Analytical Chemistry最新文献

{"title":"Localized Surface Plasmon Resonance-Mediated Fabry-Pérot Interferometer for Enzyme-Free Glucose Detection.","authors":"Hairihan Zhou, Yue Zhang, Yueyang Zhang, Yinde Wu, Chenxi Zhao, Zhida Gao, Pei Song, Yan-Yan Song, Xiaona Li","doi":"10.1021/acs.analchem.5c02134","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c02134","url":null,"abstract":"<p><p>The well-known Fabry-Pérot (F-P) cavity serves as a crucial element of complex optical devices, offering distinctive functionalities. However, modifying reflection properties by altering the underlying optical structure remains challenging. Inspired by the optical modulation ability of plasmonic nanoparticles (NPs) and the sensitivity of reflective interferometric Fourier transform spectroscopy (RIFTS) of the F-P cavity to effective optical thickness (EOT), herein, a local surface plasmon resonance (LSPR) effect-mediated F-P interferometer with improved sensing ability is proposed. Using glucose as a model analyte, the TiO₂ nanotube (NT)-based F-P interferometer is constructed by integrating a pH-responsive block copolymer (BCP) film and LSPR-mediated enzyme-like reactions in interferometric TiO₂ NTs. The high-energy hotspots generated by the Au-LSPR effect can accelerate glucose oxidation in NTs, which generates gluconic acid and H₂O₂ as the products. By combining the experimental results with COMSOL simulations, it is found that the satisfactory response achieved in reflective interferometric Fourier transform spectroscopy (RIFTS) not only relates to the enhanced reflectivity induced by AuNPs but also depends on the EOT changes mediated by the Au-LSPR effect. The plasmon-mediated F-P interferometer offers sensitive glucose quantification with satisfactory performance in real samples, suggesting a new route to design an F-P cavity with a highly sensitive response for boosting target sensing performance.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":" ","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144281676","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Accurate Diagnosis of Colorectal Cancer Using a Combination of Lectin-Induced Recombinase Polymerase Amplification and CRISPR/Cas12a Assay on a Point-of-Care Testing Platform with Deep Learning Assistant.","authors":"Xudong Sun, Xiaotong Li, Hao Jiang, Yongjie Shan, Sifeng Zhou, Zhenxin Wang","doi":"10.1021/acs.analchem.5c00468","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00468","url":null,"abstract":"<p><p>Specific glycosylation patterns on exosome surfaces represent novel diagnostic biomarkers for cancer liquid biopsy. Lectins can induce exosome aggregation through multiple bindings with exosomal glycoproteins. In this work, we developed a one-pot lectin-induced recombinase polymerase amplification (RPA) and CRISPR/Cas12a-mediated cleavage assay (LI-RPA-CRISPR/Cas12a) for diagnosing colorectal cancer (CRC) through the interactions of abundant α-fucose residues on CRC cell-derived exosome surfaces with Ulex Europaeus Agglutinin I (UEA-I). The combination of a homemade portable isothermal amplification device, the as-proposed LI-RPA-CRISPR/Cas12a exhibits a wide detection range from 2 × 10⁶ to 1 × 10² extracellular vehicles (EVs) μL^-1 with a visual limit of detection (LOD) as low as 1.0 × 10² EVs μL^-1, and has been successfully utilized to dynamically monitor the progression of tumors in mice-bearing SW480 CRC subtype at an early stage. After integration with a long short-term memory (LSTM) deep learning model, the LI-RPA-CRISPR/Cas12a achieves accurate diagnosis of primary colorectal cancer with a drop of blood through a smartphone-based data analysis application, reaching an accuracy of 95% in 100 clinical samples. This rapid, sensitive, and user-friendly approach provides a promising platform for point-of-care testing (POCT) diagnosis of CRC, enabling early detection and monitoring of disease progression through a minimally invasive liquid biopsy.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":" ","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144281672","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Super-Resolution FLIM Imaging of Intracellular Lipid Microenvironments with a Dual-Responsive Polarity- and pH-Sensitive Fluorescent Probe","authors":"Shixian Cao, Caixia Sun, Wendong Jin, Dewang Jin, Xinru Hu, Zhiqiang Liu, Xiaoqiang Yu, Kang-Nan Wang","doi":"10.1021/acs.analchem.5c00826","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00826","url":null,"abstract":"The microenvironment is essential for the proper function of organelles and biological systems. In particular, its physical properties─such as polarity and pH profoundly influence both physiological and pathological processes. Therefore, directly visualizing and quantitatively measuring changes in the cellular microenvironment is crucial for advancing our understanding of these fundamental processes. Fluorescent probes capable of enabling direct visualization and quantitative analysis of the cellular microenvironment using STED/FLIM (stimulated emission depletion fluorescence and lifetime imaging microscopy) offer powerful tools for exploring intracellular biophysical properties with nanoscale resolution. However, such probes remain largely unexplored. Here, we present TPA-BT-CA, a highly photostable fluorescent probe that is both polarity- and pH-sensitive, enabling real-time super-resolution imaging and quantitative mapping of intracellular lipid distributions via STED/FLIM microscopy. The donor–acceptor–acceptor (D–A–A) structural design of TPA-BT-CA facilitates efficient intramolecular charge transfer, leading to strong fluorescence signals and prolonged fluorescence lifetimes in nonpolar environments, thereby allowing precise differentiation of lipid regions with varying polarity. Furthermore, protonation and deprotonation processes under acidic or alkaline conditions induce fluorescence lifetime shifts, enabling quantitative assessment of lipid distribution in living cells. This work establishes a new approach for high-resolution visualization and quantitative measurement of the cellular microenvironment, offering new insights into lipid organization and microenvironmental dynamics.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"19 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144269219","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Arg-C Ultra Simplifies Histone Preparation for LC-MS/MS.","authors":"Palina Ryzhaya, Pavlína Pírek, Zbyněk Zdráhal, Gabriela Lochmanová","doi":"10.1021/acs.analchem.5c02238","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c02238","url":null,"abstract":"<p><p>Arginine-specific cleavage is the primary method used to prepare lysine-rich histone proteins in bottom-up proteomics. As the Arg-C enzyme has demonstrated suboptimal specificity, cleavage at the carboxyl side of arginine residues is typically achieved through the chemical derivatization of lysines followed by trypsin digestion. Recent improvements in proteolytic enzymes are reflected in the introduction of Arg-C Ultra, a recombinant proteinase with a substantially improved digestion specificity. Here, using mammalian histone extract, we demonstrate that Arg-C Ultra facilitates histone preparation for LC-MS/MS. We show the performance of Arg-C Ultra in terms of digestion specificity, number of modified forms identified, and yield of quantitative information compared with Arg-C and trypsin digestion combined with chemical derivatization with trimethylacetic anhydride. Importantly, we show that chemical derivatization at the peptide level, i.e., after Arg-C Ultra digestion, is still necessary to improve the quantification of short histone peptidoforms as well as positional isomers.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":" ","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144281673","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"In Situ Quantification of Ammonia in Biofluids using High-Resolution Nuclear Magnetic Resonance.","authors":"Li-Hua Xu, Ya-Ting Chen, Xing Zhang, Xun-Cheng Su","doi":"10.1021/acs.analchem.5c00887","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00887","url":null,"abstract":"<p><p>Ammonia is an important metabolite and is involved in many physiological processes; the abnormal level of ammonia in vivo is correlated with the different phenotypes of diseases. Quantification of ammonia is important for disease diagnosis. However, in situ analysis of ammonia remains challenging due to the limitations of conventional methods, such as the toxicity of reactants and interference by amine analytes. Herein, we established a simple and reliable method for in situ quantification of ammonia using a series of ¹⁹F-Tags that are reactive to ammonia in aqueous solution and produce well-resolved NMR signals from other amine analytes in the NMR spectrum. This method has been effectively employed in the in situ quantification of ammonia at micromolar concentrations in biofluids, including cell lysates, human plasma, and human urine.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":" ","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144281675","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"On Selecting Robust Approaches for Learning Predictive Biomarkers in Metabolomics Data Sets.","authors":"Thibaud Godon, Pier-Luc Plante, Jacques Corbeil, Pascal Germain, Alexandre Drouin","doi":"10.1021/acs.analchem.5c01049","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c01049","url":null,"abstract":"<p><p>Metabolomics, the study of small molecules within biological systems, offers insights into metabolic processes and, consequently, holds great promise for advancing health outcomes. Biomarker discovery in metabolomics represents a significant challenge, notably due to the high dimensionality of the data. Recent work has addressed this problem by analyzing the most important variables in machine learning models. Unfortunately, this approach relies on prior hypotheses about the structure of the data and may overlook simple patterns. To assess the true usefulness of machine learning methods, we evaluate them on a collection of 835 metabolomics data sets. This effort provides valuable insights for metabolomics researchers regarding where and when to use machine learning. It also establishes a benchmark for the evaluation of future methods. Nonetheless, the results emphasize the high diversity of data sets in metabolomics and the complexity of finding biologically relevant biomarkers. As a result, we propose a novel approach applicable across all data sets, offering guidance for future analyses. This method involves directly comparing univariate and multivariate models. We demonstrate through selected examples how this approach can guide data analysis across diverse data set structures, representative of the observed variability. Code and data are available for research purposes.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":" ","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144281677","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Evaporation-Generated Dense Hotspots on Superwettable Patterned Microchips for Multiplex SERS Detection of Acute Myocardial Infarction-Specific miRNAs","authors":"Hongxiao Gao, Jing Xu, Manyan Wu, Yuemeng Yang, Na Li, Hong Chen, Li-Ping Xu","doi":"10.1021/acs.analchem.5c00891","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00891","url":null,"abstract":"Acute myocardial infarction (AMI) poses a threat to human health, and current clinical diagnostic methods cannot achieve early warning of AMI. The accurate detection of AMI-specific miRNAs is of great significance for the early diagnosis and treatment of AMI. However, the low abundance of miRNAs poses a major challenge to the sensitive detection of ultratrace miRNAs. Herein, a superwettable SERS microchip with an evaporation-induced SERS enhancement effect was developed for AMI-specific miRNA detection, which integrated a superwettable patterned surface and DNA walker strategy. Benefiting from the extreme difference in wettability between the superhydrophilic microwell and superhydrophobic background, both target and SERS tag can be sufficiently enriched in the superhydrophilic microwell. Abundant hotspots are generated through a simple evaporation-induced concentration and aggregation, leading to highly responsive and reproducible SERS signals. Coupled with the DNA walker strategy for signal amplification, the prepared superwettable SERS microchip enables the sensitive and multiplexed detection of AMI-specific miRNAs in both buffer and whole serum without interference. Furthermore, the fabricated microchip demonstrates accurate quantification of AMI-specific miRNAs in clinical samples, enabling differentiation among AMI patients, non-AMI individuals presenting with chest pain, and healthy individuals. This advancement provides a facile approach for the accurate diagnosis and early warning of AMI. We envision that this work will open new avenues for the fabrication of SERS biosensors and hold promise for medical diagnostics.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"25 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144269220","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Z-Scheme Bismuth-Based Ternary Heterostructured Photoelectrochemical Sensor Integrated with Cu3P Nanoparticles as a Multifunctional Signal Probe for Quantifying Circulating Tumor Cells","authors":"Chengqi Bao, Rong Shao, Yan Lu, Minghui Yang, Xiaoqing Li","doi":"10.1021/acs.analchem.5c02513","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c02513","url":null,"abstract":"Circulating tumor cells (CTCs) are widely acknowledged as critical biomarkers for early cancer diagnosis and prognosis, highlighting the urgent need for the development of sensitive and accurate detection methods for CTCs. Herein, a photoelectrochemical (PEC) sensor was developed based on dual Z-scheme Bi₂S₃/Bi₂O₂CO₃/Zn_0.5Cd_0.5S heterojunctions as the high-efficiency photoactive material and Cu₃P nanoparticles (Cu₃P NPs) as the multifunctional signal probe, thereby achieving sensitivity and precise detection of MCF-7 cells. The Z-scheme heterojunction structure significantly enhances the photoelectric conversion efficiency, while Cu₃P NPs can suppress the photocurrent through p–n semiconductor quenching and enzyme-mimetic catalytic precipitation, which involves the catalytic oxidation of 4-chloro-1-naphthol (4-CN) to form the insoluble precipitate benzo-4-chloro-hexadienone (4-CD). Coupled with aptamer-functionalized magnetic nanobeads (Apt_MUC1–MNs) for selective cell capture and enrichment, the PEC sensor achieved an ultrawide linear range (4 cells/mL to 3 × 10⁵ cells/mL) and a remarkably low detection limit (LOD) of 1 cell/mL (S/N = 3), alongside good selectivity, stability, and reproducibility. Furthermore, the successful validation of MCF-7 in human serum samples demonstrates its clinical applicability, highlighting promising potential for early cancer diagnosis and liquid biopsy applications. This work provides a novel PEC sensing platform for sensitive detection of different biomarkers in clinical diagnosis.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"8 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144269222","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Comprehensive and Ultrasensitive Isotope Calibration Method for Soil Amino Compounds Using Orbitrap Mass Spectrometry","authors":"Tao Li, Yuhua Li, Erika Salas, Ye Tian, Xiaofei Liu, Wolfgang Wanek","doi":"10.1021/acs.analchem.5c01358","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c01358","url":null,"abstract":"Bound amino compounds (amino acid and amino sugar polymers) comprise a significant proportion (∼40%) of soil organic nitrogen and therefore represent an essential source of nitrogen for plant and microbial nutrition. The analysis of their content and isotope enrichment still represents a significant challenge due to the low isotope enrichment levels reached under near-native soil conditions and the lack of isotopically labeled standards for some key amino compounds. In this study, we used both a ¹³C-labeled and an unlabeled amino acid mixture to establish isotope calibration curves for 16 amino compounds, using the 6-aminoquinolyl-<i>N</i>-hydroxysccinimidyl carbamate (AQC) derivatization method and ultrahigh-performance liquid chromatography with high-resolution Orbitrap mass spectrometry (UPLC-Orbitrap MS). Molecular ions of AQC-derivatives for all standard amino compounds were identified at the expected <i>m</i>/<i>z</i> values of the respective isotopologues. The isotope calibration curves exhibited excellent linear fits across the whole ¹³C enrichment range and polynomial fits in the low ¹³C enrichment range (<i>R</i>² &gt; 0.990). However, the polynomial fitting terms differed between individual amino acids. Subsequently, we developed equations to relate the calibrated regression terms to the physicochemical properties of the respective amino acids, here mainly the ratio of amino compound-C atoms to total C atoms in AQC-amino compound derivatives. Based on these regressions, we could ultimately predict isotope calibration curves for those amino compounds unavailable as ¹³C labeled standards, for example, muramic acid, hydroxyproline, and diaminopimelic acid. To test the model accuracy, we compared the outcomes of measured calibrations with predicted calibrations for amino acids where we had isotopically enriched standards. The results of linear regression between measured and predicted data were excellent, where <i>R</i>² was &gt;0.97, and mean absolute (percentage) deviations, MAD and MAPD, were 0.334 and 15.8%. Finally, we applied both standard and predicted calibration curves to low ¹³C amended soil samples and unlabeled controls to test the applicability of our model. The limit of detection (LOD) as the minimum detectable atom % ¹³C incorporation of amino compounds ranged from 0.0003 to 0.14 atom % among different amino compounds. This general predictive model can be used to comprehensively quantify isotope enrichments across the entire soil amino compound profile, including amino sugars and proteinogenic and nonproteinogenic amino acids, providing valuable insights for a better understanding of the overall fate of different amino compounds in soils and other complex environmental systems.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"25 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144269221","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Spectroelectrochemical Fiber-Optic Sensor Based on Localized Surface Plasmon Resonance for Simultaneous Multiselective Electroactive Species Detection","authors":"Tatsuya Orii, Takuya Okazaki, Takamichi Yamamoto, Kazuto Sazawa, Akira Taguchi, Kazuharu Sugawara, Hideki Kuramitz","doi":"10.1021/acs.analchem.4c06962","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06962","url":null,"abstract":"Herein, we report the development of a novel sensor combining electrochemistry, localized surface plasmon resonance (LSPR) in nanoparticles, and fiber-optic sensing for the first time. The sensor developed comprises an indium tin oxide (ITO)-coated multimodal optical fiber with gold nanoparticles immobilized on the ITO surface via electrostatic self-assembly. Two types of sensing methods are demonstrated: one based on shift in LSPR peak wavelength accompanying electrochemical oxidation–reduction of an analyte and the other based on potential scanning-based detection of refractive index change. Ru(NH₃)₆^2+/3+, methylene blue, and Fe(CN)₆^3–/4– are used as model analytes for the first method. Consequently, we observe that the optical responses caused by electrochemical reactions of the analytes are accompanied by a linear relationship between the LSPR peak shift and analyte concentration. In the second method, the LSPR peak potential is obtained via potential scanning in sucrose solutions with various refractive indexes. By means of avidin–biotin interaction on its surface, the sensor developed is successfully applied for biodetection of the protein NeutrAvidin.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"100 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144269218","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}