Analytical Chemistry最新文献

Multiplex and Spatiotemporal Detection of Single-Cell Antibody Secretions Using Protein-Patterned Microwells. 利用蛋白图谱微孔对单细胞抗体分泌物进行多重时空检测。

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-13 DOI: 10.1021/acs.analchem.5c03396

Julie Van Lent,Karen Ven,Maya Imbrechts,Nick Geukens,Paul Declerck,Karen Vanhoorelbeke,Jeroen Lammertyn

{"title":"Multiplex and Spatiotemporal Detection of Single-Cell Antibody Secretions Using Protein-Patterned Microwells.","authors":"Julie Van Lent,Karen Ven,Maya Imbrechts,Nick Geukens,Paul Declerck,Karen Vanhoorelbeke,Jeroen Lammertyn","doi":"10.1021/acs.analchem.5c03396","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c03396","url":null,"abstract":"Antibodies (Abs) are pivotal components in a myriad of applications including therapeutics and diagnostics. To discover novel target-specific Abs, screening and isolating Ab-expressing cells have proven to be an interesting route. Nevertheless, current single-cell technologies still come with some limitations, as they, for example, do not enable combined temporal and multiplex screening. To overcome these limitations, we present a microwell-based microfluidic device that enables in-depth analysis of Ab-secreting cells. By micropatterning several proteins of interest onto specific regions of the wells, we were able to: (i) investigate single cells' secretion profiles over time, and (ii) identify cells secreting Abs of interest against different proteins simultaneously. This was shown for hybridomas secreting Abs against either the receptor binding domain or the nucleocapsid of the SARS-COV-2 virus. Moreover, our strategy is easily adaptable to a wide range of secretome studies as it enables the patterning of different proteins of interest (e.g., ligands and cell-adhesive proteins) and thus shows great promise for applications across numerous fields, including fundamental (e.g., cell-cell communication) and applied (e.g., drug discovery) research.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"3 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145277311","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

Efficient Photochemical Generation of Germanium and Arsenic Hydrides in a Sulfite and Iodide Medium. 亚硫酸盐和碘化物介质中锗和砷氢化物的高效光化学生成。

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-13 DOI: 10.1021/acs.analchem.5c02292

Liang Dong,Xiuqin Deng,Chenyu Zhang,Xiaoqin Sheng,Yue Teng,Zeming Shi,Ying Gao

{"title":"Efficient Photochemical Generation of Germanium and Arsenic Hydrides in a Sulfite and Iodide Medium.","authors":"Liang Dong,Xiuqin Deng,Chenyu Zhang,Xiaoqin Sheng,Yue Teng,Zeming Shi,Ying Gao","doi":"10.1021/acs.analchem.5c02292","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c02292","url":null,"abstract":"In this study, highly efficient photochemical vapor generation (PVG) of germanium (Ge) and arsenic (As) in the absence of organic compounds was first reported. Volatile As and Ge species were formed in the system containing sulfite and iodide under UV irradiation. In a medium containing 12 mM Na2SO3 and 90 mM KI, the PVG efficiency was 88 ± 1% for Ge after 80 s of UV irradiation, with the limit of detection (LOD, 3σ) of 0.2 ng L-1 by ICP MS measurement. Under the conditions of 2 mM Na2SO3, 200 mM KI, and 10 s of UV irradiation, the PVG efficiency was 43 ± 1% for As with the LOD of 0.6 ng L-1. Moreover, the analytical sensitivities for As(III) and As(V) were comparable, making it possible to directly determine total As. The developed method was applied for the analysis of Ge and As in soil and water samples with satisfactory results. The mechanism for the photochemical reduction of Ge and As was explored in this study by gas chromatography-mass spectrometry (GC-MS) and electron paramagnetic resonance. It was found that the volatile species of Ge and As generated during the photochemical reaction were GeH4 and AsH3, respectively. The synergistic effect from sulfite and iodide promoted the continuous and stable generation of eaq- and increased the synthesis of •H under UV irradiation as well. The finding is significant for the understanding the photochemical conversion of Ge and As in the system without organic acids.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"209 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145277317","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 Pathological Collagen-Targeting Nanozyme Chip for Ultrasensitive Quantification of Collagen in Body Fluids. 一种用于超灵敏定量体液中胶原蛋白的病理胶原靶向纳米酶芯片。

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-13 DOI: 10.1021/acs.analchem.5c04014

Xiaoyu Qin,Wenhao Guo,Yining Wang,Xiangdong Cai,Jianxi Xiao

{"title":"A Pathological Collagen-Targeting Nanozyme Chip for Ultrasensitive Quantification of Collagen in Body Fluids.","authors":"Xiaoyu Qin,Wenhao Guo,Yining Wang,Xiangdong Cai,Jianxi Xiao","doi":"10.1021/acs.analchem.5c04014","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04014","url":null,"abstract":"Pathological collagen emerges as a critical biomarker in the progression of tumors, fibrotic disorders, and osteoarthritis. The precise quantification of pathological collagen holds critical diagnostic value, offering a noninvasive approach for early detection of collagen-associated disorders. A pathological collagen targeting nanozyme biochip (PCC) has been constructed for the first time to ultrasensitively quantify pathological collagen in body fluids. The PCC biosensor consists of a high-affinity pathological collagen targeting nanozyme (Pacotzyme) and a capture surface for efficient enrichment of unbound Pacotzyme. The PCC has been demonstrated to quantitatively analyze pathological collagen across a wide concentration range from 0.1 to 10000 ng/mL, with an LOD as low as 15 pg/mL. PCC demonstrates robust and precise performance in intricate biological environments characterized by elevated protein content, high ionic strength, and increased glucose levels. Moreover, PCC exhibits consistent and reliable functionality in diverse body fluids, including serum, urine, saliva, and synovial fluid. Notably, PCC chips have been successfully applied to detect cancer, fibrosis, and osteoarthritis by quantifying pathological collagen in body fluids. The specific nanozyme biosensor offers a promising diagnostic tool for the early screening and noninvasive diagnosis of collagen-related diseases.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"86 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145277314","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

Development of an Aptamer/CRISPR-Cas12a-Based Dual-Modal Biosensor for Fusobacterium nucleatum Detection in Non-Invasive Colorectal Cancer Screening. 基于核酸适体/ crispr - cas12的核梭杆菌双模生物传感器在无创结直肠癌筛查中的应用

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-13 DOI: 10.1021/acs.analchem.5c04132

Xinjing Wang,Shanshan Feng,Hui Chen,Bo Zhou,Tingting Fan,Ying Qin,Longshan Zhao,Yuyang Jiang,Yan Chen

{"title":"Development of an Aptamer/CRISPR-Cas12a-Based Dual-Modal Biosensor for Fusobacterium nucleatum Detection in Non-Invasive Colorectal Cancer Screening.","authors":"Xinjing Wang,Shanshan Feng,Hui Chen,Bo Zhou,Tingting Fan,Ying Qin,Longshan Zhao,Yuyang Jiang,Yan Chen","doi":"10.1021/acs.analchem.5c04132","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04132","url":null,"abstract":"Colorectal cancer (CRC) is the third most common cancer and leading cause of cancer-related deaths worldwide. However, current CRC screening methods are complex, invasive, and tend to exhibit low sensitivity. Recent evidence has highlighted gut microbiota dysbiosis, especially elevated Fusobacterium nucleatum levels, as a promising biomarker for CRC. In this study, a sensitive and specific detection platform was developed for F. nucleatum by combining a highly specific aptamer with rolling circle amplification (RCA) and the CRISPR/Cas12a technology. The aptamer enables specific target recognition, while RCA amplifies the target signal, and the Cas12a-mediated cleavage of a fluorescence-quenching substrate generates a quantifiable fluorescence or grayscale signal. Using a microplate reader, this assay achieved a limit of detection (LOD) of 3.68 CFU/mL; furthermore, by incorporating smartphone-assisted ImageJ grayscale analysis, it elevated the LOD to 4.30 CFU/mL, thereby enabling a dual-mode output along with on-site applicability. Additionally, the strong correlation between the two signals allowed for mutual validation. Upon application to clinical fecal samples, the developed method sensitively distinguished CRC patients from healthy controls, and its results correlated with the quantitative polymerase chain reaction results. This triple-synergistic platform, integrating aptamer specificity, RCA amplification, and CRISPR/Cas12a sensitivity, enables the noninvasive, ultrasensitive detection of F. nucleatum, supporting early CRC screening, prognosis monitoring, and microbiome-targeted therapy. Moreover, this approach overcomes the challenges of detecting low-abundance bacteria in early stage CRC and advances the precision of microbiome-based diagnostics for CRC.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"116 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145277313","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

Bioinspired Kirigami Origami Card for Spray Collection toward Facile Airborne Viruses Monitoring. 生物启发的Kirigami折纸卡片喷雾收集到简单的空气传播病毒监测。

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-13 DOI: 10.1021/acs.analchem.5c03678

Liwei Cao,Hao Wu,Danna Yang,Hailan Zhong,Weijian Song,Zilong He,Fengyu Li

{"title":"Bioinspired Kirigami Origami Card for Spray Collection toward Facile Airborne Viruses Monitoring.","authors":"Liwei Cao,Hao Wu,Danna Yang,Hailan Zhong,Weijian Song,Zilong He,Fengyu Li","doi":"10.1021/acs.analchem.5c03678","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c03678","url":null,"abstract":"There is an urgent need for efficient airborne virus monitoring to proactively cut off transmission sources in the public. However, infected respiratory sprays can remain stable in the airborne aerosols, and the sampling of airborne viruses has low efficiency. In this work, inspired by the cactus conical leaves and redbud venation, we propose an approach for the capture of airborne virus and in situ detection. A paraffin kirigami with cactus cone-shaped spine units arranged to mimic leaf veins was designed to integrate with electrochemical monitoring as an origami card. With the combined effect of Laplace pressure, gravity assistance, leaf vein-mimicking structure, and aerodynamic vortices induced by the assembly of the origami card, the paraffin kirigami card demonstrates excellent ability to collect virus-containing sprays from air and facilitate directional transport and aggregation. The peak fog harvesting rate reaches 5424.2 mg/cm2/h, demonstrating exceptional efficiency in atmospheric droplet capture. A triad electrode system is accommodated at the root of the spray collector to monitor airborne virus in the collected droplets. The paraffin kirigami card achieves a low limit of detection (LOD) of 0.10776 copies/mL and shows a good linear relationship between the impedance and influenza A (H1N1) virus concentration. Validation using thrombin as a model target analyte confirmed the system's integrated capability for rapid collection, identification, and sensitive detection of viruses. This cactus-inspired paraffin kirigami card demonstrates significant potential for real-time, in situ airborne virus collection and detection, contributing to efforts to control the spread of viruses.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"39 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145277319","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

Deep Learning-Assisted Lens-Free Holography Integrated Pd Nanozyme-Armed Phages for the Rapid and Extraction-Free Detection of Viable Bacteria. 深度学习辅助无透镜全息集成Pd纳米酶噬菌体用于活菌快速无提取检测。

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-13 DOI: 10.1021/acs.analchem.5c04259

Chen Zhan,Peng Lu,Minjie Han,Xiaoqian Hao,Sanyang Han,Yang Zhou,Shu Wang,Yiping Chen

{"title":"Deep Learning-Assisted Lens-Free Holography Integrated Pd Nanozyme-Armed Phages for the Rapid and Extraction-Free Detection of Viable Bacteria.","authors":"Chen Zhan,Peng Lu,Minjie Han,Xiaoqian Hao,Sanyang Han,Yang Zhou,Shu Wang,Yiping Chen","doi":"10.1021/acs.analchem.5c04259","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04259","url":null,"abstract":"Bacterial infections represent a serious global threat to public health, often leading to severe infectious diseases and even fatalities. The most effective approach to prevent outbreaks is through the implementation of rapid, accurate, and simple point-of-care testing. Here, we developed a deep learning-assisted lens-free holography biosensing platform integrated with Pd nanozyme-armed phages for the rapid and extraction-free detection of viable bacteria, enabling on-site testing. Phages specifically recognize and capture target viable bacteria. Surface ligand-engineered Pd nanozyme-armed phages then trigger a tyramine signal amplification reaction, resulting in the formation of polystyrene microsphere-bacteria-magnetic nanoparticle complexes. Consequently, the number of unbound polystyrene microspheres decreases with bacterial capture. Additionally, the combination of Pd nanozyme and phage can eliminate bacteria in situ while preventing secondary cross-contamination. Portable lens-free holographic microscope offers several advantages, including an ultrawide field of view, low cost, and a lightweight design, enabling the accurate capture of microsphere holograms in the supernatant through a high-throughput manner. The transformer-based deep learning algorithm integrated with digital holographic reconstruction has been trained to precisely process the probe holograms at high speed. As proof of concept, our approach has successfully enabled the quantitative detection of viable Salmonella typhimurium with high sensitivity (∼20 CFU/mL) in 16 min, without additional nucleic acid extraction. It has been evaluated using various real samples, demonstrating great promise as an intelligent bioassay for next-generation biosensing.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"11 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145277320","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

Physicochemical Tuning of Bispecific Antibody Fragment Immobilization for Robust Digital SERS Biosensing. 用于数字SERS生物传感的双特异性抗体片段固定化的物理化学调整。

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-13 DOI: 10.1021/acs.analchem.5c03980

Jing Wang,Quan Zhou,Christopher B Howard,Matt Trau

{"title":"Physicochemical Tuning of Bispecific Antibody Fragment Immobilization for Robust Digital SERS Biosensing.","authors":"Jing Wang,Quan Zhou,Christopher B Howard,Matt Trau","doi":"10.1021/acs.analchem.5c03980","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c03980","url":null,"abstract":"Surface-enhanced Raman scattering (SERS) biosensing platforms offer exceptional sensitivity and multiplexing capabilities for biomarker detection, but their performance is often limited by uncontrolled ligand orientation on nanotags. To address this, we developed a SERS nanotag incorporating a bispecific antibody fragment (BsAb) engineered to bind the SARS-CoV-2 receptor-binding domain (RBD) and methoxy polyethylene glycol (mPEG) simultaneously, enabling orientation-controlled immobilization onto mPEG-grafted plasmonic nanostructures. We systematically evaluated how immobilization conditions─particularly pH relative to the BsAb's isoelectric point (pI)─influence surface density, antigen accessibility, and overall assay performance using a combination of orthogonal physicochemical and functional assays. Our results show that immobilization at pH above the BsAb's pI improves antigen accessibility and nanotag stability, despite reduced immobilization density. When integrated into a digital SERS biosensing platform, the BsAb-functionalized SERS nanotags enabled highly specific digital detection of RBD in plasma, achieving a low limit of detection (3.97 ng/mL) and outperforming enzyme-linked immunosorbent assay in assay time, reagent consumption, and multiplexing potential. This study establishes a robust strategy for designing and optimizing antibody fragment-based SERS nanotags, advancing their application in next-generation diagnostic platforms.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"20 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145277318","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 Competitive Antifouling Sensor with a High-Efficiency Cluster for Environmental Pollution Trace Analysis. 环境污染痕量分析的高效集群防污传感器。

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-13 DOI: 10.1021/acs.analchem.5c05663

Haorui Li,Ziqiu Huang,Xianzhen Song,Lu Zhao,Caifeng Ding

{"title":"A Competitive Antifouling Sensor with a High-Efficiency Cluster for Environmental Pollution Trace Analysis.","authors":"Haorui Li,Ziqiu Huang,Xianzhen Song,Lu Zhao,Caifeng Ding","doi":"10.1021/acs.analchem.5c05663","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c05663","url":null,"abstract":"Microcystin-LR (MC-LR) is one of the most common pollutants in freshwater ecosystems worldwide and can cause chronic poisoning in humans and induce liver cancer. To realize the sensitive detection of MC-LR, the ability of the sensor to resist adsorption by other pollutants is very important. Therefore, the competitive antifouling sensor was constructed with a methacrylate hyaluronic acid-carboxybetaine methacrylamide (HA-CB) hydrogel as the antifouling substrate and an FeCu metal-organic framework (MOF) as a bifunctional material to form the \"top-end\" antifouling mechanism. The HA-CB hydrogel forms a physical barrier on the electrode surface, preventing contaminants (such as proteins, microorganisms, and organic molecules) to reduce adsorption, and the hydrogel has an interfacial adhesion ability for enhancing the stability of the constructed sensor. In addition, the bifunctional FeCu MOF can also improve the ECL signal of the novel Eu nanoclusters (NCs) through the catalysis of the FeCu MOF. This high-efficiency sensor realized the sensitive detection of MC-LR under the competitive strategy between MC-LR and its antigen. The signals of the competitive antifouling sensor decreased linearly as the concentrations of MC-LR increased, with a low limit of detection of 9.14 fg/mL. Furthermore, the competitive antifouling sensor successfully detected MC-LR in real water samples, providing a novel strategy for environmental pollutant monitoring.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"116 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145277281","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

Advanced Dimensionality Reduction for Imaging Mass Spectrometry of Human Eye Tissue through Low-Rank Modeling with Sparse and Dense Residuals. 基于稀疏和密集残差低秩建模的人眼组织成像质谱高级降维方法。

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-13 DOI: 10.1021/acs.analchem.4c06368

Roger A R Moens,Lukasz G Migas,David M G Anderson,Jeffrey D Messinger,Olga S Ovchinnikova,Richard M Caprioli,Christine A Curcio,Kevin L Schey,Jeffrey M Spraggins,Raf Van de Plas

{"title":"Advanced Dimensionality Reduction for Imaging Mass Spectrometry of Human Eye Tissue through Low-Rank Modeling with Sparse and Dense Residuals.","authors":"Roger A R Moens,Lukasz G Migas,David M G Anderson,Jeffrey D Messinger,Olga S Ovchinnikova,Richard M Caprioli,Christine A Curcio,Kevin L Schey,Jeffrey M Spraggins,Raf Van de Plas","doi":"10.1021/acs.analchem.4c06368","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06368","url":null,"abstract":"Imaging mass spectrometry (IMS) yields high-dimensional and large data sets commonly exceeding 100,000 pixels, each reporting a mass spectrum of 200,000 intensity values or more. Reducing the dimensionality and size of IMS data is often necessary to enable downstream analysis, and matrix-factorization-based approaches are often used for this purpose. However, the model underlying most of these techniques, decomposing measurements into the sum of a low-rank term (presumed signal) and a small entry-wise residual term (presumed noise), is often not optimal for IMS. For example, while spatially or spectrally sparse signals are common in IMS data, they can heavily distort the low-rank approximation. Therefore, we propose capturing the IMS data structure using low-rank models that, in addition to a dense residual, allow for sparse variation to be captured separately. We implement two such methods, principal component pursuit (PCP) and stable principal component pursuit (SPCP), apply them to IMS data, and compare them to a classical factorization method, principal component analysis (PCA). We investigate their dimensionality and noise reduction performance on MALDI Q-TOF IMS measurements of human cornea and retina tissue since the human eye is a complex organ with lots of small, tightly packed tissue substructures that are spatially sparse. Our results suggest that if parameters are set adequately, PCP and SPCP enable stronger dimensionality reduction and higher compression of IMS data compared to PCA, while concurrently reducing signal overestimation.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"119 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145277315","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

In-Capillary Chemoselective Tagging-Facilitated Direct nESI-MS Profiling of Carboxyl- and Carbonyl-Containing Metabolites in Urine. 毛细管化学选择性标记-促进尿液中含羧基和羰基代谢物的直接nESI-MS分析。

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-12 DOI: 10.1021/acs.analchem.5c04351

Yifan Wei,Xiumei Zheng,Zili Huang,Chunxiao Mou,Xiaobo Xie,Yi Lv

{"title":"In-Capillary Chemoselective Tagging-Facilitated Direct nESI-MS Profiling of Carboxyl- and Carbonyl-Containing Metabolites in Urine.","authors":"Yifan Wei,Xiumei Zheng,Zili Huang,Chunxiao Mou,Xiaobo Xie,Yi Lv","doi":"10.1021/acs.analchem.5c04351","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04351","url":null,"abstract":"Carboxyl- and carbonyl-containing metabolites (CCMs) are essential for energy metabolism and signaling in living cells and can serve as diagnostic biomarkers for various diseases. However, their low ESI ionization efficiencies and structural diversities could bring difficulties for their direct detection by mass spectrometry. In this work, a chemoselective tagging and acid-trigged release (CTAR) strategy-based nanoelectrospray ionization-mass spectrometry (nESI-MS) platform was developed by immobilizing a cis-diol-containing amine probe (i.e., 3-((2-aminoethyl)amino)propane-1,2-diol, denoted as AEAP-diol) on a coated ESI capillary with boronate esters as acid cleavage site, which can directly and selectively \"fish out\" targeted CCMs from biological matrices. Following the removal of unwanted species, the AEAP-diol tagged CCMs derivatives can be online released and directly detected by nESI-MS within 1 min. MS/MS fragmentation profiles of these CCMs derivatives exhibited a neutral loss of 91 Da and diagnostic fragments at m/z 118 for carboxyl- and carbonyl-containing metabolites, respectively, thereby enabling unambiguous structural elucidation of unknown CCMs. With high specificity, superior salt tolerance, and outstanding robustness, our CTAR-nESI-MS platform enabled direct and sensitive analysis of CCMs from a single drop of biofluid (2.5 μL of urine), achieving a low detection limit of 0.1 ppb for butyric acid. Using this method, 26 carboxyl- and carbonyl-containing metabolites were identified and quantified in urine samples from esophageal cancer patients and healthy volunteers, revealing significant differences in several reported CCM biomarkers. These findings collectively underscore the potential of CTAR-nESI-MS as a sensitive, cost-effective, and versatile tool for comprehensive metabolite profiling and high-throughput screening applications.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"26 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145277344","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