{"title":"A Dual-Ion Synergistic Catalysis Utilizing Zn2+-Regulated CdSySe1–y ECL Immunosensor Employed for the Ultrasensitive CA19-9 Detection","authors":"Dawei Fan, Zhengxing Gong, Guangyue He, Hanxiao Liu, Yingli Wang, Hongmin Ma, Dan Wu, Huan Wang, Qin Wei","doi":"10.1021/acs.analchem.4c05034","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05034","url":null,"abstract":"Carbohydrate antigen 19-9 is a well-known malignancy biomarker, and its sensitive detection is particularly crucial in the diagnosis and assessment of pancreatic cancer. In this study, an ultrasensitive CA19-9 immunosensor was constructed using the Zn<sup>2+</sup>-regulated CdS<sub><i>y</i></sub>Se<sub>1–<i>y</i></sub> (Zn-CdS<sub><i>y</i></sub>Se<sub>1–<i>y</i></sub>) nanospheres (NSs) as the electrochemiluminescence (ECL) emitter and FeCoS<sub>2</sub> nano octahedrons (NOs) as a coreactant enhancer. The microstructure of ternary transition metal chalcogenide CdS<sub><i>y</i></sub>Se<sub>1–<i>y</i></sub> was precisely tuned by Zn<sup>2+</sup> doping to avoid aggregation and thus enable stable and efficient cathodic ECL responses. The bimetallic sulfide FeCoS<sub>2</sub> was synthesized using a metal organic framework (MOF) as the template by ion permeation. It was able to catalyze the coreactant efficiently due to the synergistic effect of the Fe<sup>2+</sup> and Co<sup>2+</sup>. The immunosensor exhibited low detection limit (7.6 × 10<sup>–5</sup> U mL<sup>–1</sup>) in the wide linear range of 0.0001–100 U mL<sup>–1</sup>, offering a sensitive CA19-9 detection method.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"61 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142684918","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":"Laser-Induced Thermophoretic SERS Enhancement on Paper for Facile Pesticide and Nanoplastic Sensing","authors":"Shuang Mu, Zhaowei Tian, Wei Ren, Chenghui Liu","doi":"10.1021/acs.analchem.4c05728","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05728","url":null,"abstract":"Surface-enhanced Raman scattering (SERS) has emerged as a powerful tool for contamination detection. Fabricating efficient nanostructures with hotspots for signal enhancement and concentrating diluted target analyte molecules to the hotspots are critical for ultrasensitive SERS detection, which generally requires advanced instruments and intricate manipulations. Herein, we report a simple, low-cost, and high-efficiency paper device that can simultaneously concentrate the analytes and generate SERS hotspots rapidly with the assistance of laser-induced thermophoresis. After dropping the target- and plasmonic nanoparticle-containing solution on a paper substrate, the evaporative gradient created by the laser-induced thermophoresis can promote the delivery of the analytes and plasmonic nanoparticles simultaneously to the tiny area of the laser spot, forming compact SERS hotspots to significantly amplify the analyte’s Raman scattering signals. This convenient thermophoretic strategy can be accomplished rapidly within ∼4 min and exhibits more than 10<sup>4</sup>-times higher sensitivity than that without the assistance of laser-based thermophoresis. This elegant paper device is successfully applied to the detection of contaminants such as pesticides and nanoplastics in fruit and water samples, holding the potential to provide a simple, fast, and cost-effective approach for on-site detection of environmental contaminants.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"70 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142685042","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}
Min Shi, Yun Zhang, Jia-Xing Chen, Yanyuan Wu, Zongping Wang, Peng-Fei Shi, Xudong Jin, Xue-Qiang Wang
{"title":"A Bicyclic Dioxetane Chemiluminescence Nanoprobe for Peroxynitrite Imaging in Vivo","authors":"Min Shi, Yun Zhang, Jia-Xing Chen, Yanyuan Wu, Zongping Wang, Peng-Fei Shi, Xudong Jin, Xue-Qiang Wang","doi":"10.1021/acs.analchem.4c04510","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c04510","url":null,"abstract":"Peroxynitrite (ONOO<sup>–</sup>) is a critical biomarker associated with a wide array of diseases including cancer, inflammatory conditions, and neurodegenerative disorders. This study introduces an innovative chemiluminescence nanoprobe (CLNP) based on a bicyclic dioxetane structure, designed for highly sensitive and specific in vivo imaging of ONOO<sup>–</sup>. Our CLNP demonstrates exceptional capabilities in generating high-contrast imaging of disease lesions, with applications verified across tumor models, acute inflammation, and acute liver injury scenarios. Key findings highlight the probe’s rapid response to oxidative species, superior tissue penetration, and high signal-to-noise ratio, underscoring its potential for real-time diagnostic applications. This work represents an important advance in the field of diagnostic imaging using CL probes, offering promising avenues for the early detection and treatment of ONOO<sup>–</sup>-related pathologies.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"1 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678924","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}
Zhaowei Meng, Amir Ata Saei, Hezheng Lyu, Massimiliano Gaetani, Roman A. Zubarev
{"title":"One-Pot Time-Induced Proteome Integral Solubility Alteration Assay for Automated and Sensitive Drug–Target Identification","authors":"Zhaowei Meng, Amir Ata Saei, Hezheng Lyu, Massimiliano Gaetani, Roman A. Zubarev","doi":"10.1021/acs.analchem.4c05127","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05127","url":null,"abstract":"The proteome integral solubility alteration (PISA) assay is widely used for identifying drug targets, but it is labor-intensive and time-consuming and requires a substantial amount of biological sample. Aiming at enabling automation and greatly reducing the sample amount, we developed one-pot time-induced (OPTI)-PISA. Here, we demonstrate OPTI-PISA performance on identifying targets of multiple drugs in cell lysate and scaling down the sample amount to sub-microgram levels, making the PISA method suitable for NanoProteomics. OPTI-PISA can be implemented using only the standard equipment of a proteomics lab.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"3 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142679138","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}
Kaineng Huang, Yi He, Xingyu Li, Yuanjiang Pan, Yuanji Gao
{"title":"Unlocking the Mysteries of the Desorption–Ionization Mechanism via Separate Thermal and Charge Strategies","authors":"Kaineng Huang, Yi He, Xingyu Li, Yuanjiang Pan, Yuanji Gao","doi":"10.1021/acs.analchem.4c03823","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c03823","url":null,"abstract":"Herein, a new strategy is employed to build a controllable thermal-coupled charge ionization (TCCI) device to elucidate the desorption–ionization mechanism of plasma ion sources. Efficient synergistic desorption and ionization are achieved within the TCCI device by independently controlling the desorption temperature and plasma charges. The TCCI device efficiently ionizes samples using abundant free electrons, charges, and active species from arc plasma. The coexistence of free electrons and hydroxide radicals confers redox capability to the TCCI system, implying the presence of a unified redox mechanism even when the arc plasma is transmitted through a metal conductor over a distance. In addition, molecular ions of the analytes facilitate the differentiation between primary and secondary amines during their analysis. Notably, the TCCI device enables a switch between hard and soft ionization by adjusting the thermal desorption temperature. At high temperatures (>400 °C), the TCCI device exhibits hard ionization characteristics, producing fragment ions beneficial for isomer discrimination. The TCCI mass spectrometry exhibits robust performance in terms of sensitivity and accuracy for detecting antibiotics and sterols in saline solutions, achieving linearity with correlation coefficients ≥0.99 and excellent reproducibility. The successful analysis of seven pharmaceuticals and four sterols in complex matrices using the TCCI device demonstrates its excellent salt and matrix tolerance. Overall, the TCCI device, with its independent control over thermal desorption and arc plasma, achieves efficient synergistic desorption and ionization, overcoming limitations in existing ionization technologies and contributing to the study of gas-phase ion dynamics and mechanisms.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"84 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678922","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}
Hao Zhang, Jingde Fang, Kaiqin Chu, Zachary J. Smith
{"title":"Real-Time Analysis of Lipid Droplet Morpho-Chemical Dynamics in Living Human Hepatocytes via Phase-Guided Raman Sampling","authors":"Hao Zhang, Jingde Fang, Kaiqin Chu, Zachary J. Smith","doi":"10.1021/acs.analchem.4c03633","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c03633","url":null,"abstract":"Lipid droplets (LDs) are highly dynamic organelles, undertaking many important functions such as maintaining lipid metabolism and cellular homeostasis. Traditional methods to analyze LD dynamics focus on morphological changes, while chemical dynamics cannot be easily probed with traditional analytical chemistry techniques. To overcome this challenge, we show here how our phase-guided Raman sampling method, where high-resolution phase microscopy images direct a Raman sampling beam, can perform label-free, multimodal characterization of LD dynamics in living cells at both the single-cell and single-LD levels with submicron accuracy and high temporal resolution. We demonstrate the study of the morphological–compositional dynamics of human hepatocellular carcinoma cells (PLC cells) under different environmental conditions and with and without fatty acid supplementation, providing insight into LD heterogeneity and heterogeneity of response. Finally, we introduce a measurement method for the dynamics of cell-average LD composition, which can quickly and accurately characterize the lipid dynamics at the single-cell level with <30 s temporal resolution. The results here show the promise of the phase-guided Raman sampling method for dynamic morpho-chemical profiling of organelle populations.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"7 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678849","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-Electrode Flow Cell for Electrochemiluminescent Flow Analysis","authors":"Zhiyong Dong, Yequan Chen, Shiyu Xia, Ala’a Mhmoued Abdllh Alboull, Altaf Hussain, Yu Tian, Guobao Xu","doi":"10.1021/acs.analchem.4c04322","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c04322","url":null,"abstract":"Flow injection analysis and liquid chromatography are frequently combined with electrochemiluminescence (ECL) for flow analysis. Almost all electrochemistry flow analyses employ traditional three-electrode electrochemical flow cells which have working electrode, counter electrode, and reference electrode; however, it is expensive and difficult to fabricate a traditional three-electrode electrochemical flow cell and inconvenient to renew the electrode. In this study, we have developed a single-electrode flow cell using commercially available conductive polyethylene film as the only electrode through potential differences induced by the electrode resistance for the first time. The single-electrode flow cell features a simple structure, easy renewal of the electrode, and low cost compared to the traditional three-electrode electrochemical flow cells. Taking the typical Ru(bpy)<sub>3</sub><sup>2+</sup>/oxalate ECL system as the analytical model, flow analysis of clinically important oxalate was achieved using single-electrode flow cell. A regression linear equation was obtained over the oxalate concentration ranges from 1 to 200 μM, with a detection limit of 0.92 μM. The single-electrode flow cell is promising for ECL flow analysis.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"1 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673056","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}
Tao Tang, Fushou Liu, Biao Huang, Hao Li, Wen-Ping Lin, Zhi-Jun Sun, Mingxi Zhang, Ran Cui
{"title":"Logically Activatable Nanoreporter for Multiplexed Time-Phased Imaging Assessment of Hepatic Ischemia-Reperfusion Injury and Systemic Inflammation","authors":"Tao Tang, Fushou Liu, Biao Huang, Hao Li, Wen-Ping Lin, Zhi-Jun Sun, Mingxi Zhang, Ran Cui","doi":"10.1021/acs.analchem.4c04416","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c04416","url":null,"abstract":"Hepatic ischemia-reperfusion injury (HIRI) and induced systemic inflammation is a time-dependent multistage process which poses a risk of causing direct hepatic dysfunction and multiorgan failure. Real-time in situ comprehensive visualization assessment is important and scarce for imaging-guided therapeutic interventions and timely efficacy evaluation. Here, a logically activatable nanoreporter (termed QD@IR783-TK-FITC) is developed for time-phase imaging quantification of HIRI and induced systemic inflammation. The nanoreporters could be used for in vivo ratiometric NIR-IIb fluorescence sensing of reactive oxygen species (ROS), which can depict the in situ hepatic ROS fluctuation for the early diagnosis of HIRI in the initial 3 h. Meanwhile, the ROS-specific reaction releases renal-clearable fluorophore fragments from nanoreporters for monitoring the systematic inflammation induced by HIRI via longitudinal urinalysis. In addition, a functional relationship between digitized signal outputs (NIR-IIb ratios, urinary fluorescence) with hepatic injury scores has been established, realizing precise prediction of HIRI severity and preassessment of therapeutic efficacy. Such a time-phased modular toolbox can dynamically report HIRI-induced systemic inflammation in vivo, providing an efficient approach for HIRI treatment.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"74 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678923","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":"Analyte-Induced Specific Regulation of Light-Responsive COF-Cu Nanozyme Activity for Ultrafast Thiram Colorimetric Sensing.","authors":"Ling Liang, Ruitao Yang, Jia Wu, Yuan Qin, Yuting Jiang, Shulin Zhao, Fanggui Ye","doi":"10.1021/acs.analchem.4c04534","DOIUrl":"10.1021/acs.analchem.4c04534","url":null,"abstract":"<p><p>A light-responsive covalent-organic framework (COF) nanozyme, which integrates the advantages of the COF structure and light-stimulated nanozyme catalysis, is a class of sensing star materials with wide application prospects. However, the sensing methods based on light-responsive COF nanozymes are relatively single at present. Therefore, it is necessary to develop new sensing strategies to broaden its application in chemical sensing and achieve highly efficient detection. Here, a Cu<sup>2+</sup>-modified COF composite material (TpDA-Cu) was rationally designed. The addition of Cu significantly inhibits the excellent light-responsive nanozyme activity of TpDA itself. However, because of the restoration of the enzyme activity by thiram (Tr) and the oxidase mimic activity of the newly formed Cu/Tr complex, TpDA-Cu/Tr exhibits stronger light-responsive nanozyme activity. Enzyme kinetic data show that compared with TpDA, TpDA-Cu/Tr has a larger <i>V</i><sub>max</sub> value, which can achieve efficient catalytic oxidation of 3,3',5,5'-tetramethylbenzidine (TMB). In addition, the strong coordination effect of Tr and TpDA-Cu also plays a key role in achieving ultrafast, sensitive, and selective colorimetric detection of Tr. This work develops a dual activity regulation strategy of light-responsive COF nanozymes based on analyte induction and provides a new perspective for the application of light-responsive COF nanozymes in the field of sensing.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":" ","pages":"18545-18554"},"PeriodicalIF":6.7,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574825","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":"Dual-Modality Accurate Visualization of Drug Synergy Based on Mass Spectrometry and Fluorescence Imaging.","authors":"Jinlong Zhang, Yida Zhang, Taihe Han, Shuai Mu, Duolong Di, Xuezhao Shi, Xiaoyan Liu, Haixia Zhang","doi":"10.1021/acs.analchem.4c03848","DOIUrl":"10.1021/acs.analchem.4c03848","url":null,"abstract":"<p><p>There is a potential synergistic effect between nonsteroidal anti-inflammatory drugs and hydrogen sulfide (H<sub>2</sub>S), but direct evidence for the study is lacking. With a single fluorescence detection method, it is difficult to accurately confirm the effectiveness of the synergistic effect. In this study, the fluorescent probe and the nonsteroidal anti-inflammatory drug naproxen were combined via different self-immolative spacer groups to obtain a diagnostic and therapeutic integrated fluorescent probe <b>Nap-NP-NSB</b>, which can release H<sub>2</sub>S. The quantitative release of H<sub>2</sub>S by <b>Nap-NP-NSB</b> was evaluated <i>in vitro</i> and in cells, and the synergistic effect of H<sub>2</sub>S and naproxen was confirmed by monitoring the treatment process of cellular inflammation and oxidative damage of gastric mucosa cells. Finally, <i>in vivo</i> fluorescence imaging and mass spectrometry imaging of the liver and stomach tissues and their sections were performed in the mouse model of acute hepatitis. The dual-modal detection method not only confirmed that <b>Nap-NP-NSB</b> had better anti-inflammatory activity and less gastric mucosal damage, but also enabled a more accurate visualization of the drug synergistic effect of naproxen and H<sub>2</sub>S. This work provides a dual visualization imaging method combining fluorescence and mass spectrometry imaging and develops a new idea for studying drug synergies based on self-immolative structures.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":" ","pages":"18474-18482"},"PeriodicalIF":6.7,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574827","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}