Detection, identification and determination of chiral pharmaceutical residues in wastewater: Problems and challenges

Chiral pharmaceuticals (CPs) are widely used in different areas of human life, thus they are frequentlydetected in different ecosystems. However, before CPs reach the environment, wastewater is subjected todifferent treatment processes in order to remove them. Nevertheless, such processes may affect thechirality of CPs, thus it is very important to monitor CP levels during the wastewater treatment.This review addresses the present state of knowledge concerning the input, occurrence, fate and ef-fects of CPs in the environment. It focuses primarily on wastewater analysis, problems and challengesconnected with trace levels of CP enantiomers and highly complex matrices of samples. Analytical ap-proaches used in detection, identification and determination of enantiomers are presented. The appli-cation of the results of wastewater analysis to obtain information on the population's health andbehaviour has been included and discussed. Moreover, the prospects of the future trends in greenenantiomeric analysis are described.

Determination of bromhexine and its metabolites in equine serum samples by liquid chromatography – Tandem mass spectrometry: Applicability to the elimination study after single oral dose

Bromhexine (BH), expectorant used in the treatment of respiratory disorders associated with viscid or excessive mucus, is not permitted for use in the competing horse by many authorities in horseracing and Olympic disciplines. Metabolic studies are of the great importance in anti-doping field because they allow for updating the selection of the most appropriate markers for prohibited substances, such as metabolites present at higher concentration levels and/or lasted for a longer period of time in biological samples than a parent drug. This study describes LC-MS/MS-based method for simultaneous determination of BH and its metabolites, including 4-(2-amino-3,5-dibromobenzylamino)cyclohexanol (4-HDMB), 3-(2-amino-3,5-dibromobenzylamino)cyclohexanol (3-HDMB), in equine serum samples. The 2-(2-amino-3,5-dibromobenzylamino)cyclohexanol (2-HDMB) was monitored as well. The assay was validated in terms of linearity (R2 greater than 0.9951), intra- and inter-assay accuracy (91.6 – 109.1%) and precision (CV < 9.6%) as well as recovery (94.8 – 105.65%). The LODs were 0.0052, 0.0053, 0.0056 and 0.0043 ng/mL for BH, 2-HDMB, 3-HDMB and 4-HDMB, respectively. The developed method was applied to determine the time curses of BH and its metabolites concentrations in equine serum collected for 95.25 h following a single oral administration of BH to two healthy mares (in dose of 0.8 mg/kg). The parent drug was found at higher concentration levels than 3-HDMB (major metabolite) and 4-HDMB (minor metabolite), however, both BH metabolites lasted for a longer period of time in equine serum than the parent drug. Thus, both metabolites of BH can be considered as BH abuse markers.

Development and validation of a GC–MS/MS method for the determination of 11 amphetamines and 34 synthetic cathinones in whole blood

M. Woźniak , L. Banaszkiewicz , M. Wiergowski, E. Tomczak, M. Kata, B. Szpiech, J. Namieśnik , M. Biziuk Forensic Toxicology – 2020
Purpose Psychoactive compounds that contain a phenylethylamine structure (such as amphetamine-type stimulants and synthetic cathinones) are one of the major classes of stimulants on the recreational drug market. Approximately 670 new psychoactive substances (NPS) are monitored only in Europe; however, new psychoactive compounds are being developed for illicit trade each year. In this context, the development of new analytical procedures for the determination of such compounds in biological specimens for forensic toxicology is of great importance. Methods Gas chromatography–tandem mass spectrometry (GC–MS/MS) technique was applied for analysis of amphetamines and synthetic cathinones. The volumes of 200 µL of each whole blood sample and 1 mL of liquid-liquid extraction solvent were used for extraction, followed by pentafuoropropionyl derivatization. Results A high-throughput, robust, rapid, and sensitive procedure involving a simple liquid-liquid extraction for the simultaneous determination of 45 amphetamine-type stimulants and synthetic cathinones in whole blood was developed. The assay was validated based on its recovery (83.2–106%), interday accuracy (89.0–108%), and interday precision (≤8.1%). In view of the low limits of detection (ranged between 0.02 and 0.72 ng/mL) and limits of quantifcation (1 and 2.5 ng/mL), the developed method can serve as a less expensive and more ecologically friendly alternative to the liquid chromatography–tandem mass spectrometric methods. Conclusions To the best of our knowledge, this is the frst work presenting a GC–MS/MS method for the determination of NPS in blood samples. The presented procedure was applied to authentic samples from forensic cases, demonstrating its utility in the quantifcation of a wide number of psychoactive substances in routine toxicological analyses. The developed procedure can also be easily expanded to additional compounds.

Green Chromatography: State-of-the-art, Opportunities and Future Perspectives

It is well known that chromatographic procedures could have a significant impact on the environment if laboratory practice is not in line with the principles of green analytical chemistry (GAC). However, chromatographic techniques have the potential to be greener in all steps of the analysis. The approaches used to make chromatographic separations greener differ depending on the type of chromatographic method. This chapter considers the ways in which chromatography can become greener. Liquid and gas chromatography are compared from the GAC point of view. In addition, the importance of miniaturization in sample preparation and chromatographic separations is pointed out. On-line process analysers and portable chromatographs are also discussed.

Production of certified reference materials - homogeneity and stability study based on the determination of total mercury and methylmercury

Reference materials (RMs) play an important role in all elements of the quality assurance system of measurements. In this work, ``package'' 4 new CRMs (bottom sediment, herring tissue, cod tissue, cormorant tissue) were prepared and characterised to carry out the quality control in monitoring analysis of mercury and methylmercury in environmental samples. Materials - candidates were collected in Poland and south part of the Czech Republic. All materials were freeze-dried, milled, sieved, homogenised, sterilized and distributed in amber bottles. For the homogeneity and stability study of the samples of materials several statistical tests were applied. Materials - candidates for CRMs with certified mercury and methylmercury content meet the heterogeneity requirement and can be considered homogenous both between bottle and within bottle. Each material meets also the requirements for the stability condition of reference material with certified mercury content.

Recent Applications of 1D GC-MS and 2D GC-MS in Foodomics Studies

Gas chromatography coupled with mass spectrometry and food chemistry have been tightly linked since the 1960s. This setup is also an integral part of the omics studies when it comes to low mass metabolites. Therefore, the marriage of GC-MS and foodomics is obvious. Two-dimensional gas chromatography coupled with mass spectrometry fits perfectly within the latest trends in foodomics, since it is tailored for holistic food analysis. In this article, the authors will focus on the current trends in 1D and 2D GC-MS-based foodomics.

Ultrasound assisted solvent extraction of porous membrane-packed samples followed by liquid chromatography-tandem mass spectrometry for determination of BADGE, BFDGE and their derivatives in packed vegetables

The problem of the presence of trace organic pollutants in food is of growing importance due to increasing awareness about their impact on newborns, infants and adults of reproductive age. Despite the fact that packaged food products offer many advantages, packaging can be a source of contamination for stored food. Thus, monitoring such pollution in food is of high importance. In this work, a novel methodology based on the solvent extraction of porous membrane-packed samples followed by liquid chromatography-tandem mass spectrometry was applied for the determination of bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE) and their derivatives in packed vegetables. Several parameters of the extraction process were optimized, including the volume and type of extraction solvent as well as the sonication time. Due to advantages such as simplicity of use, short analysis time, and a reduction in the required amount solvent, the developed procedure can be considered green. In addition, the developed methodology was characterized by good validation parameters. Limit if quantitation (LOQ) was found to be in the range of 0.8 to 1.5 ng/g. The obtained recoveries varied from 78.3% to 111.2%. The repeatability of the extraction ranged between 0.6% and 5.8% (RSD). The proposed method was successfully applied to determine the presence of BADGE, BFDGE and their derivative compounds in the vegetable samples stored in different types of containers. The obtained data indicate that the majority of investigated samples were contaminated by chlorinated and hydroxyl derivatives of BADGE.

A new dilution-enrichment sample preparation strategy for expanded metabolome monitoring of human breast milk that overcomes the simultaneous presence of low- and high-abundance lipid species

The complex nature of human breast milk (HBM) makes samples difficult to analyze, requiring several extraction techniques and analytical platforms to obtain high metabolome coverage. In this work, we combined liquid-liquid extraction (LLE) and solid-phase extraction (SPE) techniques to prepare HBM samples to overcome the challenge of low- and high-abundance lipid species, enabling the semiquantitative analysis of total HBM lipids in one liquid chromatography-mass spectrometry (LC-MS) run. A nonorganic fraction obtained during the LLE step was used to analyze small polar metabolites. This analytical approach allows extensive metabolome coverage, especially for low-abundance glycerophospholipids and sphingolipids. The method was applied to monitor short-term metabolome changes in HBM composition within individual mothers and the results showed variable metabolite composition patterns. Simultaneous detection of high-abundance glycerolipids and low-abundance but not less significant phospholipids in one LC-MS run saves time, decreases cost, and enables comprehensive insight into the dynamics of HBM composition.

A Three-Step Approach to Estimation of Reduction Potentials of Natural Mixtures of Antioxidants Based on DPPH Test; Illustration for Catechins and Cocoa

The aim of this study is to propose a methodology to assess electrochemical properties of complex mixtures of antioxidants, such as plant extracts, based on the results of simple and popular DPPH test. The first, most difficult step, involves determinations of standard reduction potentials (E0) for the series of purified compounds (here catechins). The next step is the calculation of stoichiometric values (n10) based on the results of DPPH test for the same compounds. Finally, a correlation equation is formulated, which is then employed to estimate “cumulative reduction potential” (Ec) for the mixture of interest (here cocoa) using DPPH test results.

Adsorption of Cr(VI) in aqueous solution using sago bark (Metroxylon sagu) as a new potential biosorbent

S. Fauzia , A. Hermansyah, D. Dahyunir, J. Namieśnik , R. Zein – Desalination and Water Treatment – 2019
This paper investigated the ability of sago bark (Metroxylon sagu) as a new potential biosorbent in removing Cr(VI) in batch system. The optimum adsorption capacity of sago bark (Metroxylon sagu) was 61.73 mg/g achieved at pH 3, agitation rate of 100 rpm, contact time 60 min, particle size ≤32 μm, and initial concentration of Cr(VI) 1,000 mg/L at room temperature (25°C). The adsorbent regeneration was carried out using 0.01 M HNO3 with regeneration efficiency of 78.35%. The adsorption data fitted better to Freundlich and Langmuir equilibrium isotherm models. The data confirmed that Cr(VI) sorption onto sago bark (Metroxylon sagu) has good agreement with pseudo-second-order model. The thermodynamic study indicated that Cr(VI) sorption onto sago bark (Metroxylon sagu) occurred as exothermic in nature (DH = –72.55 kJ/mol), which was required energy for adsorption process, and the disorderliness decreased as temperature increased (DS = –263.06 J/mol). Thus, it can be concluded that sago bark (Metroxylon sagu) can be utilized as a potential adsorbent in Cr(VI) removal.