Analytical Chemistry最新文献

{"title":"Background-Free Mid-Infrared Photothermal Microscopy via Single-Shot Measurement of Thermal Decay","authors":"Rylie Bolarinho, Jiaze Yin, Hongli Ni, Qing Xia, Ji-Xin Cheng","doi":"10.1021/acs.analchem.4c03689","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c03689","url":null,"abstract":"Mid-infrared photothermal (MIP) microscopy is an emerging tool for biological imaging, offering high sensitivity, subcellular resolution, and rapid image acquisition. However, the MIP signal of low concentration molecules in biological systems is often hindered or masked by background absorption, largely contributed by water, resulting from the H–O–H scissors-bending band in the fingerprint window or the bend-libration combination band in the cell-silent window. To preserve all desired signals while suppressing the background, we report a single-shot time-resolved MIP measurement that allows differentiation between the background and analyte signal based on their distinct photothermal dynamics. The results show that the thermal decay of the background is significantly longer than that of the desired intracellular signal, mainly due to the larger mass and heat capacity of water compared to those of intracellular features. Through two-component exponential fitting, we successfully differentiated and suppressed the background, while preserving the desired intracellular signal in both the fingerprint and cell-silent windows. By leveraging the thermal dynamics differences obtained from a single-shot measurement, we effectively remove the background and enhance the detection of small signals in a biological system.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"13 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443891","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":"Advancing Biomarker Research: In Situ Cu Isotope Analysis in Liver Tumors by LA-MC-ICP-MS","authors":"Mathias Schannor, Marcus Oelze, Heike Traub, Yubei He, Robin Schmidt, Luisa Heidemann, Lynn Jeanette Savic, Jochen Vogl, Björn Meermann","doi":"10.1021/acs.analchem.4c05626","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05626","url":null,"abstract":"Stable metal isotopes have received increasing attention as medical biomarkers due to their potential to detect changes in metal metabolism related to diseases. In particular, copper stable isotopes are a powerful tool to identify isotopic variation between tumors and healthy tissue, suggesting application in cancer diagnosis. However, potential mechanisms causing isotope fractionation, such as redox- or bond-forming reactions and interactions of metals during transmembrane import and export, are less well understood. Here, we established an <i>in situ</i> method using laser ablation-multicollector-inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) to advance our understanding of the underlying processes responsible for isotope fractionation between normal and diseased tissues. Gelatin-based bracketing standards and quality control reference materials, crucial for laser ablation analysis, were developed to allow correction for instrumentally induced isotope fractionation during LA-MC-ICP-MS analysis. Using such matrix-matched standards, the method achieved intermediate precisions for delta values of better than 0.15 ‰ (2 <i>s</i>) for inorganic reference materials and of better than 0.17 ‰ (2 <i>s</i>) for biological reference materials. The developed routine was tested on rabbit VX2 liver tumor samples, a model system resembling human hepatocellular carcinoma (HCC) used to study liver cancer. <i>In situ</i> Cu isotope compositions between healthy (<i></i><span style=\"color: inherit;\"></span><span data-mathml='<math xmlns=\"http://www.w3.org/1998/Math/MathML\" display=\"inline\"><msubsup><mrow><mi>δ</mi></mrow><mrow><mi>NIST</mi><mn>976</mn></mrow><mrow><mi>65/63</mi></mrow></msubsup><mrow><mo stretchy=\"false\">(</mo><mi>Cu</mi><mo stretchy=\"false\">)</mo></mrow></math>' role=\"presentation\" style=\"position: relative;\" tabindex=\"0\"><nobr aria-hidden=\"true\"><span style=\"width: 5.514em; display: inline-block;\"><span style=\"display: inline-block; position: relative; width: 5.003em; height: 0px; font-size: 110%;\"><span style=\"position: absolute; clip: rect(1.48em, 1004.95em, 3.014em, -999.997em); top: -2.554em; left: 0em;\"><span><span><span style=\"display: inline-block; position: relative; width: 3.185em; height: 0px;\"><span style=\"position: absolute; clip: rect(3.128em, 1000.46em, 4.151em, -999.997em); top: -3.974em; left: 0em;\"><span><span style=\"font-family: STIXMathJax_Normal-italic;\">𝛿</span></span><span style=\"display: inline-block; width: 0px; height: 3.98em;\"></span></span><span style=\"position: absolute; clip: rect(3.298em, 1001.71em, 4.151em, -999.997em); top: -4.372em; left: 0.457em;\"><span><span style=\"font-size: 70.7%; font-family: STIXMathJax_Main;\">65/63</span></span><span style=\"display: inline-block; width: 0px; height: 3.98em;\"></span></span><span style=\"position: ab","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"21 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435625","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":"Two-Dimensional Nanozyme-Catalyzed Colorimetric CRISPR Assay for the Microfluidic Detection of Monkeypox Virus","authors":"Hong Chen, Xiaodan Cheng, Yunxiang Wang, Ning Han, Liyan Liu, Hongjuan Wei, Zhijie Tu, Zhixia Gu, Rui Song, Shengqi Wang, Zhen Rong","doi":"10.1021/acs.analchem.4c05570","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05570","url":null,"abstract":"The recent monkeypox epidemic outbreaks worldwide highlight the urgent need for fast and precise diagnostic solutions, especially in resource-limited settings. Here, a two-dimensional nanozyme-catalyzed colorimetric CRISPR assay for the microfluidic detection of the monkeypox virus (MPXV) was established. We utilized graphene oxide as a substrate for the adsorption of gold seeds and the deposition of a porous Pt shell to prepare high-performance two-dimensional GO@Pt nanomaterials. The viral nucleic acids released from clinical samples initiated a single-step recombinase polymerase amplification-CRISPR/Cas13a for the trans-cleavage of ssRNA reporters labeled with FAM and biotin. These reporters can be recognized by FAM antibody-conjugated GO@Pt nanozymes and streptavidin-coated magnetic beads. The formed sandwich immunocomplexes can catalyze the oxidation of a colorless 3,3′,5,5′-tetramethylbenzidine substrate with a distinct color change. The proposed GO@Pt-catalyzed colorimetric CRISPR assay exhibited a limit of detection of 1 copy/μL of MPXV in 60 min. Forty clinical samples, including rash fluid swabs and oral swabs, were tested with 100% agreement with the real-time PCR. These results indicate the excellent potential of GO@Pt-catalyzed colorimetric CRISPR for the sensitive and accurate testing of MPXV under resource-constrained conditions.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"49 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443873","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":"Electrochemiluminescence Biosensor Based on a Self-protected DNAzyme Walker with a Circular Bulging DNA Shield for MicroRNA Detection","authors":"Juan Zhang, Haonan He, Shimao Du, Benting Xie, Hejun Gao, Hongquan Fu, Yunwen Liao","doi":"10.1021/acs.analchem.4c06552","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06552","url":null,"abstract":"Herein, an electrochemiluminescence (ECL) biosensor is established for the ultrasensitive detection of microRNA (miRNA) by integrating a self-protected DNAzyme walker machine on a Au nanoparticle–modified electrode. Using Let-7a miRNA as the model target and by introducing a target-binding domain into the middle of the catalytic core, the catalytic core of the DNAzyme walker is separated by a target-binding domain that can inhibit the cleavage activity and serve as an arch-like protective shield, resulting in a self-protected DNAzyme walker. High-efficiency hybridization between the target Let-7a miRNA and the target-binding domain activates the DNAzyme walker machine, enabling high catalytic cleavage of its substrate without requiring additional energy input. Importantly, each step of the DNAzyme walker results in the cleavage of a substrate strand and the liberation of a Ru(bpy)₂(mcpbpy)²⁺ (Ru)-labeled DNA fragment, considerably reducing the ECL signal of Ru. Under optimized experimental conditions, the limit of detection of Let-7a miRNA is 51.4 aM within a wide linear range of 100 aM–100 pM. This proposed strategy is a bold innovation in the rapid and sensitive detection of low-abundance biomarkers, offering a promising application for early cancer diagnosis and relevant research.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"24 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435626","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-Cell/Particle Sample Introduction Device for Mass Cytometry Based on Gas-Driven Flow Focusing","authors":"Huaiyi Chen, Jinhui Liu, Yu Zhao, Haitao Xu, Weiliang Liu, Zhi Xing, Fei Tang, Sichun Zhang, Xinrong Zhang","doi":"10.1021/acs.analchem.4c06466","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06466","url":null,"abstract":"Mass cytometry is considered the second generation of flow cytometry technology, which uses metal-labeled antibodies instead of traditional fluorescent antibodies and can measure much more markers from a single cell simultaneously. However, due to frequent clogging of the capillary and nebulizer, it is still a complicated task to perform the sample introduction smoothly for a long-term determination. Herein, a plug-and-play sample introduction device for mass cytometry analysis was developed based on a gas-driven flow focusing protocol. The device is integrated with a virtual hole to generate liquid jet and omit a conventional nebulizer. Single-cell monodispersion can be achieved by liquid jet breakup instead of the commonly used nebulization by the Venturi effect, thus avoiding clogging of thin central capillary. The device has high universality and compatibility and can be plug-and-play on a mass cytometry instrument or common inductively coupled plasma mass spectrometry for single-cell or single-particle determination. High-speed microscopy imaging was used to capture and study the dynamic processes of monodispersion on microsphere suspensions achieved by the device. We also compared the analysis capabilities when using the device and a conventional nebulizer in mass cytometry analysis of four element calibration beads and cell samples. The results obtained by using the flow focusing device and the conventional nebulizer show great consistency, which means the device has no negative impact on the detection performance of mass cytometry and single-cell/particle monodispersion can be achieved without clogging.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"49 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427106","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":"Removal of Homogeneous Broadening from 1H-Detected Multidimensional Solid-State NMR Spectra","authors":"Frédéric A. Perras, Songlin Wang, Jacob Mayer, Mita Halder, Alexander L. Paterson, Damien B. Culver, Chad M. Rienstra","doi":"10.1021/acs.analchem.4c06696","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06696","url":null,"abstract":"¹H-detected magic-angle spinning (MAS) NMR experiments have revolutionized the NMR studies of biological and inorganic solids by providing unparalleled sensitivity and resolution. Despite these gains, homogeneous broadening, originating from the incomplete removal of homonuclear dipolar interactions under fast MAS, remains highly prevalent and limits the achievable resolution. In direct analogy to super-resolution microscopy methods, we show that resolution beyond that currently achievable by fast MAS alone can be obtained by experiment-driven deconvolution. Following the acquisition of a single 2D NMR spectrum to measure the frequency-dependent homogeneous lineshapes, any number of ¹H-detected spectra can be enhanced in resolution, yielding comparable spectra as obtained with twice the MAS frequency. The versatility of this approach is demonstrated in the enhancement of single- and double-quantum homonuclear correlation spectra, in addition to heteronuclear correlation spectra acquired on a surface organometallic complex and the protein GB1.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"64 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435728","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":"Electronic Chemical Sensors Based on Conductive Framework Materials","authors":"Emma K. Ambrogi, Katherine A. Mirica","doi":"10.1021/acs.analchem.4c02522","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c02522","url":null,"abstract":"The development of portable electronic chemical sensors is key to solving a number of challenges, including monitoring environmental and industrial hazards, as well as understanding and improving human health. Framework materials possess several desirable characteristics that make them well-suited for electroanalytical applications, including high surface area, atomically precise distribution of active sites, and tunable properties that can be leveraged through modular reticular chemistry. This review highlights the emergence of conductive framework materials as active components in electrically transduced chemical sensors, including the development of new materials for the detection of a wide variety of analytes in both gas and liquid phase. The efforts to gain fundamental understanding of the molecular interactions and sensing mechanisms between framework materials and analytes are described, along with applications of these materials on portable and flexible substrates. The review suggests areas for further study, including the study of material–analyte interactions at the molecular level and the continued development of scalable methods for the integration of framework materials into low-power, portable sensing devices.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"32 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427104","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":"Bidirectionally Favorable Platform: A Dual-Targeting Probe-Encoded Maple Leaf-Type Fluorescent Lateral Flow Immunoassay for Multiple Biomarker Detection","authors":"Siqi Zeng, Wanchao Zuo, Huilin Zhang, Jiaren Song, Qing Yang, Qiannan Hu, Xiangming Meng, Wenxuan Chen, Yazhou Wang, Jianjun Dai, Yanmin Ju","doi":"10.1021/acs.analchem.4c06414","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06414","url":null,"abstract":"In the traditional multiplexed lateral flow immunoassay (LFIA), different detection probes against different targets are necessary. However, the relative complexity and high cost of probe preparation, as well as the insufficient user-friendliness, limit the application of the multiplexed LFIA in disease diagnosis. Here, we reported a bidirectionally favorable LFIA (BDF-LFIA) platform to maximize convenience for both manufacturers and users. Red-emitting time-resolved fluorescent nanoparticles were coated with different antibodies to recognize multiple targets simultaneously, which greatly simplified probe preparation by the manufacturers. Ultrabright green-emitting gold nanoclusters were pre-embedded on the test line as a reference signal to achieve a target concentration-dependent maple leaf-type hue readout from green to yellow to red, which was quite user-friendly. Taking cancer biomarkers alpha-fetoprotein and carcinoembryonic antigen as examples, this assay achieved a visual detection limit of 2 ng/mL. Compared with the conventional fluorescent LFIA, the BDF-LFIA could generate a more discernible signal around the threshold concentration of the targets. Moreover, the assay successfully diagnosed 54 clinical samples. Overall, the BDF-LFIA showed bidirectional benefits for both manufacturers and users and provided a new concept for the LFIA in multiplexed detection.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"49 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435652","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":"Structural Lipidomics Enabled by Isomer-Resolved Tandem Mass Spectrometry","authors":"Yikun Liu, Yu Xia, Wenpeng Zhang","doi":"10.1021/acs.analchem.4c06680","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06680","url":null,"abstract":"This article has not yet been cited by other publications.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"64 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427107","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":"Increased Sensitivity in VOC Detection by Using a Novel Photoinduced Multiple Ionization Mass Spectrometry","authors":"Xun Bao, Qu Liang, Qiangling Zhang, Xue Zou, Chaoqun Huang, Chengyin Shen, Yannan Chu","doi":"10.1021/acs.analchem.4c05873","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05873","url":null,"abstract":"Proton transfer reaction mass spectrometry (PTR-MS) is an important online monitoring technique for volatile organic compounds (VOCs). VOCs have the characteristics of many types, rapid change, and low concentration. Enhancing the detection sensitivity and expanding the detection range of VOCs have been key challenges in PTR-MS research. In this work, we have developed and characterized a novel photoinduced multiple ionizations (PMI) source, which consists of four direct current (DC) vacuum ultraviolet Kr lamps and a V-shaped focusing quadrupole ion funnel (FQ-IF) drift tube. The novel PMI source has four ionization processes: proton transfer reaction, charge transfer reaction, single photon ionization, and photoelectron impact ionization. It is capable of detecting VOCs detectable by conventional PTR-MS via the PTR, as well as VOCs (carbon disulfide and acetylene) that are difficult to detect by conventional PTR-MS through other ionization processes, thus effectively expanding the detection range. In further comparative experiments, the improvements in sensitivity for the PMI-MS in FQ-IF mode range from 122.5 to 647.7 times compared to the PTR-MS in DC mode (conventional PTR-MS) for 12 test VOCs. Notably, the sensitivities of four BTEXs in 12 VOCs were more than 10,000 cps/ppb. Moreover, compared with PTR-MS in DC mode, the LOD of PMI-MS in FQ-IF mode for 12 test VOCs increased by 26–128.6 times. PMI-MS not only expands the detection range but also improves the sensitivity by 2 orders of magnitude, which would provide an important tool for the detection of ultratrace VOCs.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"2 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427105","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}