Analytical and Bioanalytical Chemistry最新文献

{"title":"A novel method for the determination of synthetic cathinones and related substances in postmortem blood samples using cork-based dispersive solid-phase microextraction prior to LC-MS/MS analysis.","authors":"Letícia Birk, Bruno Pereira Dos Santos, Sarah Eller, Tiago Franco de Oliveira","doi":"10.1007/s00216-025-05907-y","DOIUrl":"https://doi.org/10.1007/s00216-025-05907-y","url":null,"abstract":"<p><p>The detection of new psychoactive substances in postmortem blood is of primary importance for the investigation of related deaths. A method using cork as a biosorbent in a solid-phase microextraction with LC-MS/MS analysis was developed and validated for the determination of synthetic cathinones and related substances in blood. The sample preparation method employed 200 µL of sample and 30 mg of cork powder, and the complete procedure was optimized using multivariate strategies. LC-MS/MS analysis was performed in gradient mode, with a total run time of 7.5 min for the determination of cathinone, ethylone, fentanyl, MDA, MDMA, mephedrone, N-ethylpentylone, and pentylone. Comprehensive validation was performed through the ASB/ANSI Standard 036. Lower limit of quantification (LLOQ) values ranged between 0.5 and 1 ng/mL, with linear ranges between LLOQ and 85 ng/mL. Accuracy and precision results were satisfactory, and significant ion suppression was found (2.9-63.4%). Applicability of the method was evaluated by the analysis of three postmortem blood samples from forensic casework, suspected to have the presence of synthetic cathinones. All samples were positive for MDMA and MDA, with concentrations between 79.2-198.1 ng/mL and 23.1-26.6 ng/mL, respectively. The greenness of the method was also evaluated by AGREEprep, with an overall score of 0.53. This study is the first to apply a cork-based extraction to blood analysis. The method has proven to be reliable and a valuable greener alternative for the determination of synthetic cathinones and related substances in postmortem blood.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144075311","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":"Amino acid regulation of peroxidase-like activity of Cu₂O nanozyme for detection of tetracycline antibiotics.","authors":"Yueqiang Wang, Shengwei Sun","doi":"10.1007/s00216-025-05904-1","DOIUrl":"https://doi.org/10.1007/s00216-025-05904-1","url":null,"abstract":"<p><p>Tetracycline antibiotics (TCs) are widely used in medicine, agriculture, and animal husbandry. However, their overuse has led to environmental pollution, posing a significant threat to water sources, soil, and food safety. Therefore, there is an urgent need for efficient, sensitive, simple, and low-cost detection methods for environmental pollution monitoring. In this study, the catalytic activity of copper-based nanozymes was regulated by AAs. Lysine, aspartic acid, glycine, and arginine were chosen as ligands to synthesize different copper-based nanozymes. The results showed that the type of amino acid significantly influenced the particle size, morphology, and peroxidase (POD)-like catalytic activity of Cu₂O. Based on these amino acid-regulated Cu₂O nanozymes, we further developed a highly sensitive, easy-to-use, and low-cost colorimetric sensor array that can effectively distinguish TCs. This sensor array was successfully validated in binary mixtures and wastewater environments. This study not only provides important insights into the small-molecule regulation of copper-based nanozyme catalytic performance but also offers a novel approach for the detection of TCs in environmental monitoring.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143961057","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":"Traceability and discrimination of opium poppy shell analogues using HS-GC-IMS combined with machine learning algorithms.","authors":"Yinghua Qi, Junchao Ma, Mingyuan Lei, Hongbin Guo, Xuebo Li, Yuhao Song, Wenhui Lu, Xinhua Lv, Nianfeng Sun","doi":"10.1007/s00216-025-05909-w","DOIUrl":"https://doi.org/10.1007/s00216-025-05909-w","url":null,"abstract":"<p><p>Illegal adulteration has been a critical issue in food safety, emerging as a focal point in forensic science. This situation has led to an increased demand for effective detection and monitoring technologies. Opium poppy shells are a critical source of drugs, and the accurate tracing and identification of their analogues are essential in drug-related cases. The features of volatile compounds in six opium poppy shell analogues (OPSA) were characterized using headspace-gas chromatography-ion mobility spectrometry (HS-GC-IMS) in this study, and an accurate model for origin tracing was established through the integration of machine learning algorithms. A total of 213 volatile compounds were accurately identified, with esters, ketones, aldehydes, alcohols, and alkenes being the most abundant compounds. Additionally, two supervised machine learning algorithm classification models were established based on the HS-GC-IMS dataset to predict the categories of OPSA, including the orthogonal partial least squares discriminant analysis (OPLS-DA) and random forest models, and were subsequently compared with unsupervised models. By employing the random forest classification model, significant volatile compound characteristics were recognized, resulting in enhanced efficiency. Furthermore, the model achieved an out-of-bag (OOB) error value of 0, indicating excellent predictive capability for tracing and distinguishing OPSA. Our research findings indicate that the integration of HS-GC-IMS with machine learning is expected to enhance the efficiency and accuracy of tracing and identifying the categories of OPSA, thereby providing theoretical support for litigation and judicial processes.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143951714","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":"Plastic and rubber polymers in urban PM₁₀ by pyrolysis-gas chromatography-mass spectrometry.","authors":"Tatu Martinmäki, Sanna Saarikoski, Hilkka Timonen, Jarkko V Niemi, Markus Sillanpää","doi":"10.1007/s00216-025-05906-z","DOIUrl":"https://doi.org/10.1007/s00216-025-05906-z","url":null,"abstract":"<p><p>Microplastics, including tyre and road wear particles, have been detected in every environmental compartment in both urban and remote areas. However, their contribution to atmospheric particulate matter is still sparsely explored. These airborne micro- and nanosized particles are continuously inhaled and pose risks to the environment and public health. The objectives of this study were to develop and validate a thermoanalytical method for the quantification of microplastics in urban particulate matter. Aerosol particles smaller than 10 µm in aerodynamic diameter (PM₁₀) were sampled at the kerbside in Helsinki, Finland, during spring 2024. The samples were pretreated by homogenization and thermal desorption prior to chemical analysis by micro-furnace pyrolysis-gas chromatography-mass spectrometry. The developed method was validated in terms of selectivity, limits of quantification, linear range, trueness, precision, and measurement uncertainty. Instrument quantification levels were 8-270 ng. Expanded measurement uncertainties were 25-30% and 50-70% for the studied tyre wear rubbers and thermoplastics, respectively. Polyethylene, polyethylene terephthalate, polypropylene, polystyrene, and tyre and road wear particles were detected in urban PM₁₀ samples, and their sum accounts for 1-3% of total PM₁₀. These results represent the level of airborne microplastic particles to which people can be exposed in urban environments.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143957075","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":"Mid-IR laser measurement of acetaldehyde in the headspace gas of cell culture media samples from growth of breast cancer cells in hydrogel scaffolds.","authors":"Parker Bryant, Patrick McCann, Khosrow Namjou, Vassilios Sikavitsas, Roger Harrison","doi":"10.1007/s00216-025-05899-9","DOIUrl":"https://doi.org/10.1007/s00216-025-05899-9","url":null,"abstract":"<p><p>A mid-IR laser absorption spectrometer configured with an interband cascade laser (ICL) was used to measure acetaldehyde concentrations in the headspace gas of cell culture media samples obtained from the culturing of breast cancer cells in a flow perfusion bioreactor. Measurements were performed by bubbling lab air through a media sample and passing the exhaust gas through a long optical path gas cell where rotational-vibrational modes of acetaldehyde were excited by the ICL. Acetaldehyde concentrations were determined from peak-to-peak voltages for the two strongest acetaldehyde absorption features within a spectral region spanning 1770.20 cm^-1 to 1770.35 cm^-1. Three different media samples obtained from cells cultured with the same nominal conditions had headspace acetaldehyde concentrations of 412 ppb, 513 ppb, and 390 ppb, while two media samples with imposed hypoxia or cobalt chloride stabilization of hypoxia inducible factor 1-alpha (HIF-1α) had higher acetaldehyde concentrations, 815 ppb and 536 ppb, respectively. These results establish experimental proof-of-concept for the ability of mid-IR laser absorption spectroscopy to measure acetaldehyde in cell culture media headspace, allowing observation of HIF-1α driven shifts in cancer cell metabolism.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143958400","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":"The quest for the perfect \"total PFAS\" method: how can the total oxidisable precursor (TOP) assay be made reliable?","authors":"Xavier Dauchy","doi":"10.1007/s00216-025-05902-3","DOIUrl":"https://doi.org/10.1007/s00216-025-05902-3","url":null,"abstract":"<p><p>Per- and polyfluoroalkyl substances (PFAS) make up a large and complex class of manmade chemicals. They have been widely used in numerous industrial branches and are incorporated into many consumer products. Today, there is a consensus on the fact that PFAS are present in all environmental compartments and that populations all over the world are subjected to them via internal exposure. It has been estimated that thousands of individual PFAS have been manufactured and marketed since the 1950s, to which impurities present in commercial products and intermediate environmental transformation products should be added. Since it is unrealistic to be able to individually identify, detect and quantify all the PFAS present in a sample, several analytical approaches have been developed to assess the presence of \"hidden/unseen\" PFAS. One of these, known as the total oxidisable precursor (TOP) assay, was first described in 2012. Basically, it converts some PFAS, hereafter referred to as precursors, into stable terminal products readily measurable by routine target methods. This review is based on more than 100 studies in which the original TOP assay was simply applied or optimised. The review found that the TOP assay was selective, sensitive, applicable to many matrices, useful within a forensic context, inexpensive, and easy to implement and has been assessed in the literature on a wide range of precursors. However, this method comprises many subtleties and has some flaws that operators should be made aware of so that they may be addressed as far as possible. Finally, this review tries to lay the foundations for better practices and quality assurance/quality control measures, in order to improve accuracy and reliability of TOP assay results.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143952000","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":"A candidate reference measurement procedure for quantification of human insulin in serum based on immunoaffinity extraction and isotope dilution-liquid chromatography-tandem mass spectrometry.","authors":"Huixia Liu, Yanlin Han, Huimin Wang, Yuefeng Zhang, Chunlong Liu, Man Liang","doi":"10.1007/s00216-025-05900-5","DOIUrl":"https://doi.org/10.1007/s00216-025-05900-5","url":null,"abstract":"<p><p>Accurate measurement of human insulin is critical for proper diagnosis, monitoring, and treatment of diabetes. But the insulin results of clinical immunoassay are inconsistent mainly due to antibody cross-reactivity. To standardize and ensure the accuracy of clinical assays, reference measurement procedures (RMPs) with higher metrological order are required. An isotope dilution-liquid chromatography-tandem mass spectrometry (ID-LC-MS/MS) for quantification of human insulin in serum as a candidate reference measurement procedure (cRMP) was developed and validated. Insulin was enriched from human serum by insulin antibodies immobilized on magnetic beads. The eluent was analyzed by ID-LC-MS/MS. The cRMP separated human insulin from potentially interfering compounds and enabled measurement over a range of 0.05-40 ng/g, with no matrix effects and carryover. The limit of detection (LOD) and the limit of quantitation (LOQ) in serum were 24.6 pg/g and 48.8 pg/g, respectively. Imprecision (intra-assay and inter-assay) was <2.77% at 0.436, 2.003, and 11.449 ng/g. Recoveries ranged from 99.5% to 101.7% at three spiked levels. Extraction recovery was measured at 85% or higher. Insulin analogues caused no interference for the determination of endogenous insulin. Expanded measurement uncertainty of target value-assigned samples was ≤3.5%. The cRMP was applied to measure human insulin in serum and was compared with two immunoassays using 46 serum samples. Also, a discrepancy of three candidate reference materials for the calibration of cRMP was discussed.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143955863","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":"Integrating metabolite-based molecular networking with database matching and LC-MS-guided targeted isolation for the discovery of novel chemical constituents: application to Euphorbia helioscopia L.","authors":"Tianren Wu, Yaling Deng, Weijia Hu, Caihong Bai, Han Yu, Kaifeng Hu","doi":"10.1007/s00216-025-05893-1","DOIUrl":"10.1007/s00216-025-05893-1","url":null,"abstract":"<p><p>Molecular networking (MN) analysis facilitates the targeted discovery of novel constituents and enhances the understanding of natural products. While various molecular networks could reduce the effects of redundant nodes, current research is still limited by the interference from the same and coeluted metabolites, including isotopic peaks, a variety of adduct ions, in-source fragmentations, and dehydration. This research proposes a novel strategy: stratified precursor lists (SPLs)-guided Metabolite-Based Molecular Networking (MBMN), which ensures a high-quality MS² spectrum for each metabolite precursor due to the absence of retention time overlap with other coeluted metabolites, and each node represents a unique metabolite. By collecting over 40 MS² databases from multiple online platforms and public databases, an integrated MS² database (IM2DB) containing more than two million MS² fragmentation data was constructed. In addition, a customized MS¹ database (M1DB) of reported compounds was also created. Nodes representing known compounds were annotated compared to the IM2DB and M1DB. Combining with MBMN analysis significantly enhances compound identification and characterization, thereby facilitating the discerning of potential novel constituents. To demonstrate the applicability of this strategy, we selected Euphorbia helioscopia L. as an example. 135 nodes were annotated, and three reference nodes were obtained. From the selected 35 target nodes, 10 purified compounds were isolated and elucidated. Among these, three were identified as novel compounds, while the remaining nine were discovered for the first time in Euphorbia helioscopia L. By using this strategy, we can effectively minimize the interference from redundant nodes and discover potentially new compounds.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143955054","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":"Enhanced electrochemical detection of acetaminophen using CoNi-LDH-based sensor with ultra-wide linear range and superior performance.","authors":"Jianxia Gu, Li Fan, Jian Bai, Zhanbin Jin, Tingting Wei","doi":"10.1007/s00216-025-05901-4","DOIUrl":"https://doi.org/10.1007/s00216-025-05901-4","url":null,"abstract":"<p><p>Electrochemical sensors for acetaminophen (AP) determination often face limitations in linear range, rarely achieving millimolar levels. This work synthesized CoNi-LDH (cobalt-nickel layered double hydroxide) via a simple hydrothermal method. By optimizing the Co/Ni ratio, the sensor based on CoNi-LDH-1 demonstrates efficient AP detection with an ultra-wide linear range spanning from 5 μM to 5 mM, enabling versatile AP monitoring in diverse samples. Furthermore, the sensor also exhibits exceptional stability, reproducibility, and selectivity. Notably, it successfully quantified AP in real-world samples (tap water and urine) while maintaining a wide linear range. The superior performance of the sensor stems from CoNi-LDH-1's unique spiky sphere morphology, abundant active sites, enhanced electron transport capability, and the synergistic effect between Co and Ni components. This work provides valuable insights for expanding the linear range of electrochemical sensors, advancing their application in analytical chemistry.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143960757","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":"Effects of defined organic layers on the fluorescence lifetime of plastic materials.","authors":"Nina Leiter, Maximilian Wohlschläger, Martin Versen, Sonja D Harter, Tina Kießlich, Franziska Lederer, Stefanie Clauß, Dietmar Schlosser, Emanuel Gheorghita Armanu, Christian Eberlein, Hermann J Heipieper, Martin G J Löder, Christian Laforsch","doi":"10.1007/s00216-025-05888-y","DOIUrl":"https://doi.org/10.1007/s00216-025-05888-y","url":null,"abstract":"<p><p>Plastics have become an integral part of modern life, and linked to that fact, the demand for and global production of plastics are still increasing. However, the environmental pollution caused by plastics has reached unprecedented levels. The accumulation of small plastic fragments-microplastics and nanoplastics-potentially threatens organisms, ecosystems, and human health. Researchers commonly employ non-destructive analytical methods to assess the presence and characteristics of microplastic particles in environmental samples. However, these techniques require extensive sample preparation, which represents a significant limitation and hinders a direct on-site analysis. In this context, previous investigations showed the potential of fluorescence lifetime imaging microscopy (FLIM) for fast and reliable identification of microplastics in an environmental matrix. However, since microplastics receive an environmental coating after entering nature, a challenge arises from organic contamination on the surface of microplastic particles. How this influences the fluorescence signal and the possibility of microplastic detection are unknown. To address this research gap, we exposed acrylonitrile butadiene styrene (ABS) and polyethylene terephthalate (PET) plastic samples to peptides, proteins, bacteria, and a filamentous fungus to induce organic contamination and mimic environmental conditions. We analyzed the fluorescence spectra and lifetimes of the samples using fluorescence spectroscopy and frequency-domain fluorescence lifetime imaging microscopy (FD-FLIM), respectively. Our results demonstrate that reliably identifying and differentiating ABS and PET was possible via FD-FLIM, even in the presence of these biological contaminations. These findings highlight the potential of this technique as a valuable tool for environmental monitoring and plastic characterization, offering a rapid and efficient alternative to currently used analytical methods.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143951824","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}