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Synthesis and characterization of molecularly imprinted polymers for the selective extraction of oxazepam from complex environmental and biological samples
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - Fanny Varenne, Porkodi Kadhirvel, Pauline Bosman, Loïc Renault, Audrey Combès, Valérie Pichon
Anal. Bioanal. Chem - - doi: 10.1007/s00216-021-03268-w. - 2021
Oxazepam, one of the most frequently prescribed anxiolytic drugs, is not completely removed from wastewater with conventional treatment processes. It can thus be found at trace levels in environmental water, with human urine constituting the major source of contamination. This study focused on the development and characterization of molecularly imprinted polymers (MIPs) for the selective solid-phase extraction of oxazepam at trace levels from environmental water and human urine samples. Two MIPs were synthesized, and their selectivity in pure organic and aqueous media were assayed. After optimizing the extraction procedure adapted to a large sample volume to reach a high enrichment factor, the most promising MIP was applied to the selective extraction of oxazepam from environmental water. Extraction recoveries of 83 ± 12, 92 ± 4 and 89 ± 10% were obtained using the MIP for tap, mineral and river water, respectively, while a recovery close to 40% was obtained on the corresponding non-imprinted polymer (NIP). Thanks to the high enrichment factors, a limit of quantification (LOQ) of 4.5 ng L-1 was obtained for river water. A selective extraction procedure was also developed for urine samples and gave rise to extraction recoveries close to 95% for the MIP and only 23% for the NIP. Using the MIP, a LOQ of 357 ng L-1 was obtained for oxazepam in urine. The use of the MIP also helped to limit the matrix effects encountered for the quantification of oxazepam in environmental samples and in human urine samples after extraction on an Oasis HLB sorbent.

Identification and semi-relative quantification of intact glycoforms of human chorionic gonadotropin alpha and beta subunits by nano liquid chromatography-Orbitrap mass spectrometry
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - AmiraAl Matari, Anastasia Goumenou, Audrey Combèsa, Thierry Fournier, Valérie Pichon, Nathalie Delaunay
J. Chromatography A - 1640 461945 - doi.org/10.1016/j.chroma.2021.461945 - 2021
The human chorionic gonadotropin (hCG) protein belongs to a family of glycoprotein hormones called gonadotropins. It is a heterodimer made of two non-covalently linked subunits. The α-subunit structure, hCGα, has 2 N-glycosylation sites, while the beta subunit, hCGβ, has 2 N- and 4 O-glycosylation sites. This leads to numerous glycoforms. A method based on the analysis of hCG glycoforms at the intact level by nano-reversed phase liquid chromatography coupled to high resolution mass spectrometry (nanoLC-HRMS) with an Orbitrap analyzer was previously developed using a recombinant hCG-based drug, Ovitrelle®, as standard. It allowed the detection of about 30 hCGα glycoforms, but didn't allow the detection of hCGβ glycoforms. This method was thus here significantly modified (addition of a pre-concentration step of the sample to increase the sample volume from 70 nl to 1 µl, optimization of the gradient slope and the nature and content of the acidic additive in the mobile phase). It led to an improvement of the separation of hCGα and hCGβ glycoforms, which allowed for the first time the detection of 33 hCGβ glycoforms at intact level. In addition, a higher number of hCGα glycoforms (42 in total, i.e. a 40% increase) was detected. The figures of merit of this new method were next assessed. The relative standard deviations (RSDs) of the retention time ranged between 0.02 and 0.95% (n = 3), with an average value of 0.36% for the alpha glycoforms and between 0.01 and 1.08% (n = 3) with an average value of 0.23% for the beta glycoforms. The RSDs of the relative peak area measured on the extracted ion chromatogram of each glycoform were below 20% (n = 3), with an average value of 9.8%, thus allowing semi-relative quantification. Therefore, this method has a high potential for rapid quality control aiming for the detection and comparison of glycoforms present in glycoprotein-based pharmaceutical preparations.


Development of a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the analysis of tryptic digest of human hemoglobin exposed to sulfur mustard
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - Florine Hallez, Audrey Combès, Charlotte Desoubries, Anne Bossée, Valérie Pichon
J. Chromatography A - 1163 122518 - doi.org/10.1016/j.jchromb.2020.122518 - 2021
Sulfur mustard is a highly reactive chemical warfare agent that causes severe damages to the victims exposed by alkylating multiple biomolecules such as proteins. Resulting alkylated products can be used as biomarkers of exposure to this chemical agent. A liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) method was thus developed to detect alkylated peptides after the tryptic digestion of hemoglobin (50 mg.mL−1) incubated with sulfur mustard at different concentrations (0.25, 0.5, 1, 10 and 100 µg.mL−1). Five new alkylation sites were accurately identified on the protein (α-His72, α-His87, α-His89, β-His2 and β-Val98) and fifteen adducted peptides were detected, among which eight of them resulted from the alkylation of four peptides, each presenting two potential sites of adduction that could be discriminated by the method specificity. Similarly, it was possible to discriminate the three potential adduction sites of the peptide α-T9. Moreover, the method allowed the quantification of all the alkylated peptides with a satisfying repeatability, with RSD ranging from 0.5 to 9.3% for an exposure of hemoglobin to sulfur mustard at 100 µg.mL−1. The analysis of hemoglobin incubated with different concentrations of sulfur mustard levels led to a linear response for all the alkylated peptides with the studied concentrations (0.25, 0.5, 1, 10 and 100 µg.mL−1). A variation of the alkylation rate was also observed between the different peptides studied, with a preferential adduction of sulfur mustard on the histidine residues but also on the N-terminal valine residues of both globin chains and on the Val98 residue of globin β. Furthermore, the presented method proved to be sensitive, with a theoretical possibility to detect alkylated peptides resulting from in vitro incubation of hemoglobin in deionized water with sulfur mustard at 2.63 ng.mL−1. After further development, this method could potentially be used for the analysis of blood samples in vivo exposed to sulfur mustard.



COVID-19 and Dentistry in 72 Questions: An Overview of the Literature
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - Stéphane Derruau, Jérôme Bouchet, Ali Nassif, Alexandre Baudet, Kazutoyo Yasukawa, Sandrine Lorimier, Isabelle Prêcheur, Agnès Bloch-Zupan, Bernard Pellat, Hélène Chardin
J. Clin. Med. - 10 122518 - 4 - 2021
The outbreak of Coronavirus Disease 2019 (COVID-19), caused by Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2), has significantly affected the dental care sector. Dental professionals are at high risk of being infected, and therefore transmitting SARS-CoV-2, due to the nature of their profession, with close proximity to the patient’s oropharyngeal and nasal regions and the use of aerosol-generating procedures. The aim of this article is to provide an update on different issues regarding SARS-CoV-2 and COVID-19 that may be relevant for dentists. Members of the French National College of Oral Biology Lecturers (“Collège National des EnseignantS en Biologie Orale”; CNESBO-COVID19 Task Force) answered seventy-two questions related to various topics, including epidemiology, virology, immunology, diagnosis and testing, SARS-CoV-2 transmission and oral cavity, COVID-19 clinical presentation, current treatment options, vaccine strategies, as well as infection prevention and control in dental practice. The questions were selected based on their relevance for dental practitioners. Authors independently extracted and gathered scientific data related to COVID-19, SARS-CoV-2 and the specific topics using scientific databases. With this review, the dental practitioners will have a general overview of the COVID-19 pandemic and its impact on their practice. View Full-Text



Molecularly imprinted polymers in miniaturized extraction and separation devices
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - Thomas Bouvarel, Nathalie Delaunay, Valérie Pichon
First published - 44(8) 1727-1751 - doi.org/10.1002/jssc.202001223 - 2021
Molecularly imprinted polymers are highly selective and cost-effective materials, which have attracted significant interest in various areas such as sample pretreatment and chromatographic and electrophoretic separations. This review aims to present the state of the art concerning the miniaturization of these materials in order to meet the societal demand for reliable, fast, cheap, and solvent/sample saving analyses. The polymerization route specificities for the production of miniaturized molecularly imprinted polymers in capillaries or chip channels, such as open tubular, packed particles, magnetic nanoparticles, and in situ imprinted monoliths, are investigated. Their performances as selective supports in solid phase extraction and as stationary phases in electrochromatography and liquid chromatography, as well as their possible perspectives are discussed.




Using an Untargeted Metabolomics Approach to Identify Salivary Metabolites in Women with Breast Cancer
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - Daniele Xavier Assad ,Ana Carolina Acevedo, Elisa Cançado Porto Mascarenhas, Ana Gabriela Costa Normando,Valérie Pichon,Helene Chardin,Eliete Neves Silva Guerra and Audrey Combes
Metabolites - 10(12) 1727-1751 - doi.org/10.3390/metabo10120506 - 2020
Metabolic alterations are a hallmark of the malignant transformation in cancer cells, which is characterized by multiple changes in metabolic pathways that are linked to macromolecule synthesis. This study aimed to explore whether salivary metabolites could help discriminate between breast cancer patients and healthy controls. Saliva samples from 23 breast cancer patients and 35 healthy controls were subjected to untargeted metabolomics using liquid chromatography-quadrupole time-of-flight mass spectrometry and a bioinformatics tool (XCMS Online), which revealed 534 compounds, characterized by their retention time in reverse-phase liquid chromatography and by the m/z ratio detected, that were shared by the two groups. Using the METLIN database, 31 compounds that were upregulated in the breast cancer group (p < 0.05) were identified, including seven oligopeptides and six glycerophospholipids (PG14:2, PA32:1, PS28:0, PS40:6, PI31:1, and PI38:7). In addition, pre-treatment and post-treatment saliva samples were analyzed for 10 patients who experienced at least a partial response to their treatment. In these patients, three peptides and PG14:2 were upregulated before but not after treatment. The area under the curve, sensitivity, and specificity for PG14:2 was 0.7329, 65.22%, and 77.14%, respectively. These results provide new information regarding the salivary metabolite profiles of breast cancer patients, which may be useful biomarkers. View Full-Text




Synthesis and characterization of molecularly imprinted polymers for the selective extraction of oxazepam from complex environmental and biological samples
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - Daniele Xavier Assad Elisa Cançado Porto Mascarenhas Ana Gabriela Costa Normando Hélène Chardin Gustavo Barcelos Barra Riccardo Pratesi Yanna Karla De Medeiros Nóbrega Ana Carolina Acevedo Eliete Neves Silva Guerra
Molecular and Clinical Oncology - 155-161 - doi.org/10.3892/mco.2020.2062 - 2020
The early detection of breast cancer enables the use of less aggressive treatment and increases patient survival. The transmembrane glycoprotein mucin 1, which is also known as cancer antigen 15‑3 (CA15‑3), is aberrantly glycosylated and overexpressed in a variety of epithelial cancers, and serves a crucial role in the progression of the disease. CA15‑3 is currently used as a marker of breast cancer. In the present study, CA15‑3 concentrations in saliva and blood of patients with breast cancer were evaluated to test new assays to detect salivary CA15‑3 in addition to ELISA and its diagnostic value. To the best of our knowledge, there are no previous reports of the use of chemiluminescence assay (CLIA) and electrochemiluminescence assay (ECLIA) in saliva. Saliva and blood were collected on the same day from patients with breast cancer (n=26) and healthy controls (n=28). For each subject, the level of serum CA15‑3 was measured using ECLIA, and the level of salivary CA15‑3 was measured using ECLIA, CLIA and enzyme‑linked immunosorbent assay (ELISA). ELISA and CLIA were able to detect CA15‑3 in saliva; however, ECLIA could not detect salivary CA15‑3. There was no significant difference between the mean serum and salivary CA15‑3 levels in patients with breast cancer or healthy controls. The levels of CA15‑3 were highest for luminal breast cancer subtypes and stage IV cases. A moderate correlation was observed between salivary and serum CA15‑3 levels as measured by ELISA in breast cancer patients (r=0.56; P=0.0047). The results demonstrated that ECLIA was not a good method to detect salivary CA15‑3, although it is the gold standard for detecting serum CA15‑3. The presence of CA15‑3 in saliva was confirmed, and this will be useful in future research. Further investigations are necessary to confirm the ability to detect salivary CA15‑3 and its correlation with serum CA15‑3.
How high resolution mass spectrometry can help for the accurate quantification of difficult fragrance allergens
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - Pierre‐Alain Remy, C. Pérès, J. Dugay, E. Corbi, Nathalie David, J. Vial
Flavour and Fragrance Journal - 36(1) - DOI:10.1002/ffj.3639 - 2020
Two high‐resolution mass spectrometers (HRMS) with different analyzer technology, Orbitrap and hybrid quadrupole time‐of‐flight (QTOF), were compared with a low‐resolution mass spectrometer, quadrupole, to analyse a set of 35 difficult allergens. These difficult allergens are commonly coeluted fragrance allergens with matrix compounds, using standard gas chromatography‐mass spectrometer conditions, from the extended list of the Scientific Committee on Consumer Safety (SCCS). Although the fundamental role of chromatographic separation has been demonstrated many times, the aim of this work is to demonstrate the benefits of high‐resolution. The added value of high‐resolution was illustrated in both a qualitative and a quantitative way. For qualitative aspect, the high resolution extracted ion signals of these two detectors were compared with the low‐resolution extracted ion signals. About 50% of the coeluted cases observed with the low‐resolution detector are easily resolved by the two high‐resolution detectors. For the quantitative aspect, an accuracy profile methodology and a performance metric were used to propose an overall evaluation. The Orbitrap mass spectrometer demonstrated a better overall performance, while the QTOF presented similar or even lower quantification performances than the quadrupole on the set of analysed fragrance
Impact of the Oil Matrix on Anionic and Nonionic Surfactant Separation Using Ultra-High-Performance Liquid Chromatography Hyphenated to High-Resolution Mass Spectrometry
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - Alizée Dufour, Didier Thiébaut, Matthieu Loriau, Leticia Ligiero, and Jérôme Vial
American Chemical Society - 34(11) 13943–13953 - doi.org/10.1016/j.jchromb.2020.122518 - 2020
For the first time, to our knowledge, anionic and nonionic surfactants were analyzed in an oil matrix by ultra-high-performance liquid chromatography hyphenated to high-resolution mass spectrometry (UHPLC-HRMS). The feasibility of this analysis was studied using synthetic mixtures of surfactants prepared in water (quality controls), binary THF/toluene 50/50 v/v (surfactant + THF/toluene), and binary THF/toluene containing 1 and 10% crude oil (Crude1% and Crude10%). These compositions were chosen in order to be as close as possible to petroleum related samples to be investigated in the future. Analyses were carried out by UHPLC methods using both reverse phase and anion-exchange mechanisms with a mixed mode column. Despite the complexity of the oil matrix and the presence of organic solvents used for dilution, the retention times of the surfactants were not affected whatever the concentration of crude oil present in the sample. Nevertheless, a significant matrix effect caused a loss of signal when the concentration of oil reached 10% in mass. For the analysis of samples with this crude oil concentration range, it would be advisable to dilute the sample.




Two-step local functionalization of fluoropolymer Dyneon THV microfluidic materials by scanning electrochemical microscopy combined to click reaction
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - Kadhirvel P, Combès A, Bordron L, Pichon V
Anal. Bioanal. Chem - 411(8) 1525-1536 - doi: 10.1007/s00216-019-01586-8 - 2019
A molecularly imprinted polymer (MIP) was designed in order to allow the selective solid-phase extraction of carbamazepine (CBZ), an anticonvulsant and mood-stabilizing drug, at ultra-trace level from aqueous environmental samples. A structural analog of CBZ was selected as a dummy template and different synthesis conditions were screened. The selectivity of the resulting imprinted polymers was evaluated by studying the retention of CBZ in a solvent similar to the one used for the synthesis. The presence of imprinted cavities in the polymers was then demonstrated by comparing the elution profiles (obtained by using MIP and a non-imprinted polymer, NIP, as a control) of the template, of CBZ, and of a structural analog of CBZ. Then, the extraction procedure was further optimized for the treatment of aqueous samples on the two most promising MIPs, with special attention being paid to the volume and composition of the percolation and washing solutions. The best MIP provided a highly selective retention in tap water with 81% extraction recovery for CBZ in the elution fraction of the MIP and only 14% for NIP. The repeatability of the extraction procedure was demonstrated for both tap and river waters (RSD below 4% in river water) for the drugs CBZ, oxcarbamazepine, and one metabolite (carbamazepine 10,11-epoxide). A MIP capacity of 1.15 μmol g-1 was determined. Finally, an analytical procedure involving the MIP was developed allowing the detection of CBZ at a concentration level of only a few nanograms per liter in river water. The selectivity provided by the MIP resulted in a 3000-fold increase of the signal-to-noise ratio in LC/MS analysis as compared to the use of conventional sorbent. Graphical abstract.
First profiling in hydrophilic interaction liquid chromatography of intact human chorionic gonadotropin isoforms.
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - Camperi J, Pichon V, Fournier T, Delaunay N
J Pharm Biomed Anal - 10;174 495-499. - doi: 10.1016/j.jpba.2019.06.014 - 2019
The study of glycoproteins is a rapidly growing field, which is not surprising considering that approximately 70% of human proteins are glycosylated and that numerous biological functions are associated to the glycosylation. In this work, our interest focused on the heterodimeric human Chorionic Gonadotropin (hCG) glycoprotein that is the specific hormone of the human pregnancy, consisting of an α and a β subunit, so-called hCGα and hCGβ, respectively. This protein possesses a very high structural heterogeneity, essentially due to the presence of 8 glycosylation sites, but also other types of post-translational modifications. In this study, for the first time, the potential of hydrophilic interaction liquid chromatography (HILIC) was investigated to separate the intact hCG isoforms. Three different HILIC stationary phases were tested using an hCG-based drug as standard, a recombinant hCG. For each stationary phase, the effect of the initial mobile phase composition based on ACN/H2O mixture, the slope of the gradient, the content and nature of the acidic additive (formic acid and trifluoroacetic acid (TFA)), and the addition of a volatile salt (ammonium formate) on the retention and the resolution were studied. The best HILIC separation was obtained with the amide column and a mobile phase composed of water/ACN containing 0.1% of TFA. The repeatability in terms of retention times and peak areas was then assessed. Finally, the method was applied to the analysis of a second hCG-based drug obtained from urine of pregnant women. Both drugs gave chromatograms with more than 10 peaks. However, they were significantly different, which demonstrated the potential of HILIC method for hCG isoform fingerprinting
Specificity of the metabolic signatures of fish from cyanobacteria rich lakes
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - Benoît Sotton, Alain Paris, Séverine Le Manach, Alain Blond, Charlotte Duval, Qin Qiao, Arnaud Catherine, Audrey Combes, Valérie Pichon, Cécile Bernard, Benjamin Marie
Chemosphere - - DOI: 10.1016/j.chemosphere.2019.03.115 - 2019
With the increasing impact of the global warming, occurrences of cyanobacterial blooms in aquatic ecosystems are becoming a main worldwide ecological concern. Due to their capacity to produce potential toxic metabolites, interactions between the cyanobacteria, their cyanotoxins and the surrounding freshwater organisms have been investigated during the last past years. Non-targeted metabolomic analyses have the powerful capacity to study simultaneously a high number of metabolites and thus to investigate in depth the molecular signatures between various organisms encountering different environmental scenario, and potentially facing cyanobacterial blooms.

In this way, the liver metabolomes of two fish species (Perca fluviatilis and Lepomis gibbosus) colonizing various peri-urban lakes of the Île-de-France region displaying high biomass of cyanobacteria, or not, were investigated. The fish metabolome hydrophilic fraction was analyzed by 1H NMR analysis coupled with Batman peak treatment for the quantification and the annotation attempt of the metabolites. The results suggest that similar metabolome profiles occur in both fish species, for individuals collected from cyanobacterial blooming lakes compared to organism from non-cyanobacterial dominant environments. Overall, such environmental metabolomic pilot study provides new research perspectives in ecology and ecotoxicology fields, and may notably provide new information concerning the cyanobacteria/fish ecotoxicological interactions.
First characterizations by capillary electrophoresis of human Chorionic Gonadotropin at the intact level
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - Benoît Sotton, Alain Paris, Séverine Le Manach, Alain Blond, Charlotte Duval, Qin Qiao, Arnaud Catherine, Audrey Combes, Valérie Pichon, Cécile Bernard, Benjamin Marie
Talanta - 193 77-86 - doi: 10.1016/j.talanta.2018.09.095 - 2019
In the present work, the first characterizations by Capillary Electrophoresis of the human Chorionic Gonadotropin (hCG) hormone at the intact level were carried out. hCG is a hetero-dimeric glycoprotein, specific to the human pregnancy, consisting of an α and a β subunit, so-called hCGα and hCGβ, respectively. hCG has 8 potential glycosylation sites leading to a high number of isoforms (including glycoforms and other post-translational modifications) that we are interesting to characterize. First, Capillary Gel Electrophoresis (CGE) was used to separate the isoforms of two hCG-based drugs: Ovitrelle® (recombinant r-hCG) and Pregnyl (hCG isolated from the urine of pregnant women, u-hCG). As expected, CGE led to a better resolution than SDS-PAGE and confirmed the large heterogeneity of hCG. Different CGE profiles were obtained for the two hCG-based drugs, varying in number of peaks, migration times, and peak intensities, thus demonstrating that the drugs contain isoforms, different in nature and proportion. This result was confirmed by Capillary IsoElectrophoretic Focusing (CIEF). The pI ranges of the hCG isoforms were found between 3.4 and 4.7, and 4.5 and 5.2 for r-hCG and u-hCG, respectively. This information was further used to develop the separation of the hCG isoforms by Capillary Zone Electrophoresis (CZE). The pH, the nature, and the concentration of the background electrolyte as well as the nature and the content of its organic modifier were optimized. The use of a coated capillary to avoid protein adsorption was also evaluated. The final CZE-UV method allowed distinguishing at least 6 peaks, corresponding to different hCG isoforms. To significantly improve the level of information obtained, the CZE instrument was then coupled by means of an electrospray ionization source to a triple quadrupole (TQ) mass spectrometer. Two detection strategies were used, one focusing on the lower m/z values (100-1000) in order to identify some sugar residues as diagnostic ions to confirm the presence of glycan chains, and the second focusing on the higher m/z values (1000-2000), corresponding to the multiple charged intact protein isoforms. For both approaches, the fragmentor and capillary voltage values were optimized. The composition and the flow-rate of the sheath liquid were then optimized for the strategy focusing on the higher m/z values in order to both increase the charge state of the ionized intact isoforms and the signal-to-noise ratio. The final method was used to compare the two hCG-based drugs, demonstrating the potential of the developed CZE-MS method for isoforms fingerprinting.
Development and application of water-compatible molecularly imprinted polymers for the selective extraction of carbamazepine from environmental waters
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - Porkodi Kadhirvel, Audrey Combès, Louis Bordron, Valérie Pichon
Anal. Bioanal. Chem - 11(8) 1525-1536 - doi: 10.1007/s00216-019-01586-8 - 2019
A molecularly imprinted polymer (MIP) was designed in order to allow the selective solid-phase extraction of carbamazepine (CBZ), an anticonvulsant and mood-stabilizing drug, at ultra-trace level from aqueous environmental samples. A structural analog of CBZ was selected as a dummy template and different synthesis conditions were screened. The selectivity of the resulting imprinted polymers was evaluated by studying the retention of CBZ in a solvent similar to the one used for the synthesis. The presence of imprinted cavities in the polymers was then demonstrated by comparing the elution profiles (obtained by using MIP and a non-imprinted polymer, NIP, as a control) of the template, of CBZ, and of a structural analog of CBZ. Then, the extraction procedure was further optimized for the treatment of aqueous samples on the two most promising MIPs, with special attention being paid to the volume and composition of the percolation and washing solutions. The best MIP provided a highly selective retention in tap water with 81% extraction recovery for CBZ in the elution fraction of the MIP and only 14% for NIP. The repeatability of the extraction procedure was demonstrated for both tap and river waters (RSD below 4% in river water) for the drugs CBZ, oxcarbamazepine, and one metabolite (carbamazepine 10,11-epoxide). A MIP capacity of 1.15 μmol g-1 was determined. Finally, an analytical procedure involving the MIP was developed allowing the detection of CBZ at a concentration level of only a few nanograms per liter in river water. The selectivity provided by the MIP resulted in a 3000-fold increase of the signal-to-noise ratio in LC/MS analysis as compared to the use of conventional sorbent. Graphical abstract.
Nano- and microplastic analysis: Focus on their occurrence in freshwater ecosystems and remediation technologies
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - Yolanda Pico, Ahmed Alfarhan and Damia Barcelo
ELSEVIER - 113 409-425 - doi: 10.1016/j.trac.2019.02.016 - 2019
Plastic pollution is a global problem since 2016 when its production reached 322 million tonnes, excluding fibers. Daily discharges of microplastics (MPs, defined as <5 mm in size) are estimated in the range of 50,000 up to 15 million particles, whereas no information on nanoplastic (NP, <100 nm) release is available yet. Different processes further degraded these materials producing more MPs and NPs. This review attempts to fill the void of information on the state-of-art analysis of MPs and NPs (recently identified as emerging contaminants) and provides a critical overview on modern instrumentation, newly developed workflows, and promising techniques for their characterization (Raman and FT-IR spectroscopies and microscopies, pyrolysis and thermal desorption gas chromatography, imaging techniques, etc.). Available analytical methods, validation as well as applications with cells have been taken into account. MP and NP sampling, identification, and characterization are discussed. Finally, recent applications to establish their occurrence in freshwater ecosystems and the effectiveness of the proposed remediation technologies are considered.
Monitoring of the blend monoethanolamine/methyldiethanolamine/water for post-combustion CO2 capture
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - Lorena Cuccia, José Dugay, Bontemps Domitille, Myriam Louis-Louisy
International Journal of Greenhouse Gas Control - 80 43-53 - DOI: 10.1016/j.ijggc.2018.11.004 - 2019
The blend MEA/MDEA (5/25%wt.) was studied on the LEMEDES-CO2 lab-scale pilot plant, with representative conditions of post-combustion CO2 capture for power generation during 900 h. CO2 loadings were determined and showed average values of 0.12 and 0.40 respectively for the lean and rich solvents. Stability of the two amines, namely MEA and MDEA, was monitored using ionic chromatography; results did not show any significant degradation of MDEA during the campaign, in contrary to MEA which showed a significant degradation in the range of 0.03 points per day. Analytical methods involving GC–MS and IC were developed in order to identify potential degradation products in the liquid phase of the solvent. Study of the gaseous emissions’ composition was also realized using sampling on different solid sorbents followed by thermal desorption and GC–MS analysis. A total of 22 compounds were listed including amines, organic acids, and pyrazines derivatives. 12 degradation products were found in the solvent itself and 11 in the treated flue gas among which MDEA, the constituent amine of the blend. A quantitative monitoring was carried out for formic and oxalic acids. Results showed concentrations reaching 500 mg/L for oxalic acid and 1400 mg/L for formic acid.
Synthesis and Characterization of Molecularly Imprinted Polymers for the Selective Extraction of Carbamazepine and Analogs from Human Urine Samples
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - 287–295
Chromatographia - 82 287–295 - doi:10.1007/s10337-018-3680-4 - 2019
Two molecularly imprinted polymers (MIPs) were synthesized according to a previous work from our group dealing with the extraction of carbamazepine from environmental water. The potential of these MIPs, which differ in the nature of the monomer used for their synthesis, to selectively extract the drugs carbamazepine and oxcarbazepine and the metabolite 10,11-epoxycarbamazepine was first studied in spiked pure water, and high selectivity was obtained with both MIPs for the three target molecules in this pure medium. This selectivity was maintained when applying one of the MIPs to urine samples. Indeed, extraction recoveries were higher than 82% on the MIP and lower than 20% on the corresponding non-imprinted polymer used as a control. The repeatability of the extraction procedure applied to urine was also demonstrated, with relative standard deviation (RSD) below 20% for extraction recoveries of the three targets at a spiking level of 20 ng L−1. Limits of quantification between 1 and 7 ng L−1 were determined for urine samples using the MIP as extraction sorbent combined with LC–MS analysis. The potential of the MIP was compared to that of the Oasis HLB sorbent. This study shows that the MIP constitutes a powerful tool for avoiding matrix effects encountered in the quantification of the target molecules in urine samples extracted on Oasis HLB.
Online coupling of immunoextraction, digestion, and microliquid chromatography-tandem mass spectrometry for the analysis of sarin and soman-butyrylcholinesterase adducts in human plasma
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - Maud Bonichon, Valentina Valbi, Audrey Combès, Charlotte Desoubries, Anne Bossée & Valérie Pichon
- 410 pages1039–1051 - doi.org/10.1007/s00216-017-0640-z - 2018
Organophosphorus nerve agent (OPNA) adducts formed with human butyrylcholinesterase (HuBuChE) can be used as biomarker of OPNA exposure. Indeed, intoxication by OPNAs can be confirmed by the LC/MS2 analysis of a specific HuBuChE nonapeptide on which OPNAs covalently bind. A fast, selective, and highly sensitive online method was developed to detect sarin and soman adducts in plasma, including immunoextraction by anti-HuBuChE antibodies, pepsin digestion on immobilized enzyme reactors (IMER), and microLC/MS2 analysis of the OPNA adducts. The potential of three different monoclonal antibodies, covalently grafted on sepharose, was compared for the extraction of HuBuChE. The online method developed with the most promising antibodies allowed the extraction of up to 100% of HuBuChE contained in plasma and the digestion of 45% of it in less than 40 min. Moreover, OPNA-HuBuChE adducts, aged OPNA adducts, and unadducted HuBuChE could be detected (with S/N > 2000), even in plasma spiked with a low concentration of OPNA (10 ng mL−1). Finally, the potential of this method was compared to approaches involving other affinity sorbents, already described for HuBuChE extraction.
Human odor and forensics: Towards Bayesian suspect identification using GC × GC–MS characterization of hand odor
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - lVincent Cuzuel Roman Leconte Guillaume Cognon Didier Thiébaut Jérôme Vial Charles Sauleau Isabelle Rivals
Journal of Chromatography B - 1092 379-385 - https://doi.org/10.1016/j.jchromb.2018.06.018 - 2018
A new method for identifying people by their odor is proposed. In this approach, subjects are characterized by a GC × GC–MS chromatogram of a sample of their hand odor. The method is based on the definition of a distance between odor chromatograms and the application of Bayesian hypothesis testing. Using a calibration panel of subjects for whom several odor chromatograms are available, the densities of the distance between chromatograms of the same person, and between chromatograms of different persons are estimated. Given the distance between a reference and a query chromatogram, the Bayesian framework provides an estimate of the probability that the corresponding two odor samples come from the same person. We tested the method on a panel that is fully independent from the calibration panel, with promising results for forensic applications.
Active modulation in neat carbon dioxide packed column comprehensive two-dimensional supercritical fluid chromatography
Laboratoire Sciences Analytiques Bioanalytiques et Miniaturisation - Orjen Petkovic Pierre Guibal Patrick Sassiat Jérôme Vial Didier Thiébaut
ELSEVIER - 1536 176-184 - https://doi.org/10.1016/j.chroma.2017.08.063 - 2018
After demonstrating in a first paper the feasibility of SFCxSFC without decompression of the mobile phase, a modified interface has been developed in order to perform active modulation between the two SFC dimensions. In this paper, it is shown that the new interface enabled independent control of modulation parameters in SFCxSFC and performed a band compression effect of solutes between the two SFC dimensions. The effectiveness of this new modulation process was studied using a Design of Experiments. The SFCxSFC prototype was applied to the analysis of a real oil sample to demonstrate the benefits of the active modulator; in comparison to our previous results obtained without active modulation, better separation was obtained with the new interface owing to the peak compression occurring in the modulator.

33 publications.