ACS Publications最新文献

Orchestrated Nanozyme/Natural Enzyme Combination Strategy for a Machine Learning-Powered Biosensor Array toward High-Through‐put Screening of Antidiabetic Herbs 基于机器学习驱动的生物传感器阵列的纳米酶/天然酶组合策略用于抗糖尿病草药的高通量筛选

IF 7.3 1区化学

Analytical Chemistry Pub Date : 2026-11-10 Epub Date: 2026-10-07 DOI: 10.1021/acs.analchem.6c04734

Qingjie Fu, Hao Wang, Shun Wang, Mengke Wang, Kelong Fan, Xiyun Yan, Jiuyang He

{"title":"Orchestrated Nanozyme/Natural Enzyme Combination Strategy for a Machine Learning-Powered Biosensor Array toward High-Through‐put Screening of Antidiabetic Herbs","authors":"Qingjie Fu, Hao Wang, Shun Wang, Mengke Wang, Kelong Fan, Xiyun Yan, Jiuyang He","doi":"10.1021/acs.analchem.6c04734","DOIUrl":"10.1021/acs.analchem.6c04734","url":null,"abstract":"Screening for α-glucosidase (α-GLU) inhibitors is vital for the discovery of antidiabetic drugs, and traditional Chinese herbal medicines (TCMs) are promising antidiabetic agents. However, traditional high-throughput screening strategies are labor intensive. The integration of nanozymes with machine learning provides prospects for convenient and highly efficient screening strategies. To advance this status, a dual-active MnO2-decorated Ce metal−organic framework nanozyme (MnPCe) with outstanding oxidase-like (OXD-like) and laccase-like (LAC-like) activity was synthesized for the first time. After the conjugation of MnO2 on CeMOF, the OXD-like and LAC-like activities of MnPCe increased. Inspired by the cascade reaction and signal complementarity between the dual-active MnPCe nanozyme and natural α-GLU, a machine learning-assisted triple-channel biosensor array for α-GLU inhibitors was constructed based on the combination of the nanozyme and natural enzyme catalytic channels. The three colorimetric signals were integrated into a unique fingerprint pattern, enabling the sensor array to accurately discriminate nine common α-GLU inhibitors. It also successfully distinguished TCMs containing different types of α-GLU inhibitors, highlighting its potential for high-throughput screening of antidiabetic agents from complex herbal matrices. It inspires the innovation of multifunctional nanozymes, the development of high-throughput screening of promising drugs, and the extraction of valuable compounds from herbal medicines.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"98 44","pages":"31205–31216"},"PeriodicalIF":7.3,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092140","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}

引用次数: 0

A Pseudo-Targeted Method for Global Profiling of Cholesteryl Esters by Liquid Chromatography-Zeno High-Resolution Multiple Reaction Monitoring Mass Spectrometry 液相色谱- zeno高分辨率多反应监测质谱分析胆固醇酯的伪靶向方法

IF 7.3 1区化学

Analytical Chemistry Pub Date : 2026-11-10 Epub Date: 2026-09-30 DOI: 10.1021/acs.analchem.6c04131

Jiarun Huang, Lan Huang, Kaikun Xu, Xinyi Wan, Hanjie Ren, Pei Jiang, Fuchu He, Ya-Li Bai

{"title":"A Pseudo-Targeted Method for Global Profiling of Cholesteryl Esters by Liquid Chromatography-Zeno High-Resolution Multiple Reaction Monitoring Mass Spectrometry","authors":"Jiarun Huang, Lan Huang, Kaikun Xu, Xinyi Wan, Hanjie Ren, Pei Jiang, Fuchu He, Ya-Li Bai","doi":"10.1021/acs.analchem.6c04131","DOIUrl":"10.1021/acs.analchem.6c04131","url":null,"abstract":"Cholesteryl esters (CEs) play critical roles in diverse physiological processes, yet their comprehensive analysis remains challenging due to the limited availability of authentic standards and the low abundance of many CE species. To address this, we developed a pseudo-targeted screening strategy that integrates virtual database construction with retention time prediction for the global analysis of CEs using optimized liquid chromatography-Zeno high-resolution multiple reaction monitoring (LC-Zeno MRM-HR). Compared to conventional data-dependent acquisition (DDA), our method demonstrated superior sensitivity and specificity. Application of this strategy to biological samples resulted in the identification of 80 CE species. Among these, 18 are reported here for the first time, and 9 were unequivocally validated using authentic standards, underscoring the method’s extended coverage and reliable identification accuracy. We further applied this method to analyze CE metabolism in hepatocellular carcinoma (HCC) cells. Pharmacological inhibition of SOAT1 (by avasimibe) and NCEH1 (by JW480) revealed their opposing roles: SOAT1 inhibition depleted CEs, while NCEH1 inhibition promoted their accumulation, consistent with established biology understanding and affirming the utility of our approach. Finally, leveraging the analytical power of this strategy, we conducted a multi-tissue survey across brain, heart, lung, kidney, stomach, fat, and plasma. This revealed distinct, organ-specific CE profiles that correlate with local physiology, establishing a foundational blueprint for tissue-specific CE distribution.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"98 44","pages":"30837–30846"},"PeriodicalIF":7.3,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092712","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}

引用次数: 0

Simple and Isolation-Free Analysis of Tumor-Derived Extracellular Vesicles by Aggregation-Modulated Deterministic Lateral Displacement for Breast Cancer Classification 通过聚集调节的确定性侧向位移对肿瘤来源的细胞外囊泡进行简单和无分离分析，用于乳腺癌分类

IF 7.3 1区化学

Analytical Chemistry Pub Date : 2026-11-10 Epub Date: 2026-10-09 DOI: 10.1021/acs.analchem.6c04739

Xueer Huang, Ting Wu, Haixia Li, Jinyu Liu, Bihong Diao, Jiayi Xiao, Lihong Liu

{"title":"Simple and Isolation-Free Analysis of Tumor-Derived Extracellular Vesicles by Aggregation-Modulated Deterministic Lateral Displacement for Breast Cancer Classification","authors":"Xueer Huang, Ting Wu, Haixia Li, Jinyu Liu, Bihong Diao, Jiayi Xiao, Lihong Liu","doi":"10.1021/acs.analchem.6c04739","DOIUrl":"10.1021/acs.analchem.6c04739","url":null,"abstract":"Tumor-derived extracellular vesicles (EVs) are increasingly recognized as potential biomarkers for breast cancer (BC) diagnosis and molecular subtyping; however, most current analytical methods rely on laborious EV isolation and sophisticated instrumentation, limiting their routine clinical implementation. Herein, we report an aggregation-modulated deterministic lateral displacement (AM-DLD) platform for simple, label-free analysis of tumor-derived EVs without EV isolation. In this strategy, aptamer-functionalized polystyrene microspheres convert nanoscale EV recognition into microscale microsphere aggregates through target EV-mediated cross-linking, enabling direct analysis using a conventional DLD chip. Because EV-induced aggregation generates microsphere aggregates with heterogeneous sizes, a weighted lateral displacement index (LDI) was developed to integrate particle distributions across multiple DLD outlets into a single quantitative readout. Using EpCAM-positive EVs for BC detection and PD-L1-positive EVs for triple-negative BC (TNBC) classification, the AM-DLD platform achieved limits of detection of 8.20 × 105 and 1.67 × 106 particles mL−1, respectively, together with high linearity, specificity, stability, and recovery. Clinical validation using serum samples from 153 individuals yielded AUC values of 0.9806 for BC detection and 0.9642 for TNBC classification. This work establishes a generalizable signal-conversion strategy that extends conventional DLD technology from microscale particle manipulation to nanoscale biomarker analysis, providing an analytical platform for EV-based liquid biopsy.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"98 44","pages":"31195–31204"},"PeriodicalIF":7.3,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151199","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}

引用次数: 0

High-Throughput Dual-Optical Droplet Screening for Quantitative Functional Bacterial Selection 高通量双光学液滴筛选定量功能性细菌选择

IF 7.3 1区化学

Analytical Chemistry Pub Date : 2026-11-10 Epub Date: 2026-10-08 DOI: 10.1021/acs.analchem.6c02939

Esther S. Richter, Andreas Link, Raymond Sparrow, Thomas Franke

{"title":"High-Throughput Dual-Optical Droplet Screening for Quantitative Functional Bacterial Selection","authors":"Esther S. Richter, Andreas Link, Raymond Sparrow, Thomas Franke","doi":"10.1021/acs.analchem.6c02939","DOIUrl":"10.1021/acs.analchem.6c02939","url":null,"abstract":"Droplet microfluidics enables ultra-high-throughput biological screening, yet most platforms rely on single-parameter optical detection, limiting the information available for selection and analysis. Here, we present a high-throughput droplet screening and sorting platform that integrates simultaneous fluorescence and absorbance (scattering) detection with acoustic actuation for robust, kHz-rate operation. By combining complementary optical modalities within a single device, we enable multi-parameter characterization and sorting of droplets based on both molecular and cellular properties. We first validate the system using model droplets containing defined combinations of fluorophores and absorbers, achieving on-demand sorting of multiple sub-populations with efficiencies exceeding 97% at kilohertz rates. We then demonstrate biological functionality by quantifying bacterial growth via optical density (scattering/absorbance) and protein expression via green fluorescent protein (GFP) fluorescence within the same droplets. This dual readout enables simultaneous assessment of cell proliferation and gene expression and allows normalization of fluorescence signals to cell number, providing single-cell-level insight within droplets. Importantly, we observe a temporal delay of ∼42 min between growth and fluorescence signals, highlighting the dynamic relationship between cell proliferation and protein expression. The ability to resolve and exploit such multi-parameter dynamics enables more precise selection of functional phenotypes, including differentiation of sub-populations based on growth and expression characteristics. This integrated acoustofluidic platform provides a versatile and scalable approach for multi-parameter droplet analysis and sorting, with applications in microbiology, diagnostics, and directed evolution, where simultaneous measurement of the cellular state and function is critical.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"98 44","pages":"30387–30397"},"PeriodicalIF":7.3,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151240","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}

引用次数: 0

Enabling Photoacoustic Imaging and Photothermal Elimination of Senescent Cells via an Activatable Theranostic Probe 通过可激活的治疗探针实现光声成像和光热消除衰老细胞

IF 7.3 1区化学

Analytical Chemistry Pub Date : 2026-11-10 Epub Date: 2026-10-08 DOI: 10.1021/acs.analchem.6c05223

Chong-Hua Zhang, Sha Zeng, Yu-Yan Sun, Luyang Chen, Jiaqi Hao, Hu Zhou, Xianjun Liu

{"title":"Enabling Photoacoustic Imaging and Photothermal Elimination of Senescent Cells via an Activatable Theranostic Probe","authors":"Chong-Hua Zhang, Sha Zeng, Yu-Yan Sun, Luyang Chen, Jiaqi Hao, Hu Zhou, Xianjun Liu","doi":"10.1021/acs.analchem.6c05223","DOIUrl":"10.1021/acs.analchem.6c05223","url":null,"abstract":"Excessive accumulation of senescent cells disrupts tissue homeostasis, induces chronic inflammation and tumorigenesis, and ultimately accelerates senescence-associated dysfunction and malignant progression. Developing reliable tools for the detection and elimination of senescent cells is critical for the precise diagnosis and timely intervention of aging-associated diseases. However, existing senolytic theranostic probes suffer from oxygen-dependent photodynamic therapy (PDT) efficacy and the inherent limitations of fluorescence imaging in penetration depth and spatial resolution. Herein, we report the first theranostic probe RPM-Gal that integrates senescence-associated β-galactosidase-activated photoacoustic imaging and photothermal elimination of senescent cells. RPM-Gal is assembled by tethering a β-D-galactopyranoside moiety to a rhodol-derived polymethine scaffold (RPM-OH) via a self-immolative benzyl spacer. In vitro tests demonstrate that RPM-Gal possesses an excellent photoacoustic response and outstanding photothermal behavior against β-galactosidase. It is found that the overexpressed β-galactosidase in senescent cells can specifically activate the PA signal and the PTT effect of RPM-Gal upon light irradiation. This probe has been further successfully implemented for PA imaging and photothermal elimination of senescent tumor cells in vivo, establishing a targeted avenue for effective senolytic therapy.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"98 44","pages":"31510–31519"},"PeriodicalIF":7.3,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152009","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}

引用次数: 0

Sink-dFCM: Microparticle Floating-to-Sinking-Enabled Digital Flow Cytometric Platform for Multiplexed microRNA Sensing Sink-dFCM：用于多路microRNA传感的微粒漂浮到下沉的数字流式细胞术平台

IF 7.3 1区化学

Analytical Chemistry Pub Date : 2026-11-10 Epub Date: 2026-10-12 DOI: 10.1021/acs.analchem.6c04043

Tianyu Zhang, Wenjiao Fan, Yuanyuan Dong, Xinyu Yu, Wei Ren, Chenghui Liu

{"title":"Sink-dFCM: Microparticle Floating-to-Sinking-Enabled Digital Flow Cytometric Platform for Multiplexed microRNA Sensing","authors":"Tianyu Zhang, Wenjiao Fan, Yuanyuan Dong, Xinyu Yu, Wei Ren, Chenghui Liu","doi":"10.1021/acs.analchem.6c04043","DOIUrl":"10.1021/acs.analchem.6c04043","url":null,"abstract":"Digital bioassays, which quantify targets by binarily counting individual microreactors, render the biomarker detection at the single-molecule level, holding great promise in biomedical applications. However, the existing digital bioassays are predominantly achieved with high reliance on complex signal amplification procedures, proprietary experiment consumables, and specialized instruments for signal readout. Here, we present a new microparticle floating-to-sinking-enabled digital flow cytometric platform, termed Sink-dFCM, for the sensitive and multiplexed microRNA (miRNA) analysis with simple operation. Specifically, the polymer microparticles (MPs), acting as the single-molecule reaction carriers, float on the surface of the liquid that is at a critical density just a little bit higher than that of the MPs. While even a single miRNA-mediated one-step click chemical ligation of magnetic nanoparticles can provide enough downward force to drag the floating MPs to sink, enabling the “one miRNA-one sunken ligation complex” signal transduction. Accordingly, by immobilizing the fluorescently encoded MPs with miRNA-specific click chemical probes, different miRNA targets induce different colors of sunken events. Therefore, the multiplexed miRNA analysis can be achieved via profiling the fluorescence and number information of colored sunken events with the versatile flow cytometer. By eliminating the need for multistep signal amplification procedures, proprietary experiment necessities and dedicated instruments, Sink-dFCM not only presents a unique concept toward rapid digital multiplexed biosensing, but also extends the diagnostic toolbox with outstanding clinical translational potential.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"98 44","pages":"30730–30738"},"PeriodicalIF":7.3,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152015","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}

引用次数: 0

Visualizing the Effect of Escape-Promoting Agents on Endosomal Escape of RNA Nanoparticles by Using High Time-Spatial Resolution Imaging 利用高时空分辨率成像技术可视化促逃逸剂对RNA纳米颗粒内体逃逸的影响

IF 7.3 1区化学

Analytical Chemistry Pub Date : 2026-11-10 Epub Date: 2026-10-12 DOI: 10.1021/acs.analchem.6c04344

Hui Wang, Siying Li, Hongda Wang, Yuping Shan

{"title":"Visualizing the Effect of Escape-Promoting Agents on Endosomal Escape of RNA Nanoparticles by Using High Time-Spatial Resolution Imaging","authors":"Hui Wang, Siying Li, Hongda Wang, Yuping Shan","doi":"10.1021/acs.analchem.6c04344","DOIUrl":"10.1021/acs.analchem.6c04344","url":null,"abstract":"The therapeutic efficacy of RNA nano-drugs is severely hampered by the endosomal delivery bottleneck, wherein internalized cargo is trapped and degraded within the endolysosomal pathway. While promoting endosomal escape strategies have been extensively pursued, their efficiency remains limited; understanding the mechanism of promoting endosome escape is urgently necessary. Herein, confocal microscopy was utilized to visually characterize how canonical chemical agents (nigericin, chloroquine, and sucrose) and cell-penetrating peptides (TAT and F-TAT) facilitate endosomal escape, with particular focus on their modulatory impacts on endosomal morphology and intracellular cargo release. It is found that the chemical agents could enhance the escape probability by enlarging the early endosomes and lysosomes with pores on the endosomes, and the degree of endosomal swelling, rather than the mere number of pores, is the principal driver of differential escape efficiency. In contrast, cell-penetrating peptides TAT could significantly promote the escape efficiency even for the late endosome, without altering the morphology of endosomes. Furthermore, the fluorinated derivative F-TAT facilitated a more rapid endosomal escape, and the most escape can be completed within 30 s. High spatiotemporal resolution direct stochastic optical reconstruction microscopy (dSTORM) imaging further revealed the conformation of pores on the endosomes after treatment with chemical agents. Our findings provide crucial insights into the mechanism of promoting endosomal escape, establishing a correlative framework between agent-induced endosomal remodeling and escape outcomes. This work will offer guideline for achieving high efficiency of intracellular RNA release, thereby maximizing therapeutic potential.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"98 44","pages":"30915–30924"},"PeriodicalIF":7.3,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152016","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}

引用次数: 0

Photobleaching-Driven Ratiometric Fluorescent Switching of ZGO:Mn Nanorods/RhB for Iodine Vapor Monitoring with Integrated Gas-Phase Separation 光漂白驱动的ZGO:Mn纳米棒/RhB比例荧光开关用于碘蒸气监测集成气相分离

IF 7.3 1区化学

Analytical Chemistry Pub Date : 2026-11-10 Epub Date: 2026-10-14 DOI: 10.1021/acs.analchem.6c04851

Xiaohan Jin, Yue Gao, Jian Zhang, Zhu Jin, Yuanhang Ming, Lianhang Li, Lifang He, Kui Zhang

{"title":"Photobleaching-Driven Ratiometric Fluorescent Switching of ZGO:Mn Nanorods/RhB for Iodine Vapor Monitoring with Integrated Gas-Phase Separation","authors":"Xiaohan Jin, Yue Gao, Jian Zhang, Zhu Jin, Yuanhang Ming, Lianhang Li, Lifang He, Kui Zhang","doi":"10.1021/acs.analchem.6c04851","DOIUrl":"10.1021/acs.analchem.6c04851","url":null,"abstract":"Conventional fluorescent sensors generally rely on complex, time-consuming structural engineering of recognition moieties. By contrast, leveraging photobleaching for eco-friendly, reagent-free signal transduction has long been impeded by irreversible fluorophore degradation. Additionally, direct liquid-phase detection of trace radioactive iodine species (I2 or I−) persistently suffers from severe matrix interference. Herein, we engineered a novel photobleaching-driven ratiometric fluorescent platform that exploits the marked difference in photostability between structurally robust manganese-doped zinc gallate nanorods (ZGO:Mn NRs) and photo-stable rhodamine B (RhB) fluorophores. Under low-power UV irradiation, photogenerated superoxide radicals and holes induce pronounced self-quenching of ZGO:Mn NRs without compromising their crystalline structure. Upon exposure to I2, these reactive species are rapidly scavenged, restoring the intrinsic green luminescence of the nanorods and producing a distinct orange-to-green color transition. The ratiometric probe exhibits excellent sensitivity, with a limit of detection (LOD) as low as 1.54 nM. To eliminate matrix interference, we seamlessly integrate a custom 3D-printed miniaturized gas-phase separation module, which converts nonvolatile I− into volatile I2, with a smartphone-based machine-vision readout system. The system was successfully applied to detect trace iodide in complex soil, raw lake water, and kelp extract samples, with recoveries ranging from 94.7% to 105.6%, demonstrating great promise for nuclear regulatory monitoring.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"98 44","pages":"31306–31316"},"PeriodicalIF":7.3,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209386","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}

引用次数: 0

Operando Raman Investigation of Interfacial Molecular Vibrations for CO2 Electroreduction on Cu-Based Gas Diffusion Electrodes under Back Pressure 背压下cu基气体扩散电极CO2电还原界面分子振动的Operando Raman研究

IF 7.3 1区化学

Analytical Chemistry Pub Date : 2026-11-10 Epub Date: 2026-10-14 DOI: 10.1021/acs.analchem.6c03442

Baoxin Ni, Wenxin Zhao, Yihao Wen, Xue Wen, Peng Shen, Sida Li, Guiru Zhang, Zi Wang, Shuiyun Shen, Hao Wei

{"title":"Operando Raman Investigation of Interfacial Molecular Vibrations for CO2 Electroreduction on Cu-Based Gas Diffusion Electrodes under Back Pressure","authors":"Baoxin Ni, Wenxin Zhao, Yihao Wen, Xue Wen, Peng Shen, Sida Li, Guiru Zhang, Zi Wang, Shuiyun Shen, Hao Wei","doi":"10.1021/acs.analchem.6c03442","DOIUrl":"10.1021/acs.analchem.6c03442","url":null,"abstract":"Back-pressure regulation serves as a promising strategy to boost electrochemical CO2 reduction performance, owing to its unique capability to enrich interfacial reactants and modulate reaction pathways. Nevertheless, dynamic tracking of gas-liquid-solid interfacial species evolution under practical milliampere-level reaction conditions remains largely underexplored. Herein, a customized flow-cell-coupled Raman platform was adopted to dynamically monitor the electrocatalytic CO2 conversion behavior of Cu-based electrodes, alongside the structural evolution of surface-adsorbed intermediates and interfacial hydrogen bond networks across a continuous back-pressure gradient (0−150 mbar). In the current density range of 0−100 mA·cm−2, elevating back pressure dramatically suppressed the hydrogen evolution reaction, with H2 selectivity dropping from 43.6% (0 mbar) to 16.7% (150 mbar). By contrast, the faradaic selectivity of C2+ products increased steadily from 19.6% to 59.3%, and the yield of oxygenated products was also positively correlated with back-pressure intensity. Operando Raman characterizations reveal that applied back pressure delivers dual interfacial modulation effects: it elevates the surface coverage of key CO reaction intermediates and reorganizes local hydrogen bond configurations. The optimized interfacial structure accumulates strongly hydrogen-bonded water molecules, which constrain the migration of protons and hydroxyl ions. Such structural regulation strengthens interfacial alkalinity and ultimately facilitates the electrocatalytic generation of C2+ products.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"98 44","pages":"30444–30453"},"PeriodicalIF":7.3,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209388","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}

引用次数: 0

A Two-Step Strategy Based on Fpg Recognition and RCA-CRISPR/Cas12a for Ultrasensitive Detection of Gene Mutation 基于Fpg识别和RCA-CRISPR/Cas12a的基因突变超灵敏检测两步策略

IF 7.3 1区化学

Analytical Chemistry Pub Date : 2026-11-10 Epub Date: 2026-10-14 DOI: 10.1021/acs.analchem.6c04145

Shiying Zhou, Tingting Xiang, Zengqin Cha, Jiayan Song, Yuanfang Xiang, Xiang Li, Chunlan Huang, Qibing Mei, Xinwu Huang, Chunxiang Zhang, Jianming Wu

{"title":"A Two-Step Strategy Based on Fpg Recognition and RCA-CRISPR/Cas12a for Ultrasensitive Detection of Gene Mutation","authors":"Shiying Zhou, Tingting Xiang, Zengqin Cha, Jiayan Song, Yuanfang Xiang, Xiang Li, Chunlan Huang, Qibing Mei, Xinwu Huang, Chunxiang Zhang, Jianming Wu","doi":"10.1021/acs.analchem.6c04145","DOIUrl":"10.1021/acs.analchem.6c04145","url":null,"abstract":"Accurate detection of gene mutations is crucial for acute myeloid leukaemia (AML) diagnosis and treatment. Although CRISPR/Cas systems enable sensitive mutation detection, their adaptability is constrained by dependence on restriction endonucleases. Herein, we propose a two-step strategy, termed Fpg-RCA-CRISPR/Cas12a for ultrasensitive detection of the p53 R175H, which integrates formamidopyrimidine DNA glycosylase (Fpg)-mediated recognition with rolling circle amplification (RCA)-coupled CRISPR/Cas12a technology. Validation confirmed that Fpg exhibits minimal activity when adenine (A) is opposite the damaged site. Based on this finding, we designed a padlock probe with a site-specific 8-oxoguanine (8-oxoG) modification. This modification enables selective recognition of G > A mutations. For the target TP53 c.524G > A (p53 R175H), the G > A substitution opposite the 8-oxoG site blocks Fpg cleavage, facilitating probe circularization and subsequent RCA. The resulting RCA products then activate the trans-cleavage activity of Cas12a, enabling cascade signal amplification and generating a strong fluorescence output. For wild-type p53, Fpg-mediated cleavage prevents circularization and amplification, yielding weak fluorescence. Taking advantage of the high specificity of the Fpg enzyme and the cascade amplification effect of the RCA−CRISPR/Cas12a system, this method achieves a limit of detection (LOD) of 0.29 fM and covers a linear range from 0.8 fM to 800 pM, along with high reproducibility, excellent selectivity, and negligible background interference. Notably, the assay can detect mutation frequencies as low as 0.1% in excess wild-type p53. Crucially, its clinical feasibility was confirmed by analyzing human serum samples, yielding results consistent with standard assays and thus demonstrating its practical reliability and translational potential.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"98 44","pages":"30873–30882"},"PeriodicalIF":7.3,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209443","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}

引用次数: 0