Oxazepam, one of the most frequently prescribed anxiolytic drugs, is not completely removed from waste waters with conventional treatment processes. It can thus also be found in environmental waters at trace levels, human urine constituting the major source of contamination. This study focussed then on the development and characterisation of molecularly imprinted polymers (MIPs) for the selective solidphase extraction of oxazepam at the trace levels from environmental water and human urine samples . Two MIPs were thus synthesized and their selectivity in pure organic and aqueous medium 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 waters. 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 obtained, the LOQ was of 4.5 ng L -1 for river water. A selective extraction procedure was also developed for urine sample and gave rise to extraction recoveries close to 95% on MIP and of only 23% on NIP, which. Using the MIP, a LOQ of 357 ng L -1 for oxazepam in urine was obtained. The use of the MIP also allowed to limit matrix effects encountered for the quantification of the oxazepam in environmental samples and in human urine samples after extraction on Oasis HLB sorbent.
The widespread use of chlordecone (CLD), an organochlorine pesticide, until the 1990s to protect banana crops in the French West Indies led to significant pollution of water and soil and, subsequently, of bovine intended for human consumption. Carcasses are submitted to official controls based on perirenal fat CLD determination. In order to allow for pre-slaughter controls, a selective analytical method based on a molecularly imprinted polymer (MIP) associated to the LC/MS-MS method was developed to determine the level of CLD in bovine serum that can be collected before slaughter. Different synthesis conditions were therefore assayed by varying the nature of the monomer and of the porogen, and the most promising MIP in terms of selective retention for CLD (extraction recovery close to 100%) was completely characterized by solid-phase extraction (repeatability of the extraction procedure, of the synthesis, and of the cartridge filling) in pure medium. The capacity of the MIP was determined at 0.13 µmol g−1 of MIP. After application of a spiked bovine serum sample on the MIP, the selective retention was maintained (87 and 21%, respectively, on the MIP and on the corresponding non-imprinted polymer). Moreover, extraction on the MIP led to a cleaner extract compared to those issued from a conventional C18 sorbent.
Despite the growing interest in salivary metabolomics, few studies have investigated the impact of aging on the salivary metabolome. The alterations in metabolic pathways that occur with aging are likely to be observed in pathologies affecting older people and may interfere with the search for salivary biomarkers. It is therefore important to investigate the age-related changes occurring in the salivary metabolome. Using reversed phase liquid chromatography and hydrophilic interaction chromatography coupled to mass spectrometry used in positive and negative ionization modes, the salivary metabolic profiles of young (22 to 45 years old) and older people (55 to 92 years old) were obtained. Those profiles were compared with the use of XCMS online to highlight the under or overexpression of some metabolites with aging. A total of 60 metabolites showed differential expression with age. The identification of 26 of them was proposed by the METLIN database and, among them, 17 were validated by standard injections. Aging seemed to affect most of the main metabolic pathways (amino acid metabolism, Krebs cycle, fatty acid synthesis, and nucleic acid synthesis). Moreover, most of the metabolites that were over- or under-expressed with age in this study have already been identified as being potential biomarkers of diseases affecting older people, such as in Alzheimer’s disease. Special attention should be paid in the search for biomarkers of pathologies affecting the elderly to differentiate age-related changes from disease-related changes.
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