Sensitive recognition of enantiomer has aroused extensive interest due to its importance in diverse fields ranging from pharmaceuticals to catalysis and biomedicine. Chiral surface-enhanced Raman scattering (SERS) by chiral plasmonic substrates has emerged as a promising tool for the recognition of enantiomers with high sensitivity as well as molecular fingerprinting capability. However, the impact of the molecular states including surface packing density and configurations of surface-adsorbed chiral molecules on chiral SERS has been largely unexplored. Herein, we demonstrate that chiral SERS by chiral plasmonic nanoparticles (NPs) is sensitively dependent on the molecular coverage of enantiomers. Au helical nanocubes with tunable optical properties and intense near-field enhancements were chosen as the chiral plasmonic substrates for chiral SERS. By changing the concentration and structure of enantiomers, the impact of the molecular states including surface packing density and configurations of enantiomers on chiral SERS is revealed. Finally, we demonstrate the use of achiral molecules as internal molecular spacers for achieving the ultrasensitive detection of enantiomer. The insights gained from this work not only shed light on the underlying mechanisms dictating the chiral SERS by chiral plasmonic NPs but also strongly suggest a promising approach to the sensitive detection of molecular chirality using Raman spectroscopy.
{"title":"Molecular Coverage Modulates Chiral Surface-Enhanced Raman Scattering on Chiral Plasmonic Nanoparticles","authors":"Dandan Lu, Guizeng Yang, Yunlong Tao, Guoxin Cao, Xuehao Sun, Chuang Liu, Lichao Sun, Qingfeng Zhang","doi":"10.1021/acs.analchem.4c06639","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06639","url":null,"abstract":"Sensitive recognition of enantiomer has aroused extensive interest due to its importance in diverse fields ranging from pharmaceuticals to catalysis and biomedicine. Chiral surface-enhanced Raman scattering (SERS) by chiral plasmonic substrates has emerged as a promising tool for the recognition of enantiomers with high sensitivity as well as molecular fingerprinting capability. However, the impact of the molecular states including surface packing density and configurations of surface-adsorbed chiral molecules on chiral SERS has been largely unexplored. Herein, we demonstrate that chiral SERS by chiral plasmonic nanoparticles (NPs) is sensitively dependent on the molecular coverage of enantiomers. Au helical nanocubes with tunable optical properties and intense near-field enhancements were chosen as the chiral plasmonic substrates for chiral SERS. By changing the concentration and structure of enantiomers, the impact of the molecular states including surface packing density and configurations of enantiomers on chiral SERS is revealed. Finally, we demonstrate the use of achiral molecules as internal molecular spacers for achieving the ultrasensitive detection of enantiomer. The insights gained from this work not only shed light on the underlying mechanisms dictating the chiral SERS by chiral plasmonic NPs but also strongly suggest a promising approach to the sensitive detection of molecular chirality using Raman spectroscopy.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"93 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143783014","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}
Pub Date : 2025-04-04DOI: 10.1021/acs.analchem.5c00648
Jing Wang, Jianpu Tang, Aiqi Liang, Zhen Cui, Jiale Huo, Qian Li, Bin Ke, Dayong Yang, Chi Yao
Circulating tumor cells (CTCs) have emerged as critical biomarkers in liquid biopsy for noninvasive tumor diagnosis and real-time monitoring of cancer progression. However, the isolation of CTCs is often required before detection due to their ultralow abundance in peripheral blood. These isolation processes are typically time-consuming and prone to cell loss, which limits the utility of CTC-based liquid biopsy. Herein, we present a DNA network-based diagnostic system that enables specific recognition, selective enrichment, and accurate detection of CTCs directly from blood samples. The DNA network comprises ultralong DNA chains embedded with polyvalent aptamers and fluorescence detection modules. The polyvalent aptamers selectively bind to the epithelial cell adhesion molecule (EpCAM) on a CTC membrane, facilitating their enrichment through base pairing-driven DNA network formation. This system semiquantitatively detects the expression level of cancer-associated microRNA within CTCs using ratiometric fluorescence imaging based on the chemical assembly of two fluorescence modules. In clinical blood samples, this diagnostic system achieves 100% precision and 96% accuracy in distinguishing breast cancer patients from healthy donors, highlighting its promising potential for clinical breast cancer diagnosis.
{"title":"A Smart DNA Network-Based Diagnostic System for Enrichment and Detection of Circulating Tumor Cells in Cancer Liquid Biopsy","authors":"Jing Wang, Jianpu Tang, Aiqi Liang, Zhen Cui, Jiale Huo, Qian Li, Bin Ke, Dayong Yang, Chi Yao","doi":"10.1021/acs.analchem.5c00648","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00648","url":null,"abstract":"Circulating tumor cells (CTCs) have emerged as critical biomarkers in liquid biopsy for noninvasive tumor diagnosis and real-time monitoring of cancer progression. However, the isolation of CTCs is often required before detection due to their ultralow abundance in peripheral blood. These isolation processes are typically time-consuming and prone to cell loss, which limits the utility of CTC-based liquid biopsy. Herein, we present a DNA network-based diagnostic system that enables specific recognition, selective enrichment, and accurate detection of CTCs directly from blood samples. The DNA network comprises ultralong DNA chains embedded with polyvalent aptamers and fluorescence detection modules. The polyvalent aptamers selectively bind to the epithelial cell adhesion molecule (EpCAM) on a CTC membrane, facilitating their enrichment through base pairing-driven DNA network formation. This system semiquantitatively detects the expression level of cancer-associated microRNA within CTCs using ratiometric fluorescence imaging based on the chemical assembly of two fluorescence modules. In clinical blood samples, this diagnostic system achieves 100% precision and 96% accuracy in distinguishing breast cancer patients from healthy donors, highlighting its promising potential for clinical breast cancer diagnosis.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"59 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143783017","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}
Pub Date : 2025-04-04DOI: 10.1021/acs.analchem.4c07042
Le Xin, Wei Zheng, Kan Lin, Shulang Lin, Zhiwei Huang
Metabolic dysregulation is a critical feature of various cancers, including brain tumors. Studying metabolic changes in tumor cells and tissues significantly improves our understanding of tumor development, progression, and treatment response. In this study, we utilize hyperspectral stimulated Raman scattering (SRS) imaging combined with biochemical spectral modeling to identify unique histological and molecular signatures linked to metabolic diversity across different glioma grades, without the need for labeling. By employing rapid label-free SRS histopathology and multivariate curve resolution analysis, we uncover changes in lipid profiles and varying levels of neuron demyelination from low-grade (LG) to high-grade (HG) gliomas. Quantitative analysis of key metabolites using non-negative least-squares regression spectral modeling reveals a significant increase in cellular proteins, DNA, and cholesterol levels, alongside a reduced redox ratio (flavin adenine dinucleotide (FAD)/NADH) in the glioblastoma (GBM, grade IV) tissue compared to pilocytic astrocytoma (PA, grade I) and healthy brain tissues, indicating a shift toward a pro-malignant metabolic state. A neural network diagnostic classifier, trained on 4547 SRS spectra (healthy: 1263; LG: 815; HG: 2469) from 45 patients with PA and GBM, achieves 99.6% accuracy in detecting and grading brain tumors. This study highlights the potential of hyperspectral SRS imaging for rapid, label-free, and spatially resolved analysis of metabolic heterogeneity in human gliomas, paving the way for metabolome-targeted therapeutic strategies in precision brain tumor treatment.
{"title":"Deciphering Metabolic Alterations Associated with Glioma Grading Using Hyperspectral Stimulated Raman Scattering Imaging","authors":"Le Xin, Wei Zheng, Kan Lin, Shulang Lin, Zhiwei Huang","doi":"10.1021/acs.analchem.4c07042","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c07042","url":null,"abstract":"Metabolic dysregulation is a critical feature of various cancers, including brain tumors. Studying metabolic changes in tumor cells and tissues significantly improves our understanding of tumor development, progression, and treatment response. In this study, we utilize hyperspectral stimulated Raman scattering (SRS) imaging combined with biochemical spectral modeling to identify unique histological and molecular signatures linked to metabolic diversity across different glioma grades, without the need for labeling. By employing rapid label-free SRS histopathology and multivariate curve resolution analysis, we uncover changes in lipid profiles and varying levels of neuron demyelination from low-grade (LG) to high-grade (HG) gliomas. Quantitative analysis of key metabolites using non-negative least-squares regression spectral modeling reveals a significant increase in cellular proteins, DNA, and cholesterol levels, alongside a reduced redox ratio (flavin adenine dinucleotide (FAD)/NADH) in the glioblastoma (GBM, grade IV) tissue compared to pilocytic astrocytoma (PA, grade I) and healthy brain tissues, indicating a shift toward a pro-malignant metabolic state. A neural network diagnostic classifier, trained on 4547 SRS spectra (healthy: 1263; LG: 815; HG: 2469) from 45 patients with PA and GBM, achieves 99.6% accuracy in detecting and grading brain tumors. This study highlights the potential of hyperspectral SRS imaging for rapid, label-free, and spatially resolved analysis of metabolic heterogeneity in human gliomas, paving the way for metabolome-targeted therapeutic strategies in precision brain tumor treatment.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"108 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775742","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}
Pub Date : 2025-04-04DOI: 10.1021/acs.analchem.4c05175
Debashis Sen, Nicholas Volya, Yusuf Muhammed, Robert A. Lazenby
Individually addressable microelectrode arrays (MEAs) enable the simultaneous and independent measurement of multiple analytes and benefit from a small size scale, which enables highly localized electrochemical detection. In this work, we describe a new methodology to fabricate low-cost and tunable MEA probes in which the number, spatial arrangement, and spacing of the electrodes and electrode material can be changed and controlled. This was achieved using a 3D printed support assembly to position wires of the electrode material into designated positions and a mold to seal the electrodes in place using epoxy resin. After curing of the epoxy, mechanical polishing exposed the surface of closely spaced disk microelectrodes embedded in the insulating material, which formed the MEA. The individual electrodes of the array were characterized using electrochemical methods and optical and electron microscopy to evaluate the surface quality and the integrity of the seal with the insulating epoxy. To validate the fabrication method and to demonstrate the controlled electrode spacing, we used a dual-disk electrode device, while four-, five-, and seven-electrode probes were used to demonstrate some of the different numbers and geometric arrangements of electrodes that are possible. While the developed probes have numerous potential applications, including as probes or substrates in scanning electrochemical microscopy, we fabricated electrochemical aptamer-based sensors on the individual electrodes, for the simultaneous detection of adenosine triphosphate and dopamine in phosphate-buffered saline solution, with and without 10% fetal bovine serum.
可单独寻址的微电极阵列（MEAs）能够同时独立测量多种分析物，而且体积小，可实现高度局部电化学检测。在这项工作中，我们介绍了一种制造低成本、可调式 MEA 探针的新方法，其中电极的数量、空间排列和间距以及电极材料都可以改变和控制。这是利用三维打印的支撑组件将电极材料线定位到指定位置，并利用环氧树脂模具将电极密封到位。环氧树脂固化后，机械抛光暴露出嵌入绝缘材料中的紧密间隔的圆盘微电极表面，从而形成 MEA。使用电化学方法、光学和电子显微镜对阵列的各个电极进行了表征，以评估表面质量以及与绝缘环氧树脂密封的完整性。为了验证制作方法并演示可控的电极间距，我们使用了双盘电极装置，同时还使用了四电极、五电极和七电极探针来演示可能存在的一些不同数量和几何排列的电极。所开发的探针有许多潜在应用，包括用作扫描电化学显微镜的探针或基底，同时我们还在单个电极上制作了基于电化学适配体的传感器，用于同时检测磷酸盐缓冲盐溶液（含或不含 10%胎牛血清）中的三磷酸腺苷和多巴胺。
{"title":"Fabrication and Characterization of a Tunable Microelectrode Array Probe for Simultaneous Multiplexed Electrochemical Detection","authors":"Debashis Sen, Nicholas Volya, Yusuf Muhammed, Robert A. Lazenby","doi":"10.1021/acs.analchem.4c05175","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05175","url":null,"abstract":"Individually addressable microelectrode arrays (MEAs) enable the simultaneous and independent measurement of multiple analytes and benefit from a small size scale, which enables highly localized electrochemical detection. In this work, we describe a new methodology to fabricate low-cost and tunable MEA probes in which the number, spatial arrangement, and spacing of the electrodes and electrode material can be changed and controlled. This was achieved using a 3D printed support assembly to position wires of the electrode material into designated positions and a mold to seal the electrodes in place using epoxy resin. After curing of the epoxy, mechanical polishing exposed the surface of closely spaced disk microelectrodes embedded in the insulating material, which formed the MEA. The individual electrodes of the array were characterized using electrochemical methods and optical and electron microscopy to evaluate the surface quality and the integrity of the seal with the insulating epoxy. To validate the fabrication method and to demonstrate the controlled electrode spacing, we used a dual-disk electrode device, while four-, five-, and seven-electrode probes were used to demonstrate some of the different numbers and geometric arrangements of electrodes that are possible. While the developed probes have numerous potential applications, including as probes or substrates in scanning electrochemical microscopy, we fabricated electrochemical aptamer-based sensors on the individual electrodes, for the simultaneous detection of adenosine triphosphate and dopamine in phosphate-buffered saline solution, with and without 10% fetal bovine serum.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"37 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776185","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}
Nanoparticle size dispersion within polymer nanocomposites is crucial for ensuring material properties and performance. Monitoring the evolution of particle size distribution during processing proves to be critical for elucidating fundamental mechanisms and optimizing manufacturing parameters. The size dispersion evaluation relies on microscopy imaging of the nanoparticles inside the polymer matrix. However, current imaging techniques face significant challenges due to resolution limitations. In this study, we introduce a method that, despite having a microscopy resolution larger than the minimal particle size, effectively assesses the evolution of nanoparticle size dispersion during the fabrication process of polymer nanocomposites. We show that this method has an amplifying effect on the observation of nanoparticles with larger size, namely, the probabilities of the “residues” of the size statistics are larger than the corresponding original probabilities. We demonstrate the utility of this method to assess the agglomeration of nanoparticles during the fabrication processes of polymer nanocomposites. We prepare zinc oxide (ZnO) nanoparticles, incorporate them into polyethylene terephthalate (PET) chips, subsequently process them into ZnO/PET composite fibers, and apply the method to inspect the whole process of the fabrication. Our findings indicate that the developed method provides a reliable evaluation of nanoparticle size dispersion across different material forms. We observed that the fabrication process from ZnO/PET chips to ZnO/PET fibers increases the degree of aggregation, whereas the step from ZnO nanoparticles to ZnO/PET chips maintains a relatively fine size dispersion. Our developed method shows a novel “residue imaging” strategy and can be listed as a useful way to inspect the filler particle dispersion in polymer nanocomposites.
{"title":"Amplifying Effect in the Size Statistics of the Residual Particles and Its Applications in Analyzing Nanoparticle Dispersion in Polymer Nanocomposites","authors":"Yuanyuan Zhong, Yangang Chen, Miaoya Zhang, Hao Zhang, Xiaomin Liao, Huan Jin, Jiaxin Feng, Xianan Qin","doi":"10.1021/acs.analchem.4c06195","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06195","url":null,"abstract":"Nanoparticle size dispersion within polymer nanocomposites is crucial for ensuring material properties and performance. Monitoring the evolution of particle size distribution during processing proves to be critical for elucidating fundamental mechanisms and optimizing manufacturing parameters. The size dispersion evaluation relies on microscopy imaging of the nanoparticles inside the polymer matrix. However, current imaging techniques face significant challenges due to resolution limitations. In this study, we introduce a method that, despite having a microscopy resolution larger than the minimal particle size, effectively assesses the evolution of nanoparticle size dispersion during the fabrication process of polymer nanocomposites. We show that this method has an amplifying effect on the observation of nanoparticles with larger size, namely, the probabilities of the “residues” of the size statistics are larger than the corresponding original probabilities. We demonstrate the utility of this method to assess the agglomeration of nanoparticles during the fabrication processes of polymer nanocomposites. We prepare zinc oxide (ZnO) nanoparticles, incorporate them into polyethylene terephthalate (PET) chips, subsequently process them into ZnO/PET composite fibers, and apply the method to inspect the whole process of the fabrication. Our findings indicate that the developed method provides a reliable evaluation of nanoparticle size dispersion across different material forms. We observed that the fabrication process from ZnO/PET chips to ZnO/PET fibers increases the degree of aggregation, whereas the step from ZnO nanoparticles to ZnO/PET chips maintains a relatively fine size dispersion. Our developed method shows a novel “residue imaging” strategy and can be listed as a useful way to inspect the filler particle dispersion in polymer nanocomposites.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"37 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775739","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}
Pub Date : 2025-04-04DOI: 10.1021/acs.analchem.5c01777
Guoliang Zhou, Pan Li, Chengxi Zhao, Xinran Guo, Ronglu Dong, Liangbao Yang
In the final published version, we inadvertently omitted Dr. Ronglu Dong, who should have been listed as a corresponding author. In fact, Dr. Dong was clearly identified as a co-corresponding author in both the initial and revised manuscripts and made significant contributions to key aspects of the study including conceptualization, experimental design, and manuscript revision. This oversight resulted solely from an error in typesetting and proofreading and does not affect the main content or the academic conclusions of the paper. We hereby submit this supplementary correction request to restore Dr. Dong’s rightful position as corresponding author and to ensure that future citations accurately reflect his academic contributions. We apologize for any inconvenience this may have caused readers and database references. The correct order is reflected in the authorship of this Correction. This article has not yet been cited by other publications.
{"title":"Correction to “Insights of Surface-Enhanced Raman Spectroscopy Detection by Guiding Molecules into Nanostructures to Activate Hot Spots”","authors":"Guoliang Zhou, Pan Li, Chengxi Zhao, Xinran Guo, Ronglu Dong, Liangbao Yang","doi":"10.1021/acs.analchem.5c01777","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c01777","url":null,"abstract":"In the final published version, we inadvertently omitted Dr. Ronglu Dong, who should have been listed as a corresponding author. In fact, Dr. Dong was clearly identified as a co-corresponding author in both the initial and revised manuscripts and made significant contributions to key aspects of the study including conceptualization, experimental design, and manuscript revision. This oversight resulted solely from an error in typesetting and proofreading and does not affect the main content or the academic conclusions of the paper. We hereby submit this supplementary correction request to restore Dr. Dong’s rightful position as corresponding author and to ensure that future citations accurately reflect his academic contributions. We apologize for any inconvenience this may have caused readers and database references. The correct order is reflected in the authorship of this Correction. This article has not yet been cited by other publications.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"10 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775745","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}
Pub Date : 2025-04-03DOI: 10.1021/acs.analchem.4c06431
Jiaxing Chang, Zhinan Zhang, Chulin Qu, Qingzhi Han, Li Xu
We report a strategy based on pyridyl-anchored organic small-molecule fluorescent probes to develop a dual-signal sensing platform. The strategy accomplishes an intelligent integration of fluorescence analysis with photoelectrochemical (PEC) sensing, thereby enabling rapid and precise detection of hypochlorite. In this work, the natural dye chromone was selected as the fluorophore for generating fluorescent signals. Meanwhile, by using phenothiazine (PTZ) as the specific recognition group and pyridine as the anchoring moiety, we designed and synthesized a novel organic small-molecule fluorescent probe. The obtained probe was used as a photosensitive material anchored to the TiO2 surface via N → Ti bonds, to form an FTO/TiO2/FPTZ-1 heterostructure-based dual-signal sensing platform for the detection of hypochlorite. This sensing platform has the characteristics of high specificity, sensitivity, and ease of preparation, enabling rapid qualitative fluorescence readout and quantitative photoelectrochemical readout of hypochlorite, with a limit of detection of 0.288 μM for fluorescence and 1.37 nM for PEC.
{"title":"Organic Molecules as a Bridge Connecting Photoelectrochemistry and Fluorescence for Dual-Signal Assay","authors":"Jiaxing Chang, Zhinan Zhang, Chulin Qu, Qingzhi Han, Li Xu","doi":"10.1021/acs.analchem.4c06431","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06431","url":null,"abstract":"We report a strategy based on pyridyl-anchored organic small-molecule fluorescent probes to develop a dual-signal sensing platform. The strategy accomplishes an intelligent integration of fluorescence analysis with photoelectrochemical (PEC) sensing, thereby enabling rapid and precise detection of hypochlorite. In this work, the natural dye chromone was selected as the fluorophore for generating fluorescent signals. Meanwhile, by using phenothiazine (PTZ) as the specific recognition group and pyridine as the anchoring moiety, we designed and synthesized a novel organic small-molecule fluorescent probe. The obtained probe was used as a photosensitive material anchored to the TiO<sub>2</sub> surface via N → Ti bonds, to form an FTO/TiO<sub>2</sub>/FPTZ-1 heterostructure-based dual-signal sensing platform for the detection of hypochlorite. This sensing platform has the characteristics of high specificity, sensitivity, and ease of preparation, enabling rapid qualitative fluorescence readout and quantitative photoelectrochemical readout of hypochlorite, with a limit of detection of 0.288 μM for fluorescence and 1.37 nM for PEC.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"25 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766648","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}
Pub Date : 2025-04-03DOI: 10.1021/acs.analchem.5c01233
Heng Wang, Jingya Zhang, Chun Sun, Xinyu Zhao, Hongchao Qi, Ke Chen
A high-sensitivity fiber-optic photoacoustic carbon monoxide (CO) sensor based on quantum cascade laser (QCL) and nonresonant multipass cell is proposed. By leveraging the mid-infrared fundamental band absorption, multipass absorption enhancement, and cantilever resonance frequency detection, a multimechanism synergy has been achieved to enable highly sensitive detection of CO. In the mid-infrared band, CO exhibits a strong absorption coefficient, thereby eliminating the need for a high-power optical amplifier. Furthermore, by integrating a miniaturized multipass cell, the photoacoustic signal is remarkably enhanced, enabling the miniaturization and ultrahigh sensitivity of the sensor. A pair of spherical reflectors are symmetrically installed at both ends of the photoacoustic cell to form a Herriott multipass cell. The light beam reflects 20 times within the multipass cell, creating 10 elliptically distributed light spots. The gas chamber volume of the sensor is only 1.28 mL, with an optical path length of 510 mm. The generated photoacoustic signals are measured by a fiber-optic Fabry–Perot (FP) cantilever microphone, which can detect weak signals with high sensitivity at the resonance frequency of the cantilever. The measured signal amplitude is 8.7 times that of a single reflection. When the averaging time is 100 s, the minimum detection limit of the system for CO is 0.8 ppb, corresponding to a normalized noise equivalent absorption (NNEA) coefficient of 4.94 × 10–9 Wcm–1/Hz1/2.
{"title":"Miniaturized Fiber-Optic Photoacoustic Gas Sensor for Sub-ppb-Level Detection of Carbon Monoxide Based on Quantum Cascade Laser and Multipass Cell","authors":"Heng Wang, Jingya Zhang, Chun Sun, Xinyu Zhao, Hongchao Qi, Ke Chen","doi":"10.1021/acs.analchem.5c01233","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c01233","url":null,"abstract":"A high-sensitivity fiber-optic photoacoustic carbon monoxide (CO) sensor based on quantum cascade laser (QCL) and nonresonant multipass cell is proposed. By leveraging the mid-infrared fundamental band absorption, multipass absorption enhancement, and cantilever resonance frequency detection, a multimechanism synergy has been achieved to enable highly sensitive detection of CO. In the mid-infrared band, CO exhibits a strong absorption coefficient, thereby eliminating the need for a high-power optical amplifier. Furthermore, by integrating a miniaturized multipass cell, the photoacoustic signal is remarkably enhanced, enabling the miniaturization and ultrahigh sensitivity of the sensor. A pair of spherical reflectors are symmetrically installed at both ends of the photoacoustic cell to form a Herriott multipass cell. The light beam reflects 20 times within the multipass cell, creating 10 elliptically distributed light spots. The gas chamber volume of the sensor is only 1.28 mL, with an optical path length of 510 mm. The generated photoacoustic signals are measured by a fiber-optic Fabry–Perot (FP) cantilever microphone, which can detect weak signals with high sensitivity at the resonance frequency of the cantilever. The measured signal amplitude is 8.7 times that of a single reflection. When the averaging time is 100 s, the minimum detection limit of the system for CO is 0.8 ppb, corresponding to a normalized noise equivalent absorption (NNEA) coefficient of 4.94 × 10<sup>–9</sup> Wcm<sup>–1</sup>/Hz<sup>1/2</sup>.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"141 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775749","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}
The versatile fluorescent dyes are essential for specifically labeling plant cell walls in vivo, monitoring plasma membrane damage, and assessing cell viability. However, such dyes are rare and often discovered accidentally due to a lack of design principles. Propidium iodide, a well-known example, has limitations like low brightness, high toxicity, and poor bacterial differentiation. To address these challenges, we developed VersaDye, a modular probe designed for specific imaging of live plant cell walls and monitoring plasma membrane damage in plant cells, human cells, and certain bacteria. The design integrates impermeability principles and environment-dependent fluorophore scaffolds. VersaDye enables bright, wash-free labeling of plant cell walls and can stain various plant organs for constructing 3D tissue organization. Notably, it can selectively distinguish live Gram-positive from Gram-negative bacteria, a feature absent in other dyes. Its impermeability and targeting ability also allow it to probe membrane damage caused by physical, chemical, and biological stimuli. This study marks the first use of VersaDye in analyzing cell damage in live plants under salt stress. VersaDye offers a robust platform for wash-free, in vivo membrane damage monitoring and simultaneous cell wall labeling. Additionally, its design suggests adaptability for regulating permeability to meet specific diagnostic needs, such as identifying membrane-compromised cells in diseases or enabling high-throughput antibiotic screening targeting specific bacteria.
{"title":"Modular Design of Membrane-Impermeable Versatile Probe for Specific Imaging of Cell Walls and Real-Time Detection of Cell Membrane Damage","authors":"Zhengdong Han, Tian Li, Ziqing He, Engao Zhu, Zhaosheng Qian, Xia Liu, Hui Feng","doi":"10.1021/acs.analchem.5c01229","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c01229","url":null,"abstract":"The versatile fluorescent dyes are essential for specifically labeling plant cell walls in vivo, monitoring plasma membrane damage, and assessing cell viability. However, such dyes are rare and often discovered accidentally due to a lack of design principles. Propidium iodide, a well-known example, has limitations like low brightness, high toxicity, and poor bacterial differentiation. To address these challenges, we developed VersaDye, a modular probe designed for specific imaging of live plant cell walls and monitoring plasma membrane damage in plant cells, human cells, and certain bacteria. The design integrates impermeability principles and environment-dependent fluorophore scaffolds. VersaDye enables bright, wash-free labeling of plant cell walls and can stain various plant organs for constructing 3D tissue organization. Notably, it can selectively distinguish live Gram-positive from Gram-negative bacteria, a feature absent in other dyes. Its impermeability and targeting ability also allow it to probe membrane damage caused by physical, chemical, and biological stimuli. This study marks the first use of VersaDye in analyzing cell damage in live plants under salt stress. VersaDye offers a robust platform for wash-free, in vivo membrane damage monitoring and simultaneous cell wall labeling. Additionally, its design suggests adaptability for regulating permeability to meet specific diagnostic needs, such as identifying membrane-compromised cells in diseases or enabling high-throughput antibiotic screening targeting specific bacteria.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"16 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766651","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}
Mycotoxins, particularly deoxynivalenol (DON) and zearalenone (ZEN), are common food contaminants that frequently co-occur in grains, posing significant health risks. This study proposed a multiplexed detection platform for simultaneous quantification and imaging of three microRNAs (miRNAs) integrated with machine learning to evaluate the combined toxicity of DON and ZEN. Based on Exonuclease III-assisted signal amplification, highly sensitive fluorescent molecular beacon probes (MBs) targeting miR-21, miR-221, and miR-27a were developed, achieving remarkable detection limits of 0.18 pM, 0.22 pM, and 0.21 pM, respectively. The MBs were efficiently delivered into cells via liposome-mediated endocytosis, enabling simultaneous intracellular imaging of the three miRNAs. By integrating machine learning algorithms, including linear discriminant analysis and principal component analysis, with RGB values extracted from cellular fluorescence images, a robust analytical platform was established for classifying miRNA expression patterns induced by various DON/ZEN concentrations. A highest single agent model was subsequently constructed to evaluate the combined toxicity, revealing that ZEN exhibited antagonistic effects on DON at low doses but synergistic effects at high doses. This sensitive and multiplexed detection method demonstrates a strong correlation between miRNA expression profiles and DON/ZEN toxicity, providing an innovative analytical tool for multicomponent toxicity assessment.
{"title":"Machine Learning-Assisted Multiplexed Fluorescence-Labeled miRNAs Imaging Decoding for Combined Mycotoxins Toxicity Assessment","authors":"Lixin Kang, Xianfeng Lin, Jiaqi Feng, Mengxia Duan, Nuo Duan, Zhouping Wang, Shijia Wu","doi":"10.1021/acs.analchem.5c00404","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00404","url":null,"abstract":"Mycotoxins, particularly deoxynivalenol (DON) and zearalenone (ZEN), are common food contaminants that frequently co-occur in grains, posing significant health risks. This study proposed a multiplexed detection platform for simultaneous quantification and imaging of three microRNAs (miRNAs) integrated with machine learning to evaluate the combined toxicity of DON and ZEN. Based on Exonuclease III-assisted signal amplification, highly sensitive fluorescent molecular beacon probes (MBs) targeting miR-21, miR-221, and miR-27a were developed, achieving remarkable detection limits of 0.18 pM, 0.22 pM, and 0.21 pM, respectively. The MBs were efficiently delivered into cells via liposome-mediated endocytosis, enabling simultaneous intracellular imaging of the three miRNAs. By integrating machine learning algorithms, including linear discriminant analysis and principal component analysis, with RGB values extracted from cellular fluorescence images, a robust analytical platform was established for classifying miRNA expression patterns induced by various DON/ZEN concentrations. A highest single agent model was subsequently constructed to evaluate the combined toxicity, revealing that ZEN exhibited antagonistic effects on DON at low doses but synergistic effects at high doses. This sensitive and multiplexed detection method demonstrates a strong correlation between miRNA expression profiles and DON/ZEN toxicity, providing an innovative analytical tool for multicomponent toxicity assessment.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"107 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767025","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}
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