Analytical and Bioanalytical Chemistry最新文献

{"title":"Speciation analysis of fungi by liquid atmospheric pressure MALDI mass spectrometry.","authors":"Lily R Adair, Ian M Jones, Rainer Cramer","doi":"10.1007/s00216-025-06094-6","DOIUrl":"https://doi.org/10.1007/s00216-025-06094-6","url":null,"abstract":"<p><p>Fungal pathogens pose a growing threat to global health, necessitating rapid and accurate identification methods. Here, liquid atmospheric pressure matrix-assisted laser desorption/ionisation (LAP-MALDI) mass spectrometry (MS) is applied to fast lipid and protein profiling of Candida albicans and Saccharomyces cerevisiae from cultured colonies. Species-specific lipid profiles were observed in the m/z 600-1100 range, dominated by phospholipids as confirmed by tandem mass spectrometry (MS/MS). Following simple solid phase extraction clean-up, LAP-MALDI mass spectra revealed multiply charged protein ions suitable for MS/MS analysis. For C. albicans, the fully mature, species-specific WHS11 protein (~ 7 kDa; P43074) was detected intact and confidently identified by top-down MS/MS proteoform sequencing, including the cleavage of the N-terminal methionine initiator and the associated N-terminal acetylation. For S. cerevisiae, a set of proteoforms were sequenced by MS/MS analysis, which led to the identification of two species-specific proteins within the 'UniProtKB reference proteomes + Swiss-Prot' target database. One of these was also detected intact, and sequenced and identified as the fully mature HSP12 protein (~ 11.5 kDa; P22943). This work demonstrates the potential of LAP-MALDI MS and MS/MS biotyping as a powerful, label-free platform for rapid fungal classification and proteoform characterisation, offering substantial improvements over conventional MALDI biotyping.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144999330","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":"Computational mass spectrometry for exposomics in non‑target screening.","authors":"Torsten C Schmidt, Gerrit Renner, Saer Samanipour","doi":"10.1007/s00216-025-06093-7","DOIUrl":"https://doi.org/10.1007/s00216-025-06093-7","url":null,"abstract":"","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145005750","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":"Novel spectrophotometric approaches for analysis of solifenacin and silodosin in pharmaceutical preparations, human plasma, and environmental water samples: assessment of the methods' greenness and practicality.","authors":"Aya Saad Radwan, Mohamed Hefnawy, Talha Bin Emran, Mohamed M Salim","doi":"10.1007/s00216-025-06076-8","DOIUrl":"https://doi.org/10.1007/s00216-025-06076-8","url":null,"abstract":"<p><p>The recent approval of a fixed-dose combination of silodosin (SOD) and solifenacin succinate (SOF) for overactive bladder syndrome has created a need for innovative analytical approaches enabling their simultaneous quantification. In this work, seven novel, eco-friendly, and cost-efficient spectrophotometric methods were developed for the concurrent determination of SOD and SOF. These methods overcome the limitations of conventional techniques by eliminating the need for complex instrumentation, labor-intensive procedures, and large volumes of hazardous organic solvents, offering a sustainable and accessible analytical alternative. A direct UV method (Method I) enabled selective quantification of SOD at 270 nm (1.0-15.0 μg/mL) with complete spectral independence from SOF. Given the substantial overlap between SOD and SOF spectra, six advanced UV-based methods including dual-wavelength, first derivative, ratio spectra difference, first derivative of ratio spectra, ratio subtraction, and absorption factor were innovatively applied for the accurate quantification of SOF (1.0-12.0 μg/mL). The applicability of the proposed methods was demonstrated through accurate analysis of SOD and SOF in combined pharmaceutical formulations and spiked human plasma, with no interference from excipients or endogenous compounds. The proposed methods were designed to be multifunctional, allowing their application in various analytical settings. They were successfully validated and applied for the quality control analysis of co-formulated pharmaceutical tablets, determination of SOD in spiked human plasma for biological use, and for environmental monitoring in different water matrices. This broad applicability highlights the methods' versatility, robustness, and practical value in routine laboratory analysis. Furthermore, their performance in environmentally relevant aqueous samples underscored their sensitivity and robustness, yielding excellent recovery rates and low %RSD values. Method greenness and practicality were critically evaluated using the GAPI, AGREE, and the recently introduced CACI tool, all confirming the exceptional eco-friendliness and economic viability of the approaches. Full compliance with ICH Q2(R2) guidelines further affirms their validity for routine quality control and environmental monitoring.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144991159","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":"Selection and characterization of novel DNA aptamers targeting colorectal cancer cells with malignant potential.","authors":"Yinuo Ma, Qun Wang, Shihan Sun, Yanxi Li, Rui Wang, Haihui Yang, Dian Wang, Yangyang Hao, Yujing Tong, Wanming Li","doi":"10.1007/s00216-025-06091-9","DOIUrl":"https://doi.org/10.1007/s00216-025-06091-9","url":null,"abstract":"<p><p>Colorectal cancer (CRC) is associated with high morbidity and mortality rates worldwide. Therefore, early diagnosis and treatment are of great significance for improving the survival rate of CRC patients. Herein, we performed subtractive cell-SELEX using two cell lines (LS174T and CL187) with the same genetic background but different malignant potentials for the target and negative cells. Two aptamers LS1 and LS52 showed high affinity with target LS174T cells and high specificity for CRC cells with malignant potential, and exhibited good biological stability. In addition, we found that aptamer LS1 had the effect of promoting in vitro proliferation and monoclonal formation of CRC cells, and upregulated the expression of proliferation related proteins. Based on the high affinity of aptamer LS52, using LS52 as a molecular probe could effectively distinguish clinical CRC tissues and adjacent normal tissues, CRC metastatic tissues and non-metastatic tissues. Analysis of protein expression in magnetic bead sorted cells showed that the expression of malignant potential related proteins in LS52^high cells was higher than that in LS52^low cells. Finally, a cell membrane protein SRSF6 was identified as the target of aptamer LS52, which may serve as a new molecular target for CRC. Therefore, our work provides a systematic novel approach of studying potential biomarkers and a promising tool for cancer diagnosis and therapy.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144937983","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":"Development of a strategy for sampling, preservation, and analysis of classical and emerging flame retardants and plasticizers in air samples","authors":"Judith Desmet,&nbsp;Maria A. Aretaki,&nbsp;Mar Viana,&nbsp;Ethel Eljarrat","doi":"10.1007/s00216-025-06057-x","DOIUrl":"10.1007/s00216-025-06057-x","url":null,"abstract":"<div><p>This study presents a methodology for sampling, preserving, and analyzing 15 organophosphate esters (OPEs), 11 phthalate esters (PEs), and 6 alternative plasticizers (APs) in indoor air. Accurate quantification is essential, given their widespread use in household items and adverse health effects associated with exposure. Solid-phase extraction (SPE) cartridges, collecting both gaseous and particulate phases, connected to a low-volume pump were used for the collection of air samples. Stability tests confirm that storing samples at 4 °C is most optimal to maintain analyte integrity for at least 2 weeks. The analytes were extracted and then purified online using turbulent flow chromatography, before analysis via liquid chromatography-tandem mass spectrometry (TFC-LC–MS/MS). Quantification was carried out by applying the isotopic dilution method with labelled standards. Recoveries ranged from 50 to 136%, with reproducibility below 21%. The relative standard deviation (RSD) varied from 2 to 31%, only exceeding the 20% threshold for certain OPEs at lower concentrations. Limits of detection (mLODs) varied between 0.02–0.89 ng/m³, 0.02–20.0 ng/m³, and 0.07–1.47 ng/m³ for OPEs, PEs, and APs, respectively. The study demonstrates that this methodology is effective, cost-efficient, and suitable for monitoring a total of 33 flame retardants and plasticizers in indoor air. It minimizes material costs and sample handling time by allowing direct analysis without pretreatment. Results from indoor air samples collected in a case study revealed that OPEs attributed to less than 20% of the chemical profile, while triethyl citrate (TEC) was detected at concentrations up to 28.9 ng/m³, confirming the method’s applicability for the added APs.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":"417 23","pages":"5335 - 5347"},"PeriodicalIF":3.8,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12432039/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144937810","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":"Large-scale generation of in silico based spectral libraries to annotate dark chemical space features in non-target analysis.","authors":"Emil Egede Frøkjær, Martin Hansen","doi":"10.1007/s00216-025-06034-4","DOIUrl":"https://doi.org/10.1007/s00216-025-06034-4","url":null,"abstract":"<p><p>In this study, we develop and present an open-access LC-electrospray-HRMS/MS forward in silico fragmentation spectral library, based on the NORMAN Suspect List Exchange containing 120,514 chemicals, that can be used for level 3 annotations to support elucidation of the dark molecular features detected in environmental, exposomic, food safety, and forensic investigations. Using these forward generated in silico spectral libraries, several pollutants previously unreported in non-targeted workflows were discovered in groundwater for the first time through retrospective non-targeted screening analysis. Among these are xenobiotics such as hexafluoroacetone, hexazinone metabolites A, B, and C, and transformation products of triflusulfuron, fluazifop-butyl, triallate, and propiconazole. The generated in silico spectral libraries are freely available at https://doi.org/10.5281/zenodo.14854025 .</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144937955","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":"Global metabolomics profiling of glucuronides in human plasma, fecal, and cerebrospinal fluid samples.","authors":"Ioanna Tsiara, Mario S P Correia, Fan Yang, Weiming Zeng, Pauline Seeburger, Belén Hervás Povo, Iben Lundgaard, Manuel Menéndez-González, Miroslav Vujasinovic, J-Matthias Löhr, Daniel Globisch","doi":"10.1007/s00216-025-06082-w","DOIUrl":"https://doi.org/10.1007/s00216-025-06082-w","url":null,"abstract":"<p><p>Glucuronidation is the major phase II biotransformation reaction that facilitates the clearance of exogenous compounds from the human body. Glucuronidated metabolites have been investigated in urine samples at a broad scale; however, their characterization in other human biospecimens is underexplored. Our study has now performed a comprehensive profiling of glucuronides in plasma, fecal, and cerebrospinal fluid (CSF) of humans. We performed a mass spectrometry-based analysis that combines enzymatic hydrolysis with a β-glucuronidase to selectively cleave the glucuronic acid moiety, a developed in-house glucuronide identification pipeline, and enzymatic synthesis of standard metabolites. In total, we identified 32 glucuronidated metabolites across the three sample types in both negative and positive mass spectrometry ionization modes using advanced MS/MS fragmentation analysis. We have utilized a straightforward enzymatic synthesis of glucuronidated metabolites for annotation at the highest confidence level. Among the identified conjugates, we detected glucuronides of different compound classes including drugs, bile acid derivatives, steroid conjugates, and phenolic compounds. Unexpectedly, we validated the glucuronides of acetaminophen and propofol in CSF samples, the latter representing a novel observation that highlights the importance of investigating phase II metabolites in uncommon sample types.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144937901","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":"Synthesis and characterization of miniaturized aptamer-based monolithic sorbent for selective extraction of β-amyloid peptides from cerebrospinal fluid.","authors":"Israel Donizeti de Souza, Caroline Fernandes Grecco, Maria Eugênia Costa Queiroz, Valerie Pichon, Audrey Combès","doi":"10.1007/s00216-025-06085-7","DOIUrl":"https://doi.org/10.1007/s00216-025-06085-7","url":null,"abstract":"<p><p>The ratio between beta-amyloid (Aβ) peptides 40 and 42 is recognized as a biomarker for Alzheimer's disease, playing a significant role in early diagnosis and disease progression monitoring. Aβ peptides are present at trace levels in cerebrospinal fluid, therefore, developing a new selective extraction procedure is essential for isolating targeted biomarkers from the matrix interferents, ensuring accurate identification and quantification. In this study, a hybrid organic-silica monolith was synthesized in a 530 µm inner diameter-capillary and used for the covalent grafting of beta amyloid peptide aptamers. The resulting miniaturized oligosorbent (mOS) was applied to selectively extract Aβ peptides 40 and 42 from artificial cerebrospinal fluid (CSF) samples. The immobilization procedure achieved grafting yields higher than 90% leading to a dense coverage of Aβ aptamers (655 + 15 pmol.µL^-1 of oligosorbent, n = 3, RSD = 2.3), and in a capacity exceeding 50 pmol.µL^-1 of mOS. After optimization in pure media, an extraction recovery of 74% and 31% for Aβ40 and Aβ42 peptides, respectively was reached on this mOS. The developed method including extraction on mOS and LC-MS analysis achieved LLOQ values of 0.1 ng.mL^-1, precision and accuracy with CV and RSD values ranging from 1.0% to 12.9% and -4.7% to 11.1%, respectively. This method was successfully applied to selectively extract Aβ peptides from artificial CSF samples, effectively isolating the two Aβ targeted peptides from this complex biological fluid and enhancing trace-level analysis reliability.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144938155","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":"Highly sensitive and high-throughput detection of human alkyladenine DNA glycosylase via hybridization chain reaction-assisted quantum dot fluorescent assay.","authors":"Xueguo Liu, Minglin Lei, Yizhuo Zhao, Xueying Meng, Dongwan Li, Keyi Zhao, Shuqi Sun, Huanhuan Xing, Xiaojing Xing","doi":"10.1007/s00216-025-06088-4","DOIUrl":"https://doi.org/10.1007/s00216-025-06088-4","url":null,"abstract":"<p><p>Human alkyladenine DNA glycosylase (hAAG) is an important enzyme in the base excision repair (BER) pathway, and its abnormal expression is correlated with various human diseases. While several methods have been developed for hAAG detection, constructing low-background, highly sensitive, and high-throughput techniques remains a significant challenge. Herein, we introduce a highly sensitive and high-throughput platform for hAAG activity detection, utilizing quantum dots (QDs) as the signal sensitizer, the hybridization chain reaction (HCR) for signal amplification, and microplate wells for high-throughput analysis. The custom-designed hairpin DNA substrate with a glycosylase recognition site undergoes a conformational change upon the addition of hAAG and apurinic/apyrimidinic endonuclease 1 (APE1), resulting in the generation of primer chains. These released primer chains then initiate HCR-mediated signal amplification, creating numerous binding sites for DNA-functionalized QD (DNA-QD) probes. This method displays minimal background signal owing to the stable structure of the hairpin substrate and demonstrates excellent sensitivity with a detection limit of 0.012 U/mL. Notably, this strategy enables versatile evaluation of the hAAG inhibitor as well as the detection of endogenous hAAG from cancer cells, highlighting its potential for early clinical diagnosis. Additionally, this strategy could be adapted to quantify various DNA repair enzymes by rationally modifying the DNA substrates.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144937934","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":"Screening and optimization of online comprehensive two-dimensional liquid chromatography conditions for the analysis of hospital wastewater.","authors":"Marie Pardon, Soraya Chapel, Peter de Witte, Deirdre Cabooter","doi":"10.1007/s00216-025-06071-z","DOIUrl":"https://doi.org/10.1007/s00216-025-06071-z","url":null,"abstract":"<p><p>Pharmaceutical residues in freshwater systems constitute a growing environmental problem. An important point source of these pharmaceuticals is hospital wastewater. The characterization of hospital wastewater is challenging because of its complex nature. Pharmaceuticals and their metabolites display a large variety of physicochemical properties, while matrix compounds create additional complexity. Innovative analytical approaches are hence needed to characterize these challenging samples. A promising technique is online comprehensive two-dimensional liquid chromatography (LC × LC), combining two orthogonal separation modes to increase the separation power significantly. Because of the many optimization parameters involved, method development in online LC × LC is complicated. It is difficult to predict which combinations will result in the highest peak capacity for a specific sample. In this work, different separation systems are evaluated for the online LC × LC analysis of pharmaceuticals, using an in-house developed Python-based 2D combination selector (PCS) tool. Practical peak capacities of different combinations, determined using an orthogonality score based on 12 different orthogonality metrics and predicted peak capacities, are used to select promising LC × LC conditions, including reversed-phase (RPLC) and hydrophilic interaction (HILIC) LC. Three promising combinations are further optimized, with special focus on their mobile phase incompatibility. To deal with these incompatibility issues, both active solvent modulation and flow splitting are investigated. After optimization, the RPLC × RPLC method displays the best ²D-peak shapes and highest effective peak capacity (1877) in line with predictions made by the PCS tool, highlighting its effectiveness for online LC × LC method development. The RPLC × RPLC method is successfully applied to identify 36 pharmaceuticals of various classes in real hospital wastewater.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144938078","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}