{"title":"An Fe(III)-Based Fluorescent Probe for Carbon Monoxide only Senses the \"CO Donor\" Used, CORM-3, but Not CO.","authors":"Hongliang Li,Dongning Liu,Binghe Wang","doi":"10.1021/acs.analchem.5c04712","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04712","url":null,"abstract":"Because of the increasing interests in carbon monoxide (CO) as an endogenous signaling molecule, there have been extensive efforts in developing fluorescent probes for CO. In doing so, metal-carbonyl complexes named \"CO-releasing molecules\" (CORMs) are often used as CO surrogates. The most widely used CORM-2 and CORM-3 are chemically reactive Ru(II) complexes; release minimal or no CO unless in the presence of a strong nucleophile or a reducing agent; and do not function as reliable CO donors. As a result, some reported CO fluorescent probes only detect the CORM used, not CO. Recently, an Fe(III)-fluorophore complex, RBF-Fe(III), has been reported to sense CO using CORM-3 as a CO surrogate. The proposed mechanism involves CO binding to Fe(III). Because of the known affinity of CO for only Fe(II), but not Fe(III), we were intrigued by the report. Re-evaluation work found fluorescence changes of RBF-Fe(III) by CORM-3, but not CO itself. Furthermore, sodium ascorbate and cysteine were found to induce fluorescent changes of the RBF-Fe(III) system. Moreover, RBF-Fe(III) was found to be unstable and to change fluorescence with time or agitation. Regardless of whether it was under N2, CO, or vacuum, vigorous stirring induced the same level of fluorescence changes, presumably due to precipitation or aggregation of Fe(III) species, which is consistent with literature findings of Fe(III) behaviors. Such results mean that the RBF-Fe(III) system does not sense CO and underscore the need to exercise extra cautions when chemically reactive CO donors are used in developing CO probes.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"28 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145254602","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}
Xingyu Tao,Xinyu Li,Qikun Lv,Gang Tian,Hengke Jia,Yuanjie Liu,Bo Shen,Xuhuai Fu,Yurong Yan
{"title":"Machine Learning-Enhanced Analysis of miRNA Biomarkers for Accurate Breast Cancer Diagnosis Using DNA Seagrass.","authors":"Xingyu Tao,Xinyu Li,Qikun Lv,Gang Tian,Hengke Jia,Yuanjie Liu,Bo Shen,Xuhuai Fu,Yurong Yan","doi":"10.1021/acs.analchem.5c03687","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c03687","url":null,"abstract":"As potential biomarkers for breast cancer, microRNAs (miRNAs) have demonstrated significant promise in clinical applications. However, accurate miRNA-based breast cancer diagnosis is hindered by the lack of simple, ultrasensitive, and highly specific detection methods and reliable biomarkers. To tackle these challenges, we introduced an innovative strategy using rolling circle amplification-generated DNA seaweed (RCA-GDS) to detect the multiple miRNA biomarkers combined with machine learning to enable precise breast cancer diagnosis. RCA-GDS effectively converts linear RCA amplification into exponential amplification, efficiently enhancing fluorescence signals and enabling the detection of miRNAs at concentrations as low as attomolar levels within 2 h under isothermal conditions. Using the TCGA database, we screened a panel of miRNAs (miRNA21, miRNA182, and miRNA183) for the precise diagnosis of breast cancer and validated their reliability in both intracellular and serum samples. Finally, we integrated machine learning algorithms with the miRNA detection system to develop a differential diagnosis model, which was further validated in an independent cohort and demonstrated excellent diagnostic accuracy. This work not only enables ultrasensitive and highly specific miRNA detection but also advances miRNA panel-based clinical applications in breast cancer diagnosis.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"26 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145247165","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}
Rachel Smith, Catherine Brookes, Michael Morris, Perdita Barran
{"title":"Twenty-Five Years of High-Throughput Screening of Biological Samples with Mass Spectrometry: Current Platforms and Emerging Methods","authors":"Rachel Smith, Catherine Brookes, Michael Morris, Perdita Barran","doi":"10.1021/acs.analchem.5c02331","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c02331","url":null,"abstract":"Robust high-throughput screening (HTS) approaches for discovering new chemical entities are desirable for research and translation. Applications for which high-throughput (HT) methods are particularly required also include the screening of potential therapeutics for drug discovery and development, profiling of biofluids for disease biomarker discovery, and clinical diagnostics. Complementing the demand for HTS from specific application areas are substantial technological advancements in the fields of automation, microfluidics, and ambient ionization that facilitate highly automated and sophisticated analytical workflows. The time period spanning 2000–2025 has witnessed a significant expansion in the mass spectrometry (MS) capabilities and technology. This has included novel ionization approaches that can achieve rapid analysis with minimal solvent and sample consumption, while retaining high sensitivity and specificity in the absence of chromatography. Despite the demand for HTS methods and the well-documented analytical capabilities of MS, optical methods dominate as the HTS detection methods of choice. This perspective provides an overview of the evolution of HTS-MS over the last 25 years, focusing on emerging approaches that also provide efficient and sustainable workflows that compete with optical detection. Additionally, this perspective will highlight challenges in the field that may hinder widespread adoption and consider lessons from the COVID-19 pandemic, as well as the impact of sustainability on the future of HTS-MS and analytical chemistry.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"39 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145247453","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}
Xiujuan Qiao, Rui Han, Linhuan Li, Yiting Hou, Xiliang Luo
{"title":"Design of Dendritic Zwitterionic Oligopeptides with Superior Antifouling Capability for Electrochemical Detection in Diverse Complex Biological Fluids","authors":"Xiujuan Qiao, Rui Han, Linhuan Li, Yiting Hou, Xiliang Luo","doi":"10.1021/acs.analchem.5c04886","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04886","url":null,"abstract":"Electrochemical biosensors are often compromised by nonspecific adsorption in complex biological fluids. Although zwitterionic peptides (ZIPs) demonstrate excellent antifouling properties through the formation of hydration layers, conventional linear ZIPs face a severe limitation: unstable hydration under dynamic complex conditions due to a longer dipole moment, local charge, and conformational flexibility. To address these limitations, we designed a novel dendritic zwitterionic oligopeptide with a three-dimensional branched architecture by alternating glutamic acid (E) and lysine (K) residues around a cysteine (C) core [e.g., EK(E)CE(K)K] according to traditional linear ZIPs (CEKEKEK). Comparative experiments revealed that the dendritic ZIPs exhibited significantly enhanced hydrophilicity and antifouling performances over linear CEKEKEK when exposed to human saliva, sweat, and even in blood. Molecular dynamics simulations revealed that the flexible CEKEKEK oligopeptide, with 2 intramolecular hydrogen bonds between hydrophilic groups distributed at termini of the polypeptide, exposing the peptide bond at the middle part, undergoes local charge and an uneven and unstable hydrated layer. However, the dendritic EK(E)CE(K)K oligopeptides formed 8 intramolecular hydrogen bonds, lowering the dipole moment between −COOH and −NH<sub>2</sub> groups with maintaining high conformational stability, which helps form a stronger hydration layer under physiological conditions than the linear CEKEKEK. Leveraging this design, we successfully developed an antifouling electrochemical biosensor based on this dendritic ZIPs as example for detecting C-reactive protein in saliva, achieving detection accuracy consistent with the ELISA method. The dendritic design provides a strategy for enhancing the contamination resistance ability and offers a significant advancement for next-generation biosensors in complex biological environments.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"1 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241634","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":"Automated Chronological Sequence Analysis of Intersecting Lines between Laser Printing and Seals via Pattern Selection-Based DESI-MS Imaging.","authors":"Ying Chen,Huimin Liu,Yiting Yuan,Da Qin,Zhuanghao Hou,Guangming Huang","doi":"10.1021/acs.analchem.5c03554","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c03554","url":null,"abstract":"Determining the chronological sequence of laser printing and seals is crucial for forensic document examination and legal evidence authentication. An automated method was developed to determine the chronological sequence between laser printing and seals via desorption electrospray ionization mass spectrometry imaging (DESI-MSI). The method employs pattern selection and an adaptive multicuster segmentation strategy, automatically adjusting segmentation parameters on the basis of similarity thresholds to handle different sample conditions. Validation on 50 samples containing intersecting laser printing and seals achieved 96% accuracy (48/50 cases) in sequence determination. An optimal similarity threshold of >0.5 was established for reliable feature selection while minimizing interference from background noise. This automated workflow eliminates manual intervention and prior knowledge requirements, providing an objective solution for forensic document authentication.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"24 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145246674","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":"H2S-Activatable Nanoagent for NIR-II Fluorescence Imaging and Photodynamic Therapy of Colon Cancer.","authors":"Diedie Cheng,Yi Feng,Yanbo Liu,Jingjing Zhao,Jiamin Xiong,Guangjin Gao,Weiwei Xu,Meng Zhao,Qingqing Miao,Qing Li","doi":"10.1021/acs.analchem.5c04539","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04539","url":null,"abstract":"Colon cancer poses a serious health threat due to its asymptomatic early progression, recurrence rate, and the limited efficacy of current diagnostic and therapeutic strategies, highlighting the urgent need for noninvasive and effective theranostic methods. Photosensitizers capable of integrating NIR-II fluorescence imaging with photodynamic therapy (PDT) in a single platform offer a promising solution but often suffer from inadequate specificity, leading to off-target effects and reduced theranostic accuracy. In this study, we exploit the elevated H2S levels in the colonic tumor microenvironment to develop a H2S-activatable NIR-II phototheranostic nanoplatform for the precise diagnosis and treatment of colon cancer. This nanoplatform is based on an optimized NIR-II fluorescent photosensitizer that is caged with H2S-cleavable 2,4-dinitrophenyl groups and then is coassembled with amphiphilic polymers to form the water-dispersible nanoparticles (BIS-NPs). Upon exposure to H2S, BIS-NPs exhibit selective activation of NIR-II fluorescence and singlet oxygen (1O2) generation under 808 nm laser irradiation. Systematic evaluation in CT26 tumor-bearing mice demonstrates that BIS-NPs enable tumor-specific NIR-II fluorescence imaging and efficient PDT performance, confirming their potential as a precise and effective phototheranostic tool for colon cancer management.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"29 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145246676","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}
Michael Rush, J. David Ricker, Pramod Prasad Poudel, Nuwan Kothalawala, Cary Watterson, Dmitriy Pastarnak
{"title":"Challenging the Database: Day-of-Analysis Calibration and UF Modeling for Reliable RRF Use in Medical Device Chemical Characterization","authors":"Michael Rush, J. David Ricker, Pramod Prasad Poudel, Nuwan Kothalawala, Cary Watterson, Dmitriy Pastarnak","doi":"10.1021/acs.analchem.5c04247","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04247","url":null,"abstract":"Accurate quantitation during chemical characterization─also referred to as extractables and leachables (E&L)─within a toxicological risk assessment for medical device biocompatibility hinges on the appropriate application of relative response factors (RRFs). This study investigates the variability of RRFs across a chemically diverse set of compounds and evaluates the implications of quantitation model selection on analytical outcomes. Using gas chromatography–mass spectrometry (GC–MS) and liquid chromatography–mass spectrometry (LC–MS), we demonstrate that RRFs are highly context-dependent and influenced by factors such as ionization mode, compound class, concentration, and instrument conditions. We propose an approach to RRF determination, emphasizing day-of-analysis calibration and uncertainty factor modeling to improve reproducibility. Our findings support a statistically grounded application of analytical evaluation thresholds, enhancing the reliability of semiquantitative assessments in medical device biocompatibility.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"10 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241637","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":"Sensor-Aided Rapid Identification of Plastic-Degrading Bacterial Strains.","authors":"Xueqing Gao,Shiling Zheng,Tianjia Jiang,Wei Qin","doi":"10.1021/acs.analchem.5c04596","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04596","url":null,"abstract":"Biodegradation has been highlighted as a promising strategy to cope with the worldwide plastic waste problems. However, its widespread application remains a major challenge, since the identification of the bacterial strains that are capable of efficiently degrading plastics from various bacterial choices is rather time-consuming. Herein, we report on a novel and universal strategy for rapid identification of plastic-degrading bacteria by using sensor technology. The proposed method is based on the biodegradation-induced Ca2+ ion release, followed by potentiometric detection with an ion-selective electrode. A core-shell structured magnetic bead serves as both the recognizer for the plastic-degrading bacterial cells and the signal reporter for their plastic-degradation capabilities. By using the proposed strategy, two Enterobacter species have been identified as the bacterial candidates for polystyrene (PS) biodegradation. Their PS-degrading capabilities were confirmed by using complete genome sequencing and transcriptomic analysis. As compared to the conventional methods for identifying plastic-degrading bacterial strains, the process could be remarkably shortened from weeks to hours by using the present methodology. Given its high efficiency, this methodology can provide a promising strategy to address the current challenges in the rapid identification of plastic-degrading bacterial strains.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"58 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145240978","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}
Huijing Zhang, Yang Bai, Huihui Xu, Rui You, Die Xu, Tiechuan Li, Xuexin Duan
{"title":"Selective Capture and Addressable Release of Single Cells Enabled by Acoustic Resonator Integrated Serpentine Microchannel","authors":"Huijing Zhang, Yang Bai, Huihui Xu, Rui You, Die Xu, Tiechuan Li, Xuexin Duan","doi":"10.1021/acs.analchem.5c04704","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04704","url":null,"abstract":"Single cell manipulation and analysis are crucial for understanding cellular heterogeneity, yet conventional microfluidic approaches suffer from poor selectivity, structural complexity, and low throughput. Here, we present an acoustofluidic-microstructure integrated platform combining a right triangle-shaped bulk acoustic wave (RTBAW) resonator with a serpentine microchannel. The platform enables selective capture (efficiency >90%) and addressable release (efficiency >90%) of single cells by leveraging acoustic streaming-induced hydrodynamic forces. Unlike existing methods relying on optical or electrical fields, our design eliminates thermal damage and ionic interference while achieving submillisecond response time and parallel processing of 4 cells per array unit. This simplified architecture reduces fabrication complexity and enhances throughput by directing untargeted cells through curved bypass channels. We validated the platform’s utility in live/dead cell sorting, demonstrating its potential for high-precision single-cell diagnostics, drug screening, and rare cell isolation.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"158 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241633","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}
Dababrata Paul, Souvick Biswas, Nureshan Dias, Matthew T. Finn, Andrew S. Lipton, Albert Epshteyn, Musahid Ahmed, Ralf I. Kaiser
{"title":"A Synchrotron-Based Vacuum Ultraviolet Photoionization Mass Spectrometer-Coupled Microreactor To Probe Thermocatalysis","authors":"Dababrata Paul, Souvick Biswas, Nureshan Dias, Matthew T. Finn, Andrew S. Lipton, Albert Epshteyn, Musahid Ahmed, Ralf I. Kaiser","doi":"10.1021/acs.analchem.5c04691","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04691","url":null,"abstract":"Vacuum ultraviolet photoionization (VUV-PI) mass spectrometry offers an isomer-selective and universal ionization with minimal fragmentation detection of organics in complex chemical systems such as pyrolysis and combustion. Here, we report a state-of-the-art experimental setup of a universal catalytic microreactor combined with a molecular beam to investigate the thermocatalytic oxidation of a heterogeneous system relevant for probing reactions at gas–solid interfaces. In strong contrast to traditional off-line analytical methods, this technique is capable of identifying and quantifying short-lived species (radicals) as well as stable products to decipher initial reaction steps via the detection of nascent products. The thermocatalytic oxidative degradation of exo-tetrahydrodicyclopentadiene (JP-10), a high energy-density hydrocarbon fuel, over solid titanium–aluminum–boron reactive mixed metal nanopowder (Ti-Al-B RMNP) is exploited to showcase potential applications. Overall, some 59 nascent gas-phase products are identified via photoionization efficiency (PIE) curves, including oxygenated species and hydrocarbons comprising closed-shell molecules and radicals. The critical temperature for complete oxidative decomposition of JP-10 was lowered by 450 K from 1400 K to 950 K, indicating an efficient thermocatalytic action of Ti-Al-B nanoparticles on JP-10. The enabling of a universal chemical microreactor along with VUV-PI mass spectrometry broadens the applicability of this technique to hydrocarbon fuel oxidation and pyrolysis characterization. This isomer-selective sensitive probing along with the detection of radical transients makes the aforementioned technique superior to other conventional analytical techniques such as microflow tube and pyrolysis-gas chromatography coupled with mass spectrometry for investigating similar pyrolysis reactions and comprehensive quantification.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"105 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241632","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}