Analytical Methods最新文献

{"title":"Amino-functionalized Fe₃O₄@SiO₂-NH₂@MIL-101(Fe)-NH₂ for magnetic solid-phase extraction of PFOA and PFOS from water and milk.","authors":"Liqun Chen, Haizhi Wu, Qian Wu, Xinyao Qu, Yuwei Peng, Li Jiang, Yuan Yang, Dengni Lai, Yang Guo","doi":"10.1039/d6ay01593j","DOIUrl":"https://doi.org/10.1039/d6ay01593j","url":null,"abstract":"<p><p>Per- and polyfluoroalkyl substances, known as PFASs, are persistent organic pollutants. Perfluorooctanoic acid and perfluorooctane sulfonate, referred to as PFOA and PFOS, respectively, require selective sample preparation before trace-level LC-MS/MS analysis. Herein, an amino-functionalized magnetic MIL-101(Fe) composite, Fe₃O₄@SiO₂-NH₂@MIL-101(Fe)-NH₂, was synthesized and applied as an MSPE sorbent for PFOA and PFOS in water and dairy matrices. The composite integrates magnetic Fe₃O₄@SiO₂-NH₂ nanoparticles with an amino-functionalized MIL-101(Fe) porous framework, enabling rapid magnetic separation and multiple adsorption interactions. Adsorption equilibrium was reached within 10 min, and the adsorption mechanism was dominated by electrostatic attraction, hydrogen-bonding, and hydrophobic interactions. Under optimized conditions, the method exhibited satisfactory linearity within the ranges of 0.05-50 ng mL^-1 and 0.5-50 ng mL^-1 for PFOA and PFOS, respectively. The limits of detection were 0.25 ng L^-1 for PFOA and 2.5 ng L^-1 for PFOS in water, and 0.005 ng g^-1 for PFOA and 0.020 ng g^-1 for PFOS in dairy samples. Recoveries ranged from 73.86% to 118.30% with RSDs no more than 15%. The sorbent remained stable over five consecutive cycles and was successfully applied to spiked water, milk, and milk powder samples. This work provides a practical strategy for designing amino-functionalized magnetic MOF composites for rapid and sensitive enrichment of PFOA and PFOS in complex environmental and food matrices.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177940","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Decoupling the kinetic fingerprints of ammonia and acetone interfacial dynamics over ZnO-rGO heterojunction gas sensors.","authors":"Namitha N N, Sree Rama Murthy Anupindi","doi":"10.1039/d6ay01747a","DOIUrl":"https://doi.org/10.1039/d6ay01747a","url":null,"abstract":"<p><p>Discriminating analytes with overlapping signals remains a significant challenge for metal oxide gas sensors. This study presents a methodology to decouple the kinetic fingerprints of ammonia and acetone using ZnO-rGO heterojunctions. <i>In situ</i> prepared rGZO_i5 composites, featuring 12 nm ZnO nanoparticles anchored on rGO defect sites, exhibited superior sensitivity compared to physical mixtures. At operating temperatures of 443 K and 453 K, the sensor revealed distinct temporal signatures: acetone follows pseudo-first-order kinetics with a sluggish sigmoidal recovery (up to 1684 s), whereas ammonia follows zero-order kinetics with rapid Elovich-type relaxation. Mechanistic analysis shows that acetone is bottlenecked by a complex redox pathway with an activation energy barrier of 0.58 eV for water desorption. Conversely, ammonia's 3-electron pathway enables near-instantaneous re-oxygenation of the surface. A Continuous Stirred-Tank Reactor (CSTR) dilution model confirms that recovery delays are dictated by surface-limited chemical bottlenecks rather than carrier transport. With theoretical limits of detection of 3.4 ppm for acetone and 14.8 ppm for ammonia at 453 K, this kinetic profiling framework offers a robust path toward high selectivity.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177994","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ratiometric differential sensing of biophosphates using a ligand-diversified Fe-MOF nanozyme array.","authors":"Runrun Yang, Zhiyuan Luo, Hailong Shi, Lingyun Cheng, Miao Zhang, Ziyi Zhao, Jihua Zeng, Siqi Li","doi":"10.1039/d6ay01951j","DOIUrl":"https://doi.org/10.1039/d6ay01951j","url":null,"abstract":"<p><p>Discriminating structurally similar biophosphates remains challenging for conventional single-channel sensing systems. Here, we develop a ratiometric differential sensing strategy based on a three-channel array of ligand-diversified Fe-MOF nanozymes, Fe-IPA-NH₂, Fe-TPA-NH₂, and Fe-TPA-OH. Each Fe-MOF combines intrinsic fluorescence with peroxidase-like activity and catalyzes the H₂O₂-mediated oxidation of <i>o</i>-phenylenediamine (OPD) to fluorescent 2,3-diaminophenazine (DAP). Phosphate-dependent modulation of the catalytic process produces coupled changes in the DAP emission and the intrinsic Fe-MOF emission. These outputs were converted into an internally referenced ratio (<i>R</i> = <i>F</i>₅₅₀/<i>F</i>_MOF) and then normalized to the phosphate-free response (<i>R</i>/<i>R</i>₀), generating self-referenced cross-reactive fingerprints. Chemometric analysis enabled discrimination of PPi, Pi, ATP, ADP, and AMP at 5 µM and maintained distinct clustering at 3, 1, and 0.5 µM. The array also differentiated PPi concentration levels and resolved binary PPi/Pi mixtures with varying compositions. By integrating ligand-diversified cross-reactivity, ratiometric normalization, and multivariate decoding, this work provides a proof-of-concept strategy for differential sensing of structurally related analytes.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177988","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An oriented epitope-imprinted fluorescent sensor based on magnetic carbon dots for specific detection of CD47.","authors":"Hai Wang, Rui Wang, Ganping Cai, Qiong Jia","doi":"10.1039/d6ay01390b","DOIUrl":"https://doi.org/10.1039/d6ay01390b","url":null,"abstract":"<p><p>Cluster of differentiation 47 (CD47), a transmembrane glycoprotein overexpressed in various tumor cells, serves as an important immunoregulatory molecule and has emerged as a promising biomarker for disease diagnosis and therapeutic targeting. This research developed a magnetic fluorescent molecularly imprinted polymers (MMIPs)-based sensor for highly selective, sensitive, and rapid detection of CD47. The sensor was constructed by creating imprinted cavities on the surface of magnetic carbon dots (MCDs) through boronate affinity-oriented immobilization of a fructose-modified CD47 epitope, combined with zinc acrylate-assisted metal chelation. This oriented epitope imprinting strategy ensures precise control over template orientation, leading to improved binding site homogeneity and enhanced recognition performance. Under optimized conditions, the performance evaluation indicates that the sensor achieves a detection limit of 4.97 µmol L^-1, coupled with excellent selectivity, a rapid response (20 min), and high accuracy in human serum samples (recovery rates of 96.4-101.6%). This platform thereby provides a reliable tool for CD47 detection in complex biological samples.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177919","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Surface chemical differentiation of fingermark samples by ToF-SIMS and multivariate statistical analysis.","authors":"Katja Andrina Varda, Matjaž Finšgar","doi":"10.1039/d6ay01563h","DOIUrl":"https://doi.org/10.1039/d6ay01563h","url":null,"abstract":"<p><p>This study demonstrates the applicability of time-of-flight secondary ion mass spectrometry (ToF-SIMS) combined with multivariate statistical analysis (MVSA) for the chemical differentiation of fingermarks from eight donors. Multiple ToF-SIMS spectra were measured on a small area of each fingermark sample to assess whether chemical variability between the fingermark samples exceeded chemical variability within each individual one. Principal component analysis (PCA) enabled the separation of fingermark samples from different donors, while multivariate curve resolution (MCR) further resolved individual fingermark-associated MCR factors and revealed characteristic <i>m</i>/<i>z</i> signals contributing to fingermark sample discrimination. Some characteristic signals were confirmed as unique donor-associated signals within the examined dataset, whereas others still enabled donor differentiation because their relative intensities within the ToF-SIMS spectra differed across the spectral dataset obtained from different donors. This work demonstrates that combining ToF-SIMS and MVSA can provide a promising complementary methodology to conventional fingermark morphology analysis, particularly when only small areas of fingermark residue are available.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177976","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical ultrasensitive detection of miRNA-21 <i>via</i> RAFT/ROMP dual polymerization amplification.","authors":"Jiaxun Zhang, Shijin Zhou, Jinming Kong, Xueji Zhang","doi":"10.1039/d6ay01493c","DOIUrl":"https://doi.org/10.1039/d6ay01493c","url":null,"abstract":"<p><p>The ultrasensitive detection of microRNAs in bodily fluids is crucial for early diagnosis of cancer. Herein, we design an electrochemical biosensor based on a dual-signal amplification strategy utilizing reversible addition-fragmentation chain transfer (RAFT) and ring-opening metathesis polymerization (ROMP) to achieve ultra-sensitive quantitative detection of miRNA-21. The sensing interface starts from a gold electrode carrying a thiol-immobilized peptide nucleic acid (PNA) capture probe. Once miRNA-21 hybridizes specifically with the PNA, we anchor the RAFT chain-transfer agent 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (CDTPA) onto the duplex by taking advantage of Zr⁴⁺ coordination chemistry. With the azo initiator 2,2'-azobis[2-(2-imidazolin-2-yl) propane] dihydrochloride (VA-044), in solution, the monomer dicyclopentenyloxyethyl acrylate (DCPEA)-which bears a cyclopentene side group-undergoes RAFT polymerization, decorating the duplex with polymer chains that bristle with pendant cyclopentene rings. Subsequently, the ruthenium-based catalyst AquaMet ((4-((4-ethyl-4-methylpiperazin-1-ium-1-yl)methyl)-1,3-dimesitylimidazolidin-2-ylidene)dichloro(2-isopropoxybenzylidene) ruthenium(II)) chloride coordinates with the cyclopentene groups, catalyzing the ROMP of cyclopentene-based ferrocene (CFc), thereby forming a polymer brush rich in ferrocene electroactive molecules on the electrode surface, achieving efficient two-stage amplification of the electrochemical signal. Under optimized conditions, the sensor returns a linear response to miRNA-21 from 10^-17 M to 10^-13 M and reaches a detection limit as low as 4.72 aM. Signals from single-mismatched RNA, triple-mismatched RNA, and miRNA-320b were all strongly suppressed relative to the target, while the sensor also proved to be stable in one week and remarkably unfazed by complex biological backgrounds.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149163353","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Aptamer-gated FRET nanosensor based on UCNPs-AuNSs for sensitive detection of methylmercury in seafood matrices.","authors":"Shiyu Li, Junrong Yang, Tong Zhu, Mengfei Wang, Quansheng Chen, Min Chen","doi":"10.1039/d6ay01774f","DOIUrl":"https://doi.org/10.1039/d6ay01774f","url":null,"abstract":"<p><p>Methylmercury (CH₃Hg⁺) is the most toxic form of mercury found in fish, shellfish, and other aquatic organisms and poses significant risks to human health through the food chain. The present study reports the development of a fluorescence aptasensor for the quantification of CH₃Hg⁺ using aptamer-functionalized gold nanostars (AuNSs) and complementary DNA-functionalized alendronic acid-modified upconversion nanoparticles (ADA-UCNPs). The ADA-UCNPs-AuNSs fluorescence aptasensor employed an on-off detection mode and completed the detection within 60 min. The developed fluorescence aptasensor exhibited a good linear response to CH₃Hg⁺ over the concentration range of 0.5 to 20.0 µM, with a limit of detection of 0.37 µM. The aptasensor exhibited satisfactory accuracy and precision, with relative standard deviations within the evaluated CH₃Hg⁺ concentration range and recoveries of 91.00% to 99.20% in aquatic products. The newly constructed aptasensor also showed satisfactory selectivity and resistance to interference and maintained good stability, supporting its potential for practical application in food monitoring.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177925","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Miniaturized multi-analytical characterization of aliphatic amines, dicarbonyls, and PAHs in PM₂.₅<i>via</i> low-mass filter aliquots: analytical workflow and environmental application.","authors":"Susana García-Alonso, María Leco, Javier Fernández-García, Rosa María Pérez-Pastor","doi":"10.1039/d6ay02187e","DOIUrl":"https://doi.org/10.1039/d6ay02187e","url":null,"abstract":"<p><p>This work presents a downscaled and resource-efficient multi-analytical workflow for the parallel determination of polar indicators (aliphatic amines, short-chain dicarbonyls, malondialdehyde) and combustion tracers (PAHs) using micro-aliquots of PM₂.₅ filters (0.07 g, equivalent to ∼60 m³ of sampled air). By implementing dedicated chemical derivatization protocols (Fmoc-Cl for amines and acid-catalyzed DNPH for dicarbonyls) alongside direct solvent extraction for PAHs, the method minimizes sample consumption and solvent waste while achieving limits of detection in the low pg m^-3 to ng m^-3 range. Procedural optimization ensured robust intermediate precision (<12% RSD across target analytes) and controlled reagent hydrolysis artifacts. The analytical performance was validated through a three-day field study during a sharp meteorological transition, demonstrating that the downscaled strategy effectively resolves short-term diurnal shifts and local chemical transformations from minimal sample mass without requiring full-filter destruction.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177954","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A machine learning-assisted analytical approach for the prediction of non-small cell lung cancer using UHPLC-HILIC-FLD serum <i>N</i>-glycan profiles.","authors":"Betül Karabudak, Fatih Karataş, Ezgi Ekinci Binici, Erkan Dikmen, Zeliha Günnur Dikmen, Ozan Yazıcı, Orhun Akdoğan, Murat Acat, Hakan Yılmaz, Bekir Salih, Hacı Mehmet Kayılı","doi":"10.1039/d6ay01803c","DOIUrl":"https://doi.org/10.1039/d6ay01803c","url":null,"abstract":"<p><p>The lack of robust early-stage molecular biomarkers severely limits the timely diagnosis of non-small cell lung cancer (NSCLC). To address this analytical challenge, we developed an integrated workflow combining serum <i>N</i>-glycan profiling with machine learning (ML) algorithms to explore the discriminatory patterns of serum <i>N</i>-glycan profiles between NSCLC and control groups and across disease stages. <i>N</i>-Glycans were analyzed using ultra-high-performance liquid chromatography with hydrophilic interaction chromatography and fluorescence detection (UHPLC-HILIC-FLD). The resulting high-dimensional chromatographic data from patient and control cohorts were subjected to statistical and ML analyses. Serum glycan profiling revealed marked dysregulation of the glycome. Twenty of the 28 <i>N</i>-glycan peaks showed significant cancer-associated alterations, with selected features also exhibiting stage-specific differences. Notably, relative quantitation showed that the agalactosylated core-fucosylated glycan G1 (H3N4F1) increased 2.55-fold in the cancer cohort. To evaluate the diagnostic utility of these glycomic profiles, nine ML models were trained and evaluated using 5-fold cross-validation. A neural network (NN) model demonstrated strong classification performance, achieving an area under the curve (AUC) of 0.93 for binary classification (NSCLC <i>vs.</i> healthy controls) and 0.91 for three-class classification. Furthermore, SHapley Additive exPlanations (SHAP) analysis elucidated the model decision-making process, identifying glycans G7 (H5N4), G23 (H6N5S3), and G2 (H3N5F1 and H5N2) as key features contributing to classification. These findings indicate that integrating UHPLC-HILIC-FLD serum glycomic profiling with explainable machine learning provides an exploratory analytical framework for identifying candidate glycan features associated with NSCLC status and stage.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149163879","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"MnFe₂O₄-based hybrid nanomaterials for high-performance electrochemical sensors: recent progress and future perspectives.","authors":"Khursheed Ahmad, Shanmugam Vignesh, Vinay Kumar Tripathi, Vivek Mani Tripathi, Rohit Kumar Singh Gautam, Tae Hwan Oh","doi":"10.1039/d6ay01584k","DOIUrl":"https://doi.org/10.1039/d6ay01584k","url":null,"abstract":"<p><p>Manganese ferrite (MnFe₂O₄) is a promising electrode material because of its redox-active Mn and Fe centers, chemical stability, and tunable spinel structure. However, its practical use in electrochemical sensing may be limited due to its poor electrical conductivity, particle aggregation, and limited access to active sites. This review discusses recent advances in the fabrication of pristine and hybrid MnFe₂O₄-based electrochemical sensors. It is understood that synthesis methods, surface morphology, crystallinity, defects, and interfacial composition influence sensing performance. Various preparation methods such as hydrothermal, sol-gel, co-precipitation, microwave-assisted, sonochemical, electrodeposition, and thermal decomposition have been briefly discussed. The analytical sensing performance of MnFe₂O₄ incorporated with carbon materials, polymers, metal-organic framework-derived materials, chitosan, and noble-metal nanoparticles (NPs) has been discussed for the detection of heavy metals, hydrogen peroxide, pharmaceuticals, pesticides, endocrine disruptors, and biomolecules. It is believed that MnFe₂O₄-based hybrid materials may exhibit improved conductivity, active surface area, analyte adsorption, and selectivity. Therefore, MnFe₂O₄-based hybrid materials demonstrate enhanced sensing performance. Subsequently, challenges and future perspectives have been discussed.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149163482","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}