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Cyclodepsipeptides (CDPs) represent a huge family of chemically and structurally diverse molecules with a wide ability for molecular interactions. CDPs are cyclic peptide-related natural products made up of both proteinogenic and nonproteinogenic amino acids linked by amide and ester bonds. The combined use of different analytical methods is required to accurately determine their integral structures including stereochemistry, thus allowing deeper insights into their often-intriguing bioactivities and their possible usefulness. Our goal is to present the various methods developed to accurately characterize CDPs. Presently, Marfey's method and NMR (nuclear magnetic resonance) are still considered the best for characterizing CDP configuration. Nevertheless, electrospray-high resolution tandem mass spectrometry (ESI-HRMS/MS) is of great value for efficiently resolving CDP's composition and sequences. For instance, recent data shows that the fragmentation of cationized CDPs (e.g., [M + Li] + and [M + Na] + ) leads to selective cleavage of ester bonds and specific cationized product ions (b series) useful to get unprecedented sequence information. Thus, after a brief presentation of their structure, biological functions, and biosynthesis, we also provide a historic overview of these various analytical approaches as well as their advantages and limitations with a special emphasis on the emergence of methods based on HRMS/MS through recent fundamental works and applications., (© 2024 The Author(s). Mass Spectrometry Reviews published by Wiley Periodicals LLC.)

Bacillus cereus is responsible for foodborne outbreaks worldwide. Among the produced toxins, cereulide induces nausea and vomiting after 30 min to 6 h following the consumption of contaminated foods. Cereulide, a cyclodepsipeptide, is an ionophore selective to K + in solution. In electrospray, the selectivity is reduced as [M + Li] + ; [M + Na] + and [M + NH 4 ] + can also be detected without adding corresponding salts. Two forms are possible for alkali-cationized ions: charge-solvated (CS) that exclusively dissociates by releasing a bare alkali ion and protonated salt (PS), yielding alkali product ions by covalent bond cleavages (CBC) promoted by mobile proton. Based on a modified peptide cleavage nomenclature, the PS product ion series (b, a, [b + H 2 O] and [b + C n H 2n O] [n = 4, 5]) are produced by Na + /Li + /K + -cationized cereulide species that specifically open at ester linkages followed by proton mobilization promoting competitive ester CBC as evidenced under resonant collision activation. What is more, unlike the sodiated or lithiated cereulide, which regenerates little or no alkali cation, the potassiated forms lead to an abundant K + regeneration. This occurs by splitting of (i) the potassiated CS forms with an appearance threshold close to that of the PS first fragment ion generation and (ii) eight to four potassiated residue product ions from the PS forms. Since from Na + /Li + -cationized cereulide, (i) the negligible Na + /Li + regeneration results in a higher sensibility than that of potassiated forms that abundantly releasing K + , and (ii) a better sequence recovering, the use of Na + (or Li + ) should be more pertinent to sequence isocereulides and other cyclodepsipeptides., (© 2024 The Authors. Journal of Mass Spectrometry published by John Wiley & Sons Ltd.)

The chemical burden on the environment and human population is increasing. Consequently, regulatory risk assessment must keep pace to manage, reduce, and prevent adverse impacts on human and environmental health associated with hazardous chemicals. Surveillance of chemicals of known, emerging, or potential future concern, entering the environment-food-human continuum is needed to document the reality of risks posed by chemicals on ecosystem and human health from a one health perspective, feed into early warning systems and support public policies for exposure mitigation provisions and safe and sustainable by design strategies. The use of less-conventional sampling strategies and integration of full-scan, high-resolution mass spectrometry and effect-directed analysis in environmental and human monitoring programmes have the potential to enhance the screening and identification of a wider range of chemicals of known, emerging or potential future concern. Here, we outline the key needs and recommendations identified within the European Partnership for Assessment of Risks from Chemicals (PARC) project for leveraging these innovative methodologies to support the development of next-generation chemical risk assessment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Chlordecone is an organochlorine pesticide used from 1972 to 1993 in the French West Indies. Its extensive use and high persistence in soils induced massive contamination of the environment and of the food chain, especially in cattle through contaminated soil ingestion. To ensure suitability for consumption of bovine meat, monitoring plans are set up based on perirenal fat concentrations after slaughtering. In the present study, we have investigated an in-vivo monitoring approach by measuring chlordecone levels in serum samples. For this purpose, a sensitive high-performance liquid-chromatography-tandem mass spectrometry (HPLC-MS/MS) method following a QuEChERS extraction method was successfully optimized and validated, reaching a limit of quantification of 0.05 ng g -1 fresh weight. This method was applied to 121 serum samples collected from bovines originating from contaminated areas of Martinique and Guadeloupe. Chlordecone was detected in 88% of the samples, and quantified in 77% of the samples, with concentrations ranging from 0.05 to 22 ng g -1 . Perirenal fat, liver, and muscle were also sampled on the same animals and the measured concentrations of chlordecone were statistically correlated to the levels determined in serum. Mean concentration ratios of 6.5 for fat/serum, 27.5 for liver/serum, and 3.3 for muscle/serum were calculated, meaning that chlordecone was not only distribute in fat (as expected), muscle and liver, but also in serum. Good correlations were found to allow prediction of chlordecone concentrations in muscle based on concentrations measured in serum. This study opens the door to possible pre-control of bovines before slaughter. In cases of probable non-compliance with maximum residue levels (MRLs), farm management could proceed to allow for depuration under controlled conditions. This would have a strong impact on both economic and food safety management measures., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Chlordecone (CLD) is an organochlorine pesticide widely used from the 1970s to the 1990s in the French West Indies that induced long-term pollution of the ecosystem. Due to involuntary soil ingestion, some species bred in open-air areas can be contaminated. As CLD is distributed in various tissues depending on the breeding species, this study focuses on the distribution of CLD in bovines. For this purpose, three tissues, i.e. fat, muscle, and liver, from 200 bovines originating from Martinique and Guadeloupe were sampled in 2016 to determine their endemic contamination levels. Analyses were performed with the official method for veterinary controls, isotopic dilution liquid chromatography-tandem mass spectrometry, which has been fully validated and which reaches a limit of quantification of 3 μg.kg -1 fresh weight (fw). Irrespective of the matrices, CLD was detected in 68% of samples (404 samples above the LOD) and quantified in 59% of samples (332 samples above the LOQ). Regarding contamination levels, the liver had a broader range of concentrations (LOQ up to 420.6 μg.kg -1 fw) than fat (LOQ up to 124.6 μg.kg -1 fw) and muscle (LOQ up to 67.6 μg.kg -1 fw). This confirms the atypical behaviour of CLD compared to other persistent organochlorine pollutants. Statistical processing demonstrated a correlation between CLD concentrations among the three studied tissues. The CLD concentration ratios were 0.54 for muscle/fat, 3.75 for liver/fat, and 0.14 for muscle/liver., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Chlordecone (CLD) is a toxic organochlorine pesticide frequently used in the French West Indies until 1993, resulting in a contamination of soil and food. This study assessed the behaviour of CLD residues and CLD processing factors (PFs) during four home cooking processes: cooking in a conventional oven ("oven"), frying ("pan"), cooking in a microwave oven ("microwave") and grilling ("grill"). These four processes were applied to six types of naturally contaminated beef (kidney, liver, rib, chuck, top-sirloin and sirloin). Targeted analyses with isotopic dilution were carried out by ID-HPLC-MS/MS to determine CLD concentrations before and after each cooking process and the corresponding processing factors. HPLC-HRMS/MS was used to find potential organochlorine degradation by-products and/or CLD metabolites present in samples by target, suspect and non-target screening. Cooking processes and especially microwave cooking led to a significant decrease in the CLD contained in beef (2% < PF < 17%). Traces of 5b-hydro-CLD and of another mono-hydro-CLD were found in the uncooked liver but no CLD degradation by-product was observed in the cooked liver., (Copyright © 2020 The Authors. Published by Elsevier Ltd.. All rights reserved.)

In 2015, tetrodotoxins (TTXs) were considered a potential threat in Europe since several studies had shown the presence of these toxins in European bivalve molluscs. In this study, we investigated the occurrence of TTXs in 127 bivalve samples (mussels and oysters) and in 66 gastropod samples (whelks) collected all along the French mainland coasts in 2017 and 2018. Analyses were carried out after optimization and in-house validation of a performing hydrophilic interaction liquid chromatography associated with tandem mass spectrometry (HILIC-MS/MS) method. The concentration set by European Food Safety Authority (EFSA) not expected to result in adverse effects (44 µg TTX equivalent/kg) was never exceeded, but TTX was detected in three mussel samples and one whelk sample (1.7-11.2 µg/kg). The tissue distribution of TTX in this whelk sample showed higher concentrations in the digestive gland, stomach and gonads (7.4 µg TTX/kg) than in the rest of the whelk tissues (below the limit of detection of 1.7 µg TTX/kg). This is the first study to report the detection of TTX in French molluscs.

When considering the geographical expansion of marine toxins, the emergence of new toxins and the associated risk for human health, there is urgent need for versatile and efficient analytical methods that are able to detect a range, as wide as possible, of known or emerging toxins. Current detection methods for marine toxins rely on a priori defined target lists of toxins and are generally inappropriate for the detection and identification of emerging compounds. The authors describe the implementation of a recent approach for the non-targeted analysis of marine toxins in shellfish with a focus on a comprehensive workflow for the acquisition and treatment of the data generated after liquid chromatography coupled with high resolution mass spectrometry (LC-HRMS) analysis. First, the study was carried out in targeted mode to assess the performance of the method for known toxins with an extended range of polarities, including lipophilic toxins (okadaic acid, dinophysistoxins, azaspiracids, pectenotoxins, yessotoxins, cyclic imines, brevetoxins) and domoic acid. The targeted method, assessed for 14 toxins, shows good performance both in mussel and oyster extracts. The non-target potential of the method was then challenged via suspects and without a priori screening by blind analyzing mussel and oyster samples spiked with marine toxins. The data processing was optimized and successfully identified the toxins that were spiked in the blind samples.

Chlordecone (CLD) is a Persistent Organic Pollutant used between 1972 until 1993 in the French West Indies (FWI). Due to its persistence and extensive application, a quarter of the total local agricultural acreage is still moderate to heavily polluted. In consequence, livestock may be contaminated at various levels. This is a major public health concern, particularly for local consumers. In order to better understand the fate of CLD in livestock organisms, in vivo studies are required. There is no information available about its metabolism and elimination in ruminants, common livestock in the FWI. To be able to monitor the fate of chlordecone and its metabolites in livestock and to assess if the compounds could be released in the environment, urinary and fecal samples were logically targeted. In order to reach this goal, robust and validated analytical methods are required. For this purpose, Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) extraction methods were validated to analyze CLD and its metabolites in the urine and feces. The analysis was carried using liquid phase chromatography with tandem mass spectrometry and validated according to French standard NF V03-110 and SANTE guidelines. Matrix effect, Accuracy, within-laboratory repeatability, specificity, Q/q relative ion intensities and uncertainty were reported. Recoveries between 70% and 120% were obtained from urine and feces. The limits of quantification (LOQ) in urine samples were 0.1 μg CLD L -1 , 0.1 μg total CLD (CLD and its conjugates)·L -1 , 1.3 μg CLDOH L -1 and 2.4 μg total CLD (chlordecol and its conjugates) L -1 of urine. LOQ in fresh feces were 3.2 μg CLD kg -1 and 5.8 μg CLDOH kg -1 . Contaminated urinary and fecal samples from ewes were analyzed to confirm the relevance of the methods. In urine, CLD and conjugated CLDOH could be quantified whereas only free CLD and free CLDOH were found in feces. These methods are essential for future toxicokinetic studies and also to estimate the environmental contamination., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A QuEChERS extraction method followed by HPLC-MS/MS analysis was developed to simultaneously analyze chlordecone and its metabolite chlordecol in animal livers. The overall method was validated with accuracy profiles according to the French Standard NF V03-110 and European Union guidelines. The validation was performed on bovine, ovine and porcine liver samples. Linearity, matrix effect, accuracy, within-laboratory repeatability, specificity, LOQ, Q/q relative ion intensities, and uncertainty were reported. Recoveries were between 70% and 120%. LOQs of 1.36 µg chlordecone kg -1 and 2.50 µg chlordecol kg -1 of fresh liver were found. Twelve contaminated livers of bovine, ovine and porcine origin from the French West Indies or samples from in vivo studies were analyzed. In these liver samples from contaminated animals, chlordecone was quantified at concentrations higher than the maximum residue limit and chlordecol in very low amounts in all the samples. In addition, these results confirm that chlordecone can be metabolized in ruminant species., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Car lubricant additives are added to mineral or synthetic base stocks to improve viscosity and resistance to oxidation of the lubricant and to limit wear of engines. In previous papers related to this purpose, it was demonstrated that SFC allows the elution of common low molecular weight additives. Since their total resolution could not be achieved owing to the limited peak capacity of packed columns, the hyphenation of selective and informative detectors, atomic emission and mass spectrometry, were also carried out for identification. This paper describes the final implementation of a packed column SFC/FID-UV-AED-FTIR-MS system to contribute to the characterisation of both the base stock, mineral or semi-synthetic, and the low molecular weight additives. SFC/FID-UV-FTIR ensures the easy confirmation of the presence of esters in the base stock. Reference additives are used to demonstrate the performances of the multi hyphenated system prior to its implementation for their identification in packages and in formulated lubricants. Identification and partial structure elucidation of additives and families of additives in package and formulated car lubricants are presented: using combined information obtained from AED traces and FTIR chemigrams, chemical families of additives can be deduced. Then, the mass spectra can be interpreted in the elution zone of interest in order to go further in the determination of the additive molecular structure. The hypernated SFC system was also employed to follow the ageing of car lubricants., (Copyright © 2012 Elsevier B.V. All rights reserved.)

A study of glyphosate and aminomethyl phosphonic acid (AMPA) transfer in the Orge watershed (France) was carried out during 2007 and 2008. Water samples were collected in surface water, wastewater sewer, storm sewer and wastewater treatment plant (WWTP). These two molecules appeared to be the most frequently detected ones in the rivers and usually exceeded the European quality standard concentrations of 0.1microg L(-1) for drinking water. The annual glyphosate estimated load was 1.9 kg year(-1) upstream (agricultural zone) and 179.5 kg year(-1) at the catchment outlet (urban zone). This result suggests that the contamination of this basin by glyphosate is essentially from urban origin (road and railway applications). Glyphosate reached surface water prevalently through storm sewer during rainfall event. Maximum concentrations were detected in storm sewer just after a rainfall event (75-90 microg L(-1)). High concentrations of glyphosate in surface water during rainfall events reflected urban runoff impact. AMPA was always detected in the sewerage system. This molecule reached surface water mainly via WWTP effluent and also through storm sewer. Variations in concentrations of AMPA during hydrological episodes were minor compared to glyphosate variations. Our study highlights that AMPA and glyphosate origins in urban area are different. During dry period, detergent degradation seemed to be the major AMPA source in wastewater.

Car lubricant additives are added to mineral or synthetic base stocks to improve viscosity and resistance to oxidation of the lubricant and to limit wear of engines. As they belong to various chemical classes and are added to a very complex medium, the base stock, their detailed chromatographic analysis is very difficult and time consuming. In a previous paper, it was demonstrated that supercritical fluid chromatography (SFC) allows the elution of common low-molecular-weight additives. Since their total resolution could not be achieved owing to the limited peak capacity of packed columns, the hyphenation of selective and informative detection methods such as atomic emission detection (AED) was required. Further to results obtained in SFC-AED, this work describes the hyphenation of SFC to atmospheric pressure chemical ionisation ion trap mass spectrometry (MS). SFC-MS hyphenation is detailed: temperature, flow rates of gas and mobile phase introduced in the source, position of the restrictor, ionisation additives and conditions of autotune are studied. Car lubricant monitoring requires negative and positive ionisation modes with or without the addition of ionisation auxiliary solvent according to the nature of additives. Moreover, when sensitivity is of major concern for a selected additive, the autotuning routine of the MS has to be performed in conditions as close as possible to analytical conditions, i.e. under subcritical conditions. Unambiguous identification and structure elucidation of several additives in formulated car lubricants are also presented.

Car lubricant additives are added to mineral or synthetic base stocks to improve viscosity and resistance to oxidation of the lubricant and to limit wear of engines. Their total amount in the commercial lubricant varies from a few percents to 20-25%. As they belong to various chemical classes and are added to a very complex medium, the base stock, their detailed chromatographic analysis is very difficult and time consuming as it should involve sample treatment and preparative scale separations in order to simplify the sample. The aim of this work is to determine the feasibility of the separation of low molecular weight lubricant additives using various packed columns with pure CO(2) as a mobile phase to enable implementation of flame ionisation detection as universal detector. This is part of a hypernated system including more sophisticated specific detectors, such as AED, FTIR or MS to obtain detailed structural information of compounds. This paper is devoted to the comparison of some stationary phases supposed to provide hydrocarbon group type separation (silica and normal phase) or separations on alkyl-bonded silica in non-aqueous mode of some selected classes of additives in test mixtures or in base stocks. Adsorption chromatography allows partial separation of additives from the base stocks while the direct elution of test additives can only be obtained on reversed phase supports having a very efficient silanol group protection so the interaction of the more polar compounds is much reduced. A two-dimensional scheme of analysis is also described. It combines adsorption chromatography to separate most of the polar additives from the base stock and alkyl-bonded silica for more detailed separation of the additives. However, overlapping between groups of compounds and the lack of resolution between some additives and the base stock should be addressed by the implementing of selective detectors.

A stationary phase derived from ristocetin was evaluated for chiral separation in subcritical fluid chromatography. Separation of various enantiomers having different structures and pK(a) values were investigated using carbon dioxide and polar modifiers. The influence of modifiers, additives, temperature, and mobile phase flow rate on separations is presented. It is concluded that this stationary phase can be used for SFC despite its structural similarity with protein-derived stationary phases that can only be used in HPLC. The separation mechanisms could not be elucidated or predicted using these initial experiments. The separations of warfarin and, especially, efavirenz demonstrate the potential of this type of stationary phase for rapid SFC chiral separations., (Copyright 2003 Wiley-Liss, Inc.)