usually found in very complex matrices, including their structural elucidation and quantification in a very fast and sensitive way. In this manuscript we will provide a critical and updated revision of this topic covering the works published in the last 4 years (2015–2018), including the different configurations in which HRMS may be used (stand alone or hyphenated), the data treatment, the strategies for the identification of unknown metabolites, the current software for structure elucidation, as well as the last trends and future outlooks in this hot area of research.
•Recent HRMS-based applications for plant secondary metabolites are reviewed.•Stand alone or hyphenated HRMS configurations are discussed and compared.•A broad variety of databases and HRMS-data mining strategies are presented.•Future challenges in dereplication and metabolite profiling are emphasized.
The quantification of antibiotics, using mass spectrometry, for monitoring therapeutic drugs is a key benefit in infection management. After an easy work-up of plasma samples, analysis were performed ...using both two widely used acquisition modes: MRM for the triple quadrupole spectrometer and fullMS/ddMS2 for the HRMS to quantify twelve antibiotics. Comparison between the two acquisition modes were performed. Validation parameters and sample values were used as comparison criteria. The results indicated a good correlation between the two methods, with an advantage for HRMS concerning the matrix effect. Both methods were applied to routine therapeutic drug monitoring.
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•MRM and HRMS acquisitions were compared for the quantification of 12 antibiotics.•Assays were applied to routine therapeutic drug monitoring on both analytical systems.•HRMS showed better sensitivity for amoxicillin and cefazoline than MRM.•HRMS was less affected by the matrix effect than MRM.
•A suspect chemical database containing 7,922 OPs were established based on the PubChem database.•A neoteric suspect screening and priority ranking strategy of typical OPs was developed.•566, 518, ...and 540 molecular formulas were detected in sediment, water, and indoor dust samples, respectively.•Three OPs candidates were tentatively identified and semiquantified.
Organophosphorus compounds (OPs) are widely used as flame retardants (FRs) and plasticizers, yet strategies for comprehensively screening of suspect OPs in environmental samples are still lacking. In this work, a neoteric, robust, and general suspect screening technique was developed to identify novel chemical exposures by use of ultra-high performance liquid chromatography-Q Exactive hybrid quadrupole-Orbitrap high resolution mass spectrometry (UHPLC-Q-Orbitrap HRMS). We firstly established a suspect chemical database which had 7,922 OPs with 4,686 molecular formulas, and then conducted suspect screening in n = 50 indoor dust samples, n = 76 sediment samples, and n = 111 water samples. By use of scoring criteria such as retention time prediction models, we successfully confirmed five compounds by comparison with their authentic standards, and prioritized three OPs candidates including a nitrogen/fluorine-containing compound, that is dimethyl {1H-indol-3-yl3-(trifluoromethyl)anilinomethyl} phosphonate (DMITFMAMP). Given that the biodegradation half-life values in water (t1/2,w) of DMITFMAMP calculated by EPI Suite is 180 d, it is considered to be potentially persistent. This strategy shows promising potential in environmental pollution assessment, and can be expected to be widely used in future research.
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•Plastic food packaging leaches chemicals and toxicity into food simulants.•Probable transfer of toxic chemicals to food, including endocrine disruptors.•Similar toxicity in methanol ...extracts and water–ethanol food simulant.•LDPE, PUR and PVC migrates induce most receptor activity.•Between 8 and 10 631 chemical features migrate into food simulants.
Plastics constitute a vast array of substances, with over 16000 known plastic chemicals, including intentionally and non-intentionally added substances. Thousands of chemicals, including toxic ones, are extractable from plastics, however, the extent to which these compounds migrate from everyday products into food or water remains poorly understood. This study aims to characterize the endocrine and metabolism disrupting activity, as well as the chemical composition of migrates from plastic food contact articles (FCAs) from four countries as significant sources of human exposure. Fourteen plastic FCAs covering seven polymer types with high global market shares were migrated into water and a water–ethanol mixture as food simulants according to European regulations. The migrates were analyzed using reporter gene assays for nuclear receptors relevant to human health and non-target chemical analysis to characterize the chemical composition. Chemicals migrating from each FCA interfered with at least two nuclear receptors, predominantly targeting pregnane X receptor (24/28 migrates). Moreover, peroxisome proliferator receptor gamma was activated by 19 out of 28 migrates, though mostly with lower potencies. Estrogenic and antiandrogenic activity was detected in eight and seven migrates, respectively. Fewer chemicals and less toxicity migrated into water compared to the water–ethanol mixture. However, 73 % of the 15 430 extractable chemical features also transferred into food simulants, and the water–ethanol migrates exhibited a similar toxicity prevalence compared to methanol extracts. The chemical complexity differed largely between FCAs, with 8 to 10631 chemical features migrating into food simulants. Using stepwise partial least squares regressions, we successfully narrowed down the list of potential active chemicals, identified known endocrine disrupting chemicals, such as triphenyl phosphate, and prioritized chemical features for further identification. This study demonstrates the migration of endocrine and metabolism disrupting chemicals from plastic FCAs into food simulants, rendering a migration of these compounds into food and beverages probable.
Bio‐oils, produced by biomass pyrolysis, have become promising candidates for feedstocks of high value‐added chemicals and alternative sources for transportation fuels. Bio‐oil is such a complicated ...mixture that contains nonpolar hydrocarbons and polar components which cover almost all kinds of organic oxygenated compounds such as carboxylic acids, alcohols, aldehydes, ketones, esters, furfurals, phenolic compounds, sugar‐like material, and lignin‐derived compounds. Comprehensive characterization of bio‐oil and its subfractions could provide insight into the conversion process of biomass processing, as well as its further utilization as transportation fuels or chemical raw materials. This review focuses on advanced analytical strategies on in‐depth characterization of bio‐oil, which is concerned with gas chromatography, high‐resolution mass spectrometry, FTIR spectroscopy and NMR spectroscopy, offering complementary information for previous reviews.
•39 phytotoxins and mycotoxins in blood and urine were extracted with methanol and analyzed by HPLC-Orbitrap MS.•The sample processing is easy to operate, and a single analysis can be completed ...within 30 min.•It provides a basis and reference for the related research of public health poisoning analysis.
Poisonings caused by plant toxins and mycotoxins occur frequently, which do great harm to human health and social public health safety. When a poisoning incident occurs, biological samples are commonly be used to conduct the detection of toxic substances and their metabolites for targeted clinical treatment and incident analysis.
To establish an efficient and accurate analysis method of 39 phytotoxins and mycotoxins in blood and urine by high performance liquid chromatography quadrupole tandem orbitrap mass spectrometry (HPLC-Orbitrap MS).
After 3 mL of methanol being added to 1 mL blood and urine respectively for extraction and protein precipitation, the supernatant was injected into HPLC-Orbitrap MS for analysis. The phytotoxins and mycotoxins were separated by Hypersil GOLD PFP column with gradient elution using methanol-5 mmol/L ammonium acetate as mobile phase. The data were collected in ESI positive ion mode using Full MS/dd-MS2 for mass spectrometry detection.
The mass database of 39 phytotoxins and mycotoxins was developed, and accurate qualitative analysis can be obtained by matching with the database using the proposed identification criteria. Limit of detections (LODs) were 1.34 × 10−4 ∼ 1.92 ng/mL and 1.92 × 10−4 ∼ 9.80 ng/mL for blood and urine samples, respectively. Limits of quantification (LOQ) of toxins in blood and urine ranged from 4.47 × 10−4 ∼ 6.32 ng/mL and 6.39 × 10−4 ∼ 32.67 ng/mL, respectively. Intra-day relative standard deviations (RSDs) were 0.79 % ∼ 10.90 %, and inter-day RSDs were 1.08 % ∼ 18.93 %. The recoveries can reach 90 % ∼ 110 % with matrix matching calibration curves.
The established method is simple and rapid to operate, which can complete the sample analysis within 30 min, providing technical support for clinical poisoning treatment and public health poisoning analysis.
The Tijuana River Estuary (TRE) has been a public health hazard and point of contention between the United States and Mexico for decades, with sources of pollution on both sides of the border. The ...goal of our study is to determine the presence and dynamics of chemical contamination in the TRE. We sampled sediment from four TRE locations in the U.S. during stable dry conditions and immediately after a wet weather period. Organic chemicals were initially screened with non-targeted analysis using gas chromatography high-resolution mass spectrometry (GC/HRMS) that tentatively identified 6978 chemicals in the NIST 20 database. These tentative identifications were filtered using the USEPA CompTox database to guide quantitative targeted analysis at detection limits below 1 ng/g dry weight sediment. Quantitative targeted analysis of 152 organic pollutants and 18 inorganic elements via GC/HRMS revealed generally higher concentrations of contaminants in dry weather sediments compared to wet weather sediments. The highest concentrations of all chemical classes were detected at the site closest to the U.S.-Mexico border, followed by an urban area near Imperial Beach, California, U.S. All sites exhibited a mixture of petrogenic and pyrogenic polycyclic aromatic hydrocarbons (PAHs). Current-use pesticides were dominated by pyrethroid insecticides and the thiocarbamate herbicide s-Ethyl dipropylthiocarbamate (EPTC), while the U.S.-banned organochlorine pesticides were dominated by chlordanes, dieldrin, and dichlorodiphenyltrichloroethane (DDT) and its degradation byproducts. Polychlorinated biphenyl (PCB) concentrations were greatest at the site closest to the U.S.-Mexico border but in the low nanogram-per-gram range. Phthalates were only found at the same site, with relatively high concentrations of bis(2-ethylhexyl) phthalate. This study provides positive identification and quantitative concentrations for organic pollutants in TRE sediments. Our data suggest that there are multiple sources of chemical contamination in the estuary, including possible transboundary movement of pollutants from Mexico.
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•PAHs are the most abundant group of chemicals across all sampling sites.•U.S.-banned pesticides were detected at the site closest to the U.S.-Mexico border.•Phthalates, mainly DEHP, were only detected at the site closest to the border.•Upstream dry weather sediments overall contain higher concentrations of pollutants.
COVID-19 pandemic spread rapidly worldwide with unanticipated effects on mental health, lifestyle, stability of economies and societies. Although many research groups have already reported SARS-CoV-2 ...surveillance in untreated wastewater, only few studies evaluated the implications of the pandemic on the use of chemicals by influent wastewater analysis. Wide-scope target and suspect screening were used to monitor the effects of the pandemic on the Greek population through wastewater-based epidemiology. Composite 24 h influent wastewater samples were collected from the wastewater treatment plant of Athens during the first lockdown and analyzed by liquid chromatography mass spectrometry. A wide range of compounds was investigated (11,286), including antipsychotic drugs, illicit drugs, tobacco compounds, food additives, pesticides, biocides, surfactants and industrial chemicals. Mass loads of chemical markers were estimated and compared with the data obtained under non-COVID-19 conditions (campaign 2019). The findings revealed increases in surfactants (+196%), biocides (+152%), cationic quaternary ammonium surfactants (used as surfactants and biocides) (+331%), whereas the most important decreases were estimated for tobacco (−33%) and industrial chemicals (−52%). The introduction of social-restriction measures by the government affected all aspects of life.
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•Findings reflect the effects of pandemic and social distancing.•Wastewater-based epidemiology was used to assess the exposure to various chemicals.•Significant changes in illicit drug consumption were observed.•Surfactants and biocides showed a notable increase 196% and 152%, respectively.•Significant reduction of the industrial chemicals (52%) due to business closure
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•The first paper identifying and quantifying mycotoxins and metabolites in human breastmilk.•QuEChERS–UHPLC–HRMS allowed rapid and reliable quantitative analysis.•The exposure of ...mothers and infants to mycotoxins was evidenced using human milk.
Humans can be exposed to mycotoxins through the food chain. Mycotoxins are mainly found as contaminants in food and could be subsequently excreted via biological fluids such as urine or human breast milk in native or metabolised form. Since breast milk is usually supposed as the only food for new-borns, the occurrence of mycotoxins in thirty-five human milk samples was evaluated by a newly developed method based on QuEChERS extraction and UHPLC–HRMS detection. The method described here allows the detection of target mycotoxins in order to determine the quality of this initial feeding. The method has been fully validated, with recoveries ranging from 64% to 93% and relative standard deviations (RSD, %) being lower than 20%. Using the method described, non-metabolised mycotoxins such as ZEA, NEO, NIV, ENA, ENA1, ENB, ENB1 and metabolites, such as ZEA metabolites, HT-2, DOM and T-2 triol were detected in human milk samples. Results obtained help to estimate the exposure of mothers and infants to mycotoxins. Moreover, to the best of our knowledge, this is the first work describing the simultaneous detection, quantification and screening of mycotoxins and their metabolites in human mature milk.
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