Analytical Chemistry最新文献

{"title":"Surface-Defect-Involved Chemiluminescence Boosted by Gold–Silver Bimetallic Nanoclusters for Bioanalysis","authors":"Tongtong Zhai, Luyao Zhang, Sipeng Tian, Zhangpeng Xu, Xiushuang Fan, Jing Li, Erkang Wang","doi":"10.1021/acs.analchem.5c00219","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00219","url":null,"abstract":"Chemiluminescence (CL) as a powerful analytical tool has garnered increasing interest. However, traditional molecular-based CL luminophores suffer from low emission efficiency due to limited total CL photons emitted per luminophore, driving efforts to explore amplified strategies or novel probes to boost the emission. Although metal nanoclusters (NCs) as luminescent nanoprobes have been extensively studied for electrochemiluminescence and photoluminescence (PL) owing to their intriguing luminescent properties, the CL performance using metal NCs as emitters is often ignored. Herein, based on the synergistic effect within the bimetallic NCs, a series of glutathione-coated Au–Ag bimetallic NCs (GSH-AuAg NCs) were optimized by adjusting precursor ratios and achieved the maximum CL response at a Au:Ag molar ratio of 5:1. To our surprise, CL emission with GSH-AuAg NCs as emitters was triggered with oxidant reagents such as KMnO₄, and bimetallic NCs display boosted CL emission (ca. 6.2-fold) compared to monometallic NCs owing to the synergistic effect on enhancing the emission efficiency. Surface-defect-involved CL was revealed by collecting the CL spectra with a maximum emission wavelength of around 750 nm and an obvious red shift of 140 nm compared to PL spectra. The mechanism reveals the KMnO₄-injected hole into the valence band through redox reactions with GSH ligands, leading to CL emission by efficient radiative charge recombination with pre-existing electron. A sensing platform based on the GSH-AuAg NCs/oxidant system was constructed for sensing H₂O₂ and glucose, demonstrating the potential of GSH-AuAg NCs as CL emitters in analytical applications.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"18 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806135","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":"Scanning Contact Force Microscope–Scanning Electrochemical Microscopy: A New Approach for Tip Positioning and Simultaneous Imaging of Interfacial Topography and Activity","authors":"Yang Wang, Xuesen Zhao, Donghua Zhao, Hantao Xu, Jiayang Lin, Suyu Zhang, Jiqiang Wang, Zhenjiang Hu, Yongda Yan, Dongping Zhan, Yanquan Geng, Lianhuan Han","doi":"10.1021/acs.analchem.5c00360","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00360","url":null,"abstract":"Scanning Electrochemical Microscopy (SECM) offers exceptional spatial and temporal resolution while enabling the detection of localized chemical activity. However, the conventional SECM methodology lacks a robust positioning mechanism, leading to the convolution of electrochemical responses with topographical features. This study presents an innovative SECM positioning feedback mechanism, termed as “Scanning Contact Force Microscopy (SCFM)”, leveraging microforce servo control principles to precisely determine the “contact zero point” between the tip and the substrate. The core innovation lies in the integration of a low-stiffness, flexible microbeam with a high-precision capacitive displacement sensor (CDS), significantly minimizing the contact force exerted on the tip. Experimental results demonstrate that SCFM exhibits a normal positioning accuracy of less than 8 nm and a contact force below 20 μN. Morphology detection errors relative to commercial AFM systems were under 2%. Through the integration with SECM, the electrochemical signal is decoupled from the morphology of glassy carbon (GC) substrate with complex structure. Fully compatible with laser-pulled SECM glass electrodes, this technique requires no modifications to electrodes or instrumentation, offering a simple, cost-effective, and versatile solution for advancing nanoscale electrochemical investigations.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"59 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806136","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":"Locked Nucleic Acid-Enhanced Entropy-Driven Amplifier Combined with Catalytic Hybridization Reaction-Based DNA Circuit for Dual Amplified Detection of Single Nucleotide Polymorphisms and Asymmetric Encryption of Gene Information","authors":"Yanlei Li, Zhongfeng Gao, Yu Du, Yujie Han, Xiang Ren, Dan Wu, Hongmin Ma, Huangxian Ju, Fan Xia, Qin Wei, Fuan Wang","doi":"10.1021/acs.analchem.5c00529","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00529","url":null,"abstract":"Single-nucleotide polymorphisms (SNPs) play a pivotal role in investigations of disease-associated genes and in the genetic analysis of animal and plant varieties. Therefore, the detection of SNPs is essential for advancing biomedical diagnostics and therapeutics. Here, we report a locked nucleic acid (LNA)-enhanced dual signal amplification strategy for high-contrast detecting single-nucleotide polymorphisms (SNPs) in the KRAS_G12C gene. By integrating entropy-driven amplification with catalytic hybridization reaction, the proposed method achieves significant amplification of fluorescence and resonance Rayleigh scattering signals. The incorporation of LNA modification enhances the thermodynamic stability and reaction kinetics of the DNA computing circuit, resulting in superior sensitivity and specificity for SNPs detection. The method exhibits a low detection limit of 0.19 fM and a wide dynamic range from 1 fM to 0.1 nM for the KRAS_G12C gene. Compared to traditional DNA-based circuits, the LNA-modified system demonstrates enhanced discrimination of single-base mismatches and improved signal gain. Moreover, the proposed method was further demonstrated for its potential application in human serum samples. Impressively, this research not only presents a highly sensitive and selective platform for SNPs detection but also demonstrates its potential for molecular-level information encryption. The incorporation of LNA in dual signal amplification significantly elevates the intricacy and robustness of information encryption. Therefore, this study underscores the potential of DNA-based technologies to serve as a bridge between the era of biomedical research and the emerging Internet of things.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"34 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798267","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":"Revealing Stress Granule Compositional Heterogeneity through Antibody-Guided Proximity Labeling","authors":"Enming Miao, Dian Yang, Xuyang Yue, Zhuo Zhang, Han Liu, Hongqiang Qin, Mingliang Ye","doi":"10.1021/acs.analchem.4c06448","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06448","url":null,"abstract":"Stress granules (SGs), transient nonmembranous cytoplasmic condensates that formed in response to cellular stresses, require precise characterization to unravel their cell-type and stress-specific protein compositions. This study introduced a G3BP1 antibody-guided proximity labeling (Ab-PL) method to explore the composition and diversity of SGs, overcoming the challenges of traditional enzyme-mediated proximity labeling techniques across various cell types, especially for the immune cells. Application of Ab-PL to HeLa and RAW264.7 cells under heat shock (HS), sodium arsenate (AS), and sodium chloride stress (SS) revealed two categories of SG proteins: “SG-core” and “SG-shell,” characterized by their different abilities to undergo phase separation. The core proteins form the SG scaffold with strong self-segregation, while shell proteins are dynamically recruited based on the type of stress. Cell- and stress-specific SG proteins were also identified, highlighting compositional heterogeneity. Intriguingly, unique nuclear-cytoplasmic shuttling behaviors of SG components were observed under varying conditions, uncovering over 10 novel SG proteins, including REXO4, RBM28, and OGFR. This study provides a versatile tool for SG analysis across diverse cell types and offers insights into SG heterogeneity, which has potential implications for human diseases, paving the way for future studies on RNA metabolism, ribosome assembly, and immune regulation.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"20 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798264","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":"Enhancing the Separation and Quantification of Perfluoroalkyl Substances Using Polymeric Ionic Liquid Sorbents in Thin Film Microextraction","authors":"Aghogho A. Olomukoro, Derek R. Eitzmann, Jared L. Anderson, Emanuela Gionfriddo","doi":"10.1021/acs.analchem.4c06522","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06522","url":null,"abstract":"The preconcentration and isolation of per- and polyfluoroalkyl substances (PFAS) remain challenging due to their varying chain lengths and diverse headgroup chemical functionalities. These substances are persistent and occur in the environment at low parts-per-trillion concentration levels, necessitating the use of efficient and selective sorbents that can enhance their preconcentration from the targeted sample prior to instrumental analysis. This study, for the first time, evaluates the use of a polymeric ionic liquid (PIL) consisting of 1-(9-carboxy-nonyl)-3-vinylimidazolium bromide [C₉COOHVim⁺] [Br^–] ionic liquid (IL) monomer and 1,12-di(3-vinylimidazolium)dodecane bromide ([C₁₂(Vim⁺)₂]2[Br^–]) IL cross-linker for the simultaneous separation and preconcentration of 15 anionic PFAS. The PIL was immobilized on a thin film microextraction device to improve preconcentration, extraction, and desorption kinetics. The addition of competing anions to the desorption solution was critical to ensure the quantitative desorption of the anionic PFAS by an ion exchange mechanism. Partition coefficient calculations revealed a balanced extraction coverage for short- and long-chain PFAS in ultrapure water, while in solutions at high ionic strength, short-chain PFAS tend to display less affinity for the sorbent compared to long-chain PFAS. Kinetic studies showed that less hydrophobic PFAS (perfluorobutanoic acid (PFBA)–perfluorohexanoic acid (PFHxA)) reached equilibrium faster and the extraction followed a pseudo-second order model with <i>r</i>² values up to 0.9874. The applicability of the PIL-thin film microextraction (TFME) device for quantitative analysis was demonstrated by a calibration curve in a concentration range from 1 ng L^–1 to 2500 ng L^–1, which showed good accuracy (70–130%), precision (&lt;20%), and limits of quantification from 1 ng L^–1 to 50 ng L^–1.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"183 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143789629","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":"Monitoring the Metabolic Activity of a Single Bacterial Cell Based on Scattering Intensity","authors":"Akira Tokonami, Miya Kawanaka, Hikaru Ikeda, Shigeki Nishii, Takashi Kamegawa, Yojiro Yamamoto, Yasuhiro Sadanaga, Hiroshi Shiigi","doi":"10.1021/acs.analchem.4c06314","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06314","url":null,"abstract":"Cell activity is evaluated using the number of colonies formed on a medium or the number of live cells in a suspension or by staining nuclei with fluorescent dyes to determine whether cells are dead. However, the culture methods generally require extended culturing times, and damage to the cell membranes observed using fluorescent dyes is not necessarily related to cell survival or activity. Hence, accurately determining the activities of individual cells is impossible. Therefore, we developed a method for quantitatively evaluating the metabolic activities of single cells by focusing on the optical and chemical properties of formazan dye, i.e., 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT). The oxidized form of MTT is soluble and highly permeable to cell membranes, but it is reduced to insoluble MTT formazan upon reaction with intracellular metabolic products. Single-cell observation using dark-field microscopy revealed that insoluble formazan aggregates within the cells formed particles that emitted characteristic scattered light. The formazan-derived scattered light component extracted via peak fitting was related to metabolic activity, demonstrating its usefulness as a parameter indicating the activity of an individual cell. This method enables the real-time evaluation of the activities of single cells, which should lead to not only the acceleration of bacterial screening and microbial control but also the development of antibiotics and suppression of drug-resistant bacteria.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"20 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798271","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":"Concentration Measurement with Ultrabroad Dynamic Range Using Few-Step Variable Optical-Path-Length Slope Method","authors":"Mingwei Zhao, Xujun Yuan, Li Wei, Bo Dai, Songlin Zhuang, Dawei Zhang","doi":"10.1021/acs.analchem.4c06129","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06129","url":null,"abstract":"Concentration measurement has important applications in many fields, including pollution assessment in environmental science and drug dosage calculation in biomedical research. In the conventional methods, concentration is determined by measuring absorbance along a fixed long optical path. However, it is not suitable for high-concentration measurement. Herein, we have proposed a few-step variable optical-path-length slope method (fs-VOSM) for ultrabroad dynamic-range concentration measurement. As a proof of the method, we devised an fs-VOSM system in which a reference path is included to enhance the accuracy and repeatability. The measurement is conducted at 5 positions along ultrashort optical path (0–20 μm) for 800 ms. In the measurement of potassium dichromate solution concentration, the fs-VOSM system exhibits a wide dynamic range from 0.879 to 70.726 g/L with coefficient of variation (CV &lt; 1.4%) and high accuracy (relative error within ±3.5%). We prospect that the fs-VOSM can be widely adopted in many advanced instruments such as process analyzer, flow injection analyzer, and turbidity meter.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"4 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798270","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":"Signal-to-Noise Ratio Imaging and Real-Time Sharpening of Tumor Boundaries for Image-Guided Cancer Surgery","authors":"Ziyang Wang, Bo Dai, Yunlong Li, Ying Cao, Dong Wang, Fayu Liu, Zhenning Li, Huiming Cai, Christopher J. Butch, Yiqing Wang, Shuming Nie","doi":"10.1021/acs.analchem.5c00530","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00530","url":null,"abstract":"Fluorescence-guided cancer surgery is of considerable current interest in bioanalytical chemistry, engineering, and medicine, but its clinical utility is still hampered by the diffusive (scattering) nature of human tissues and large variations among different patients. Here, we report a new method based on signal-to-noise (contrast-to-noise) ratio (SNR or CNR) imaging for real-time delineation and sharpening of tumor boundaries during image-guided cancer surgery. In particular, we show that in vivo tumor fluorescence signals (both intensity and standard deviation) are strongly correlated with those of the surrounding tissue of the same tissue type and that this relationship is maintained as a function of time for fluorescent tracers such as indocyanine green. This dynamic relationship permits a precise removal of nonspecific background fluorescence from tumor fluorescence. As a result, single-pixel SNR values have been calculated, mapped, and displayed across a large surgical field at 60 frames per second. Pathological validation studies indicate that these SNR values correspond to statistical confidence levels similar (but not identical) to those of normal distributions. When the tumor fluorescence has an SNR of 3, pathological data show a confidence level of approximately 95% in identifying the true tumor lesions. For clinical relevance, we have also carried out first-in-human clinical studies for both oral and esophageal tumors, achieving tumor margin precisions of 1–2 mm with 87.5% histological accuracy and no false positives.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"21 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798019","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":"Single-Component Double-Emissive Ratiometric Probe: Toward Machine Learning Driven Detection and Discrimination of Neurological Biomarkers","authors":"Razieh Motamedi-Khozani, Samira Abbasi-Moayed, Mohammad Reza Hormozi-Nezhad","doi":"10.1021/acs.analchem.4c05618","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05618","url":null,"abstract":"This study presents an attractive single-component ratiometric fluorescent sensor that utilizes the oxidation of BSA-protected Au nanoclusters (BSA-Au NCs) by <i>N</i>-Bromosuccinimide (NBS) to detect catecholamine neurotransmitters and their metabolites, which are critical biomarkers for neurological diseases like neuroblastoma, pheochromocytomas, and paragangliomas. In this detailed sensing platform, NBS induces a noticeable fluorescence change in the emission of BSA- Au NCs, including the extinction of the emission peak at 650 nm and the simultaneous appearance of an emission peak at 450 nm. This shift represents a clear transition in the emission color of the probe from red to blue. The oxidation of Au NCs offers a promising approach for developing a ratiometric probe using a single fluorophore, eliminating the need to combine two individual fluorophores. The presence of neurogenic biomarkers inhibits the oxidation of BSA-Au NCs, varying with the concentration and identity of each analyte, making distinct changes in the spectral profiles along with vivid color variations. Spectral changes and RGB data derived from emission colors were analyzed using machine learning techniques, specifically linear discriminant analysis (LDA) for classification and partial least-squares regression (PLS-R) for multivariate calibration. Results from LDA and PLS-R highlighted the strong potential of the designed sensor for differentiating and quantifying these biomarkers. Furthermore, the successful application of this sensor in detecting and distinguishing these analytes in human urine provides valuable insights for clinical analysis in screening and diagnosing neurological disorders.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"25 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143789617","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":"Efficient and Discriminative Isolation of Circulating Cancer Stem Cells and Non-Stem-like Circulating Tumor Cells Using a Click-Handle-Loaded M13 Phage-Based Surface","authors":"Huida Li, Fengting Jia, Xin Wang, Ting Yang, Jian-Hua Wang","doi":"10.1021/acs.analchem.5c00924","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00924","url":null,"abstract":"Circulating tumor cells (CTCs) are crucial for cancer research and clinical applications, with circulating cancer stem cells (cCSCs) being a rare but key subpopulation responsible for metastasis, recurrence, and therapy resistance. Current limitations in efficiently isolating these cells, particularly distinguishing cCSCs from non-stem-like CTCs (nsCTCs), hinder our understanding of cancer progression and precision medicine strategies. Herein, we developed a novel CTC isolation approach that integrates cell metabolic chemical tagging with a <i><u>c</u></i>lick-<i><u>h</u></i>andle-loaded M13 <i><u>ph</u></i>age-based surf<i><u>ace</u></i> (CHPhace). The multivalent nature of flexible M13 nanofibers, featuring thousands of modification sites for click reactions, significantly enhances CTC capture across diverse tumor types. Leveraging the unique slow-cycling characteristic of cCSCs, CHPhace demonstrated selective cCSCs isolation through metabolic labeling and demetabolism processes. The robust performance of CHPhace allows efficient isolation of both cCSCs and nsCTCs from complex blood sample matrices, achieving capture efficiencies exceeding 80%. This approach represents a promising tool for advancing our understanding of cancer progression and enhancing precision in clinical diagnosis and cancer prognosis.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"20 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143789618","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}