Beatriz Rebollo-Calderón, Antonio Calvo-López, Aida Ormazábal, Rafael Artuch, Javier Rosell-Ferrer, Julian Alonso-Chamarro, Mar Puyol
{"title":"Testing of a novel automated point-of-care analyzer for blood ammonium monitoring in a clinical setting.","authors":"Beatriz Rebollo-Calderón, Antonio Calvo-López, Aida Ormazábal, Rafael Artuch, Javier Rosell-Ferrer, Julian Alonso-Chamarro, Mar Puyol","doi":"10.1007/s00216-025-05879-z","DOIUrl":"10.1007/s00216-025-05879-z","url":null,"abstract":"<p><p>Certain diseases are marked by elevated ammonium levels in the blood, a condition known as hyperammonemia. Prompt detection and medical intervention are crucial to prevent potentially fatal outcomes. Therefore, ammonium levels should be monitored regularly, typically in referral hospitals where specialized and costly equipment is available. Although compact commercial devices are available for this purpose, none of them meet all the technical and analytical requirements needed for direct blood analysis, and current reported strategies have not been validated with enough samples to confirm results reliably. We present a robust and reliable automated point-of-care (POC) analyzer for the potentiometric determination of ammonium in blood. Comprising three computer-controlled modules-fluid management, detection, and data acquisition and transmission-this system combines portability, ease of use, and affordability. It can directly measure untreated blood samples, significantly reducing analysis time. Fully automated, it operates unsupervised with minimal lab personnel intervention. Analytical quality parameters include 5% RSD repeatability (n = 8), a limit of detection of 24 μM, a working range of 30-1000 µM and a sample volume of 215 µL. Successfully implemented in a hospital for 2 months, it analyzed 238 blood samples in parallel with the hospital's reference method showing comparable results (paired t-test, Passing-Bablok regression and Bland-Altman Plot) and randomly distributed errors, with a 4% accuracy calculated as mean error. Results indicate the POC analyzer effectiveness and reliability in a clinical setting compared to currently reported or commercially available equipment, being suitable for bedside monitoring of conditions associated with hyperammonemia in healthcare centers, including emergency rooms and clinics in developing countries.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"3477-3485"},"PeriodicalIF":3.8,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143955215","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Impact of silicon substrate on micro gas chromatographic column using ALD alumina as the stationary phase.","authors":"Shaojie Ma, Yuchen Zhu, Wenbo Li, Boxin Chen, Bin Zhao, Fei Feng","doi":"10.1007/s00216-025-05872-6","DOIUrl":"10.1007/s00216-025-05872-6","url":null,"abstract":"<p><p>Due to the high conformal films, atomic layer deposition (ALD) alumina has been used as a uniform stationary phase or support layer of stationary phase for micro gas chromatographic column. However, the severe tailing of chromatographic peaks appears when ALD alumina is used as the stationary phase. Recently, an H-diffusion model was proposed to explain the H accumulation phenomenon of ALD alumina films. Compared with the normal-resistance silicon substrates, the ALD alumina films based on low-resistance silicon substrates have fewer H impurities, which may further improve the tailing of chromatographic peaks and the theoretical number of plates. In this paper, a micro gas chromatographic column based on the low-resistance silicon (LR-μGCC) substrate (resistivity, 0.001-0.005 Ω·cm) using alumina deposited by atomic layer deposition as the stationary phase is reported. Compared with normal-resistance silicon substrates (resistivity, 1-10 Ω·cm), the micro gas chromatographic columns (μGCC) prepared on low-resistance silicon substrates have a higher separation performance. The test results showed that the LR-μGCC increased the theoretical plate number of alkane mixtures (n-hexane, n-octane, n-nonane, and n-decane) by 20.9%, 74.8%, 139.4%, and 55.4%, respectively, and reduced the tailing factor by 13.0%, 41.8%, 48.6%, and 49.1%, respectively.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"3383-3391"},"PeriodicalIF":3.8,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143955327","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Pyrolysis-GC/MS differentiates polyesters and detects additives for improved monitoring of textile labeling accuracy and plastic pollution.","authors":"Josh Forakis, Jennifer Lynch","doi":"10.1007/s00216-025-05851-x","DOIUrl":"10.1007/s00216-025-05851-x","url":null,"abstract":"<p><p>Polyesters comprise the greatest proportion of textile fibers and are found in various everyday goods; hence, polyester fibers are a significant source of microplastic pollution and textile waste. The specific chemical composition of commercial polyester fibers is often proprietary and mostly assumed to be poly(ethylene terephthalate) (PET). Polyester is a class of polymers that include poly(butylene terephthalate) (PBT), poly(cyclohexylenedimethylene terephthalate) (PCT), and poly(ethylene naphthalate) (PEN), as well as biodegradable polymers. Our study aims to clarify whether household polyester products are primarily PET, are labeled accurately, or contain phthalate additives by applying double-shot pyrolysis-gas chromatography/mass spectroscopy (Py-GC/MS). We analyzed four scientific-grade polyester reference standards, 52 manufacturer-grade polyester fibers or pellets, and 229 samples from 193 consumer polyester products. From the pyrograms, samples were predominantly identified as PET (87.4%, 95% CI [93.5-81.3%]), but five samples were identified as a different polyester, nine as non-polyester polymers, and 23 as a blend of PET with another polymer. From the thermal desorption chromatograms, diethyl phthalate was the most frequently detected phthalate, found in 23.3% (95% CI [17.3-29.3%]) of the consumer products, including children's toys. Double-shot py-GC/MS advantageously results in these empirical data that (1) counter the assumption that products labeled polyester are always PET, (2) emphasize the importance of creating spectral libraries with well-characterized materials for accurate polymer identification of unknown plastic particles, and (3) demonstrate that phthalates are common additives in household products.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"3113-3126"},"PeriodicalIF":3.8,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12103379/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143750468","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kilian Hoecherl, Simon Streif, Clemens Spitzenberg, Simone Rink, Arne Behrent, Ferdinand Holzhausen, Christian Griesche, Cornelia Rogoll, Maximilian Foedlmeier, Anna Gebhard, Kacper Kulikowski, Nicole Schaefer, Diana Pauly, Antje J Baeumner
{"title":"A homogeneous immunoassay technology based on liposomes and the complement system enables one-step, no-wash, rapid diagnostics directly in serum.","authors":"Kilian Hoecherl, Simon Streif, Clemens Spitzenberg, Simone Rink, Arne Behrent, Ferdinand Holzhausen, Christian Griesche, Cornelia Rogoll, Maximilian Foedlmeier, Anna Gebhard, Kacper Kulikowski, Nicole Schaefer, Diana Pauly, Antje J Baeumner","doi":"10.1007/s00216-025-05882-4","DOIUrl":"10.1007/s00216-025-05882-4","url":null,"abstract":"<p><p>Liposomes are a well-established carrier and controlled release system in medicine and bioanalysis. Their biomimetic capabilities are harnessed for the development of a reliable homogeneous assay platform technology that lends itself to high-throughput screening and point-of-care applications since no wash or separation steps are needed. It was developed for fluorescent, chemiluminescent, and electrochemical detection strategies and applied to antibodies directed against small or polymeric molecules and peptides as model analytes. The simplicity of the approach is achieved as mere binding of analytes or analyte-associated entities to the liposome surface leads to the activation of the complement system, which in turn lyses the liposomes. Released encapsulated marker molecules are quantified and directly correlated to the analytes. Control over the liposome chemistry, including cholesterol content, surface chemistry, and encapsulants, was identified to be key to ensure their general serum and storage stability (more than 40 months at 4 °C and up to 4 weeks at 37 °C) and their efficient and specific response to complement activity. Additional assay conditions of relevance included the concentration of liposomes and their ratio to serum proteins, the amount of complement trigger per liposome, and the activity of complement proteins. Understanding and being able to control the liposomes enable various analysis strategies including the quantification of analytes, determination of complement activity, and evaluation of the therapeutic application potential of antibodies. A time-resolved version of the assay even allows the study of the complex actions of the complement system.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"3257-3273"},"PeriodicalIF":3.8,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143958904","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"In-depth characterization of acylcarnitines: utilizing nitroxide radical-directed dissociation in tandem mass spectrometry.","authors":"Xiangyu Gao, Xue Zhao","doi":"10.1007/s00216-025-05868-2","DOIUrl":"10.1007/s00216-025-05868-2","url":null,"abstract":"<p><p>Acylcarnitines (ACs) are metabolic intermediates of fatty acids playing important roles in regulating cellular energy and lipid metabolism. The large structural diversity of ACs arises from variations in acyl chain length and the presence of chemical modifications, such as methyl branching, desaturation, hydroxylation, and carboxylation. Numerous studies have demonstrated that these structural isomers of ACs function as biomarkers for a variety of diseases. However, conventional tandem mass spectrometry (MS/MS) via low-energy collision-induced dissociation (CID) faces challenges in distinguishing these isomers. In this study, we report a radical-directed dissociation (RDD) approach for characterization of the intrachain modifications within ACs. The method involves derivatizing ACs with O-benzylhydroxylamine (O-BHA), followed by MS<sup>2</sup> CID to produce a nitroxide radical for subsequent RDD along the fatty acyl chain. The above RDD approach was employed on a cyclic ion mobility spectrometry (cIMS) and reversed-phase liquid chromatography (RPLC), enabling the identification and relative quantification of branched chain isomers of ACs. By derivatizing carboxylated ACs with O-BHA, their mass is shifted to a higher region, thereby facilitating their separation from the isobars of hydroxylated ACs. Furthermore, this RDD method effectively allows for the assignment and localization of C = C and hydroxylation positions. This RDD approach has been applied for in-depth profiling of ACs in mice plasma extracts.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"3327-3335"},"PeriodicalIF":3.8,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143810328","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yuan Liu, Jillian Johnson, Hua Zhang, Penghsuan Huang, Lingjun Li
{"title":"Direct transfer of multicellular tumor spheroids grown in agarose microarrays for high-throughput mass spectrometry imaging analysis.","authors":"Yuan Liu, Jillian Johnson, Hua Zhang, Penghsuan Huang, Lingjun Li","doi":"10.1007/s00216-025-05843-x","DOIUrl":"10.1007/s00216-025-05843-x","url":null,"abstract":"<p><p>Multicellular tumor spheroids (MCTSs) play an important role in biological studies and cancer research. There is an emerging research interest in molecular profiling and drug distribution of MCTSs by leveraging the superior sensitivity and molecular specificity of mass spectrometry imaging (MSI). Current methods for sample preparation of MCTSs can suffer from low throughput, as MCTSs are typically individually transferred from cell culture into an MSI embedding media and sectioned individually, or sometimes, a few spheroids are placed in a small block of embedding media in preparation for MSI. Here, we developed a method to minimize the sample preparation steps needed to create high-throughput MCTS frozen sections for MSI. Agarose-based microarrays created from Microtissues<sup>®</sup> molds were used during MCTS culturing, after which the entire MCTS agarose microarray was taken out of the cell culture well and then directly embedded in 5% gelatin, without the need for a transfer step for each individual MCTS into the embedding media. This method enables rapid profiling of up to 81 MCTSs for larger MCTSs (500-800 µm) or up to 256 MCTSs for smaller MCTSs (200-300 µm) in a single section, remarkably improving the throughput possible for MSI MCTS workflows. Notably, sectioning MCTSs together in the agarose microarray also improves MCTS visualization during sectioning, such that staining each MCTS section to ensure the presence of the MCTSs within the embedding media is not necessary during the sectioning process. The method described here provides a more direct, convenient strategy to achieve high-throughput sections. MSI MCTS sectioning throughput is an important advancement for both pharmaceutical testing of MCTS; the direct transfer 3D cell cultures grown within cell culture-compatible polymer scaffolding are also critical for expanding MSI for the characterization of microfluidic and complex in vitro models, where agarose is readily utilized as a non-adhesive 3D cell culture scaffold.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"3021-3031"},"PeriodicalIF":3.8,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12103265/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143741940","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Kinetic and analytical characterization of a new tropinone oxidase enzyme and its application to the simultaneous determination of the tropane alkaloids atropine and scopolamine.","authors":"Mario Domínguez, Susana de Marcos, Javier Galbán","doi":"10.1007/s00216-025-05856-6","DOIUrl":"10.1007/s00216-025-05856-6","url":null,"abstract":"<p><p>A spectrophotometric enzymatic method for the determination of atropine (Atp) and scopolamine (Scp), two tropane alkaloids (TAs), has been developed. The method is based on a previous basic hydrolysis to tropine (Trp) and scopine (Sci) respectively, and a subsequent enzymatic oxidation catalyzed by a tropinone reductase 1 (TRase) using NAD as oxidant; the absorbance of NADH (340 nm) is monitored during the reaction. First, the enzyme kinetics of both substrates are studied; it is concluded that both TAs follow a compulsory order ternary complex mechanism and the Michalis-Menten constant is calculated. Then, an enzymatic method was optimized for Atp, allowing the determination of this substrate in the range from 1.1·10<sup>-5</sup> M to 3.0·10<sup>-4</sup> M (LoD = 3.5·10<sup>-6</sup> M); it was applied to the determination of Atp in a spiked chia sample (96 ± 6% recovery). Interestingly, the equilibrium constant of the reaction decreased with temperature and increased with enzyme concentration; both effects were satisfactorily explained. A similar analytical study was carried out with Scp (linear range from 1.2·10<sup>-5</sup> M to 3.0·10<sup>-4</sup> M, LoD = 3.6·10<sup>-6</sup> M); the method was also applied to Scp in a spiked chia sample (94 ± 2% recovery). Finally, since the kinetics of Scp is slower than that of Atp, the simultaneous quantitative determination of both compounds was successfully developed by measuring the absorbance at two reaction times (70 s and 300 s). This method was applied to the simultaneous determination of both TAs first in a synthetic sample and later in a spiked chia sample, with recoveries around 98% for both compounds. Although the sensitivity of the method is lower than that of the immunoassays for Atp, it has advantages such as the simultaneous determination of Atp and Scp, and even the possible determination of Trp (another TA).</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"3169-3176"},"PeriodicalIF":3.8,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12103354/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143957494","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Bimetallic-doped carbon quantum dots with enhanced photoluminescence and peroxidase-mimicking activity for dual-mode colorimetric and ratiometric fluorescence assay of alendronate.","authors":"Jue Wang, Guanglong Yu, Shuangshuang Wu, Haifeng Zhou, Xiaoqian Liu, Jiawei Han, Rui Yang","doi":"10.1007/s00216-025-05866-4","DOIUrl":"10.1007/s00216-025-05866-4","url":null,"abstract":"<p><p>Carbon quantum dots (CQDs) are powerful signal transducers in dual-mode assays while still being challenged by their poor peroxidase-mimicking activity and photoluminescence property. Herein, bimetallic copper-iron-doped CQDs (CuFe-CQDs) as a multifunctional nanozyme were proposed for dual-mode colorimetric and ratiometric fluorescence assays of alendronate sodium (ALDS). Notably, CuFe-CQDs were identified to show enhanced and tunable photoluminescence and peroxidase-mimicking activities with bimetallic doping, ascribed to the boosting activation ability of H<sub>2</sub>O<sub>2</sub> into HO• and <sup>1</sup>O<sub>2</sub>, and the improving carrier mobility in the π-conjugated structure of CuFe-CQDs. Based on the inhibition of ALDS on the peroxidase-mimicking activity of CuFe-CQDs, which further disturbed the inner filter effect (IFE) between CuFe-CQDs and the chromatic product, a dual-mode colorimetric and ratiometric fluorescence assay for the differentiation and determination of ALDS and its analogues was developed with better quantification and high identification, reaching a limit of detection of 0.019 μM in colorimetric mode and 0.146 μM in ratiometric fluorescence mode. The developed dual-mode assay also demonstrated accurate analysis of ALDS in diluted tablets and human urine with recoveries of 92-110%. Our work provides a new approach for the development of functional nanozymes and holds great prospects in multi-mode/signal sensing in complex matrix.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"3315-3326"},"PeriodicalIF":3.8,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143810326","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Elsa Boudard, Lisa Fisson, Nabil Moumane, José Dugay, Jérôme Vial, Didier Thiébaut
{"title":"Study of sampling phases for body odor sampling prior to analysis by TD-GC×GC/ToFMS.","authors":"Elsa Boudard, Lisa Fisson, Nabil Moumane, José Dugay, Jérôme Vial, Didier Thiébaut","doi":"10.1007/s00216-025-05857-5","DOIUrl":"10.1007/s00216-025-05857-5","url":null,"abstract":"<p><p>Body odor consists of a complex matrix of volatile organic compounds (VOCs), which has garnered increasing interest in fields like medicine for its potential in disease diagnosis. However, the field of body odor analysis is advancing slowly, partly due to a lack of standardized methodologies. Although gas chromatography-mass spectrometry (GC-MS) is widely used for VOC analysis, there is a broad range of sampling and extraction methods, leading to different or even sometimes contradictory results. To move toward standardized procedures, this study compares five sampling phases for direct body odor sampling in terms of analytical cleanliness and VOC trapping/release efficiency: gauze, glass beads, PowerSorb<sup>®</sup>, Getxent<sup>®</sup> microtubes, and passive sampling pillows (PSP). Thermodesorption was employed to simplify the protocol and minimize contamination or sample loss, which often occurs during multistep processes. Given the matrix's complexity and the need to detect trace-level compounds, comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC/ToFMS) was used to achieve high sensitivity and peak capacity. PSP and PowerSorb<sup>®</sup> demonstrated the best performance, with mean recovery yields of 95% and 71%, respectively, and 22% and 10% variability, ensuring good repeatability. These findings, initially obtained under simulated conditions with a synthetic mixture, were validated with real body odor samples, with an optimal sampling duration estimated between 30 min and 1 h. This study not only highlights these effective sampling solutions but also emphasizes the risks associated with using sorbent phases that lack adequate analytical cleanliness (i.e., clean blank) such as gauze.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"3177-3190"},"PeriodicalIF":3.8,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12103381/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143957077","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Giorgi Kobidze, Alfredo Fabrizio Lo Faro, Aurora Balloni, Giorgia Sprega, Marta Massano, Sarah M R Wille, Giuseppe Basile, Tivadar Farkas, Anastasio Tini, Francesco Paolo Busardò, Bezhan Chankvetadze
{"title":"Simultaneous enantioselective determination of 2-, 3-, and 4-methylmethcathinones; their isomers; and major phase-1 metabolites in oral fluid of drug abusers using enantioselective high-performance liquid chromatography-tandem mass spectrometry.","authors":"Giorgi Kobidze, Alfredo Fabrizio Lo Faro, Aurora Balloni, Giorgia Sprega, Marta Massano, Sarah M R Wille, Giuseppe Basile, Tivadar Farkas, Anastasio Tini, Francesco Paolo Busardò, Bezhan Chankvetadze","doi":"10.1007/s00216-025-05838-8","DOIUrl":"10.1007/s00216-025-05838-8","url":null,"abstract":"<p><p>The most powerful and widely used detector for clinical and toxicological analyses is undoubtedly the mass spectrometer (MS) due to its specificity and high sensitivity. However, it cannot differentiate enantiomers from each other, as well as cannot easily distinguish between positional isomers. Therefore, the components of interest to the analysis at hand need to be separated prior to their detection by MS in order to reliably identify and quantify their enantiomers and positional isomers. In the present study, the simultaneous chemo- and enantioseparation of the drugs of abuse, 2-, 3-, and 4-methylmethcathinones, is described. The developed method was applied to 15 oral fluid (OF) samples collected by police in Belgium and found positive for mephedrone (4-methylmethcathinone, 4-MMC) based on a nonselective method for enantiomers and positional isomers. However, re-analyzing these samples with the analytical method proposed in this report indicated that mephedrone was present in only 1 of them, while 6 samples contained 3-methylmethcathinone (3-MMC) and 12 samples contained 2-methylmethcathinone (2-MMC). At the same time, four OF samples contained both 2- and 3-MMC. The developed method enabled the enantioselective analysis of major metabolites of methylmethcathinones, such as their N-demethyl derivatives (nor-MMCs), as well as, at least partially, of their dihydrometabolites. In addition to their positional isomers, other structural isomers of MMCs, such as buphedrone, metamfepramone, and ethcathinone, could also be detected enantioselectively.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"3231-3243"},"PeriodicalIF":3.8,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143708101","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}