Per- and polyfluoroalkyl substances (PFAS) presence in food: Comparison among fresh, frozen and ready-to-eat vegetables

There is a worldwide discussion to provide safety limits in food for per-and polyfluoroalkyl substances (PFAS), a group of persistent contaminants associated to human disease. Processed food is more at risk of containing increased amounts of PFAS as a consequence of intentionally or non-intentionally contamination during manipulation and packaging. Among food products, also vegetables can be submitted to industrial manipulation; therefore, a different PFAS content correlated to the level of vegetables processing is conceivable. This study assessed the amount and type of PFAS present in fresh, frozen and ready-to-eat vegetables. Differences have been observed between the three groups of samples in the average PFAS content; the difference between ready-to eat and frozen vegetables resulted statistically significative. Organic vegetables displayed a lower total amount of PFAS respect to the traditional counterpart. The impact of industrial manipulation remains to be cleared, but pesticides use during cultivation could be considered a source of PFAS contamination

Opiates

Opiates are both therapeutical and illicit drugs used by the population. Notwithstanding the introduction of new psychoactive substances (NPS), in particular of new derivatives of fentanyl, opiates and heroin in particular, represents one of the most diffused illicit drug and still accounts for most of the seizures worldwide. The article presents an overview on opiates classification and their analgesic activity and pharmacology. Their potential of abuse in relation to general population and in case of tampering activities is described. Opiates are also strictly monitored in the workplace drug testing programs worldwide for the risks of accidents correlated to their use and dependence. Analytical methods for opiates detection in biological fluids are also discussed

Application of HRAM screening and LC–MS/MS confirmation of active pharmaceutical ingredient in “natural” herbal supplements

The growing market of herbal remedies worldwide could pose severe problems to consumers’ health due to the possible presence of potentially harmful, undeclared synthetic substances or analogues of prescription drugs. The present work shows a simple but effective approach to unequivocally identify synthetic anorectic compounds in allegedly ‘natural’ herbal extracts, by exploiting liquid chromatography/time of flight (Q-TOF LC/MS) technology coupled to liquid chromatography/triple quadrupole (LC–MS/MS) confirmation and quantitation. The procedure was applied to five tea herbal extracts and pills sold as coadjutant for weigh loss. The method exploited liquid–liquid sample extraction (LLE) and separation in a C18 (2.1 mm × 150 mm, 1.8 μm) column. QTOF acquisitions were carried out both in scan mode and all ion MS/MS mode and results were obtained after search against ad hoc prepared library. Sibutramine, 4-hydroxyamphetamine, caffeine and theophylline were preliminary identified samples. Confirmation and quantitation of the preliminary identified compounds were obtained in LC–MS/MS after preparation of appropriated standards. Sibutramine, caffeine and theophylline were finally confirmed and quantitate

Application of HRAM screening and LC–MS/MS confirmation of active pharmaceutical ingredient in “natural” herbal supplements

The growing market of herbal remedies worldwide could pose severe problems to consumers’ health due to the possible presence of potentially harmful, undeclared synthetic substances or analogues of prescription drugs. The present work shows a simple but effective approach to unequivocally identify synthetic anorectic compounds in allegedly ‘natural’ herbal extracts, by exploiting liquid chromatography/time of flight (Q-TOF LC/MS) technology coupled to liquid chromatography/triple quadrupole (LC–MS/MS) confirmation and quantitation. The procedure was applied to five tea herbal extracts and pills sold as coadjutant for weigh loss. The method exploited liquid–liquid sample extraction (LLE) and separation in a C18 (2.1 mm × 150 mm, 1.8 μm) column. QTOF acquisitions were carried out both in scan mode and all ion MS/MS mode and results were obtained after search against ad hoc prepared library. Sibutramine, 4-hydroxyamphetamine, caffeine and theophylline were preliminary identified samples. Confirmation and quantitation of the preliminary identified compounds were obtained in LC–MS/MS after preparation of appropriated standards. Sibutramine, caffeine and theophylline were finally confirmed and quantitate

Fully automated analysis of Carbohydrate-Deficient Transferrin (CDT) by using a multicapillary electrophoresis system

Background: The techniques universally believed as most reliable for determination of Carbohydrate-Deficient Transferrin (CDT) are HPLC andcapillary electrophoresis (CE). Recently a reagent kit for CDT analysis to be used in a multicapillary electropherograph has been introduced. Thepresent work was aimed at a validation of this new commercial system by application of the analytical chemistry parameters and by comparisonwith validated CE and HPLC methods.Methods: One hundred forty serum samples were analyzed with multicapillary CE (Capillarys\u2122, Sebia, France) using kit reagents(CAPILLARYS\u2122 CDT assay), with single capillary electropherograph (P/ACE MDQ, Beckman Coulter, USA) using an original methoddeveloped by our group and with HPLC, performed on a gradient HPLC (Shimadzu Europe, Germany), using column and reagents provided in kit(ClinRep\uae, Recipe, Germany).Results: The separation efficiency of the multicapillary system was about 15,000 theoretical plates/column. The resolution of the transferrinisoforms ranged from 1.23 to 1.67. The variation coefficient was b10% in both intra-run and between run tests. The correlation of results ofmulticapillary CE with those obtained with single CE and HPLC was statistically significant.Conclusions: The multicapillary system shows high productivity with good analytical performances; however, a confirmation of positive resultswith an alternative method is required

Valproic acid determination by liquid chromatography coupled to mass spectrometry (LC-MS/MS) in whole blood for forensic purposes

Valproic acid (VPA) is a well-known drug prescribed as anti-epileptic. It has a narrow therapeutic range and shows great individual differences in pharmacodynamics and pharmacokinetics. Consequently, the therapeutical drug monitoring (TDM) in patient's plasma is of crucial importance. Liquid chromatography coupled to mass spectrometry (LC-MS/MS) has gained importance in TDM applications for its features of sensitivity, selectivity and rapidity. However, in case of VPA, the LC-MS/MS selectivity could be hampered by the lack of a sufficient number of MRM transitions describing the molecule. In fact, the product ion scan of deprotonated molecules of VPA does not produce any ion and thus most LC-MS/MS methods are based on the detection of the unique MRM transition m/z 143➔143. In this way, the advantages of selectivity in LC-MS cannot be effectively exploited. In the present method stable analyte adducts were exploited for the determination of VPA in blood. An Acquity HSS C18 column and mobile phases consisting of 5 mM ammonium formate and acetonitrile both added 0.1% formic acid were used. Source worked in negative acquisition mode and parameters were optimized to increase the adduct (m/z 189) and dimer (m/z 287) stability and their fragmentation were used to increase the selectivity of MRM detection. The method has been validated according to the toxicological forensic guidelines and successfully applied to 10 real blood samples. Finally, the present method showed suitable for the rapid LC-MS/MS detection of VPA in whole blood, demonstrating the possibility to increase specificity by exploiting stable in-source adducts. This should be considered of utmost importance in the case of forensic applications

Novel zwitterionic HILIC stationary phase for the determination of ethyl glucuronide in human hair by LC-MS/MS

Some recent studies have described a shift from traditional reversed-phase to more hydrophilic LC chemistry for EtG determination in hair (hEtG). The reason relies on the poor retention of C8\u2013 and C18-based columns for polar compounds, even in presence of great amount of aqueous phase. This work presents the development, validation and application of a new hydrophilic interaction liquid chromatography-tandem mass spectrometry (HILIC-LC-MS/MS) method based on a novel zwitterionic stationary phase for the analysis of hEtG. The linearity was assessed in the range of 5\u2013100 pg/mg hair, with a correlation coefficient of >0.99. The method was selective and sensitive, with a limit of detection (LOD) and limit of quantitation (LOQ) of 1.4 pg/mg and 4.5 pg/mg in hair, respectively. Suitable diagnostic sensitivity was achieved without the introduction of a sample purification step, or a post column solvent addition. The method was successfully applied to real hair samples after full validation. This method, based on a separation at neutral conditions, confirmed the optimum retention and thus selectivity for weak acids in zwitterionic HILIC columns

Study of vitreous potassium correlation with time since death in the post-mortem range from 2 to 110 hours using capillary ion analysis

The time-dependent postmortem increase of potassium concentration in the eye fluids has been studied since the 1960s. However, important discrepancies on the reproducibility of the phenomenon have hampered the use of this parameter in real cases. In recent years, a new analytical approach based on capillary ion analysis (CIA) has been reported. In the present work, the correlation between vitreous potassium and postmortem interval (PMI) has been re-evaluated by using CIA in a group of 164 cases with PMIs ranging from 2 to 110 hours. The correlation of the two parameters was described by the following regression equation: y = 0.1733x + 2.3008 (x = PMI; y = K+ concentration); correlation coefficient = 0.962. The re-calculation of PMIs on the basis of this equation provided calculated PMIs with an average error of 5.54 hours (SD = 4.16). However, the percent PMI calculation error decreased with the increase of PMI, becoming acceptable for practical application above 24 hours since death