{"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}
Elahe Naghdi,Dariush Bahrami Eisaabadi,Wim De Malsche
{"title":"Acoustic Streaming-Induced Vortex Chromatography in Micron-Scale Rectangular Open Tubular Channels.","authors":"Elahe Naghdi,Dariush Bahrami Eisaabadi,Wim De Malsche","doi":"10.1021/acs.analchem.5c04830","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04830","url":null,"abstract":"The separation resolution in the most advanced pressure-driven separation devices is predominantly limited by the Taylor-Aris dispersion. The induction of lateral flow perpendicular to the axial flow has recently been proposed and validated as a strategy to improve separation resolution by reducing Taylor-Aris dispersion. In the present study, we introduce an acoustic-based lateral flow into a microfluidic channel, which is enabled by matching the applied acoustic wavelength with the channel depth. With this approach, a small micrometer-scale (critical) dimension is foreseen for chromatographic purposes, and a larger dimension is foreseen to attain acoustic resonance. It is experimentally observed (in a 10 μm × 75 μm channel) that the induced acoustic streaming reduces Taylor-Aris dispersion by a factor of 10, hence resulting in a chromatographic system that behaves as if it has a critical dimension of 1 μm. It is also shown numerically that this gain can be further improved and what the impact of inevitable imperfections in the microfabricated chips is. The first example of the implication of the improvement in the chromatographic separation efficiency is shown for a macromolecule separation operated under reverse-phase conditions.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"101 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145246538","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":"Ratiometric Fluorescence Chiral Sensors for pH Monitoring and Its Applications in Indicator Paper and Bioimaging.","authors":"Foroozan Feizi,Fatemeh Molaabasi,Mohanna Ezati,Mojtaba Shamsipur,Farimah Mousavi,Afsaneh Roshanfekr,Reza Mahdavian,Behnam Hajipourverdom,Ali Barati,Hossien Naderimanesh","doi":"10.1021/acs.analchem.5c04243","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04243","url":null,"abstract":"Chirality is a prevalent phenomenon in nature and living organisms and plays a significant role in biological systems. The chirality of nanomaterials represents one of the most exciting and rapidly expanding fields of science. Comparing the pH response of enantiomers of a particular chiral species remains a challenge in the field of chemistry. In this work, chiral d/l-Cdots were prepared by post-modifying an achiral Cdots core with arginine enantiomers as chiral ligands for comparing the pH sensitivity of enantiomers. In this case, modified silicon quantum dots (SiQDs) were employed to harness a sensitive and accurate ratiometric method. The fluorescence response of chiral sensors is based on an \"on-off\" strategy, with different pH ranges for d- and l-probes. Surprisingly, the d- and l-probes show different sensitivities to pH, with a linear range of pH 4.0-8.0 for d-probes and 3.5-7.5 for l-probes. The response mechanism is based on aggregation caused quenching (ACQ) due to protonated-deprotonated d-Cdots/Ca-SiQDs and l-Cdots/Ca-SiQDs probes in acidic and basic environments. Quantum mechanical (QM) calculations were in excellent agreement with the experimental results, confirming the stronger binding affinity of d-Cdots to protonated and aggregation in acidic conditions compared to l-Cdots. Crucially, these chiral probes have been successfully utilized as indicator paper and accurately detect intracellular pH (pHi) in SK-BR-3 breast cancer cells.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"54 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145246716","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":"Europium(III) Coordination-Mediated Self-Assembly of N-Doped Carbon Dot Nanoclusters for Ratiometric Detection of Tetracycline","authors":"Ying Wang, Yujing Han, Wei Wang, Yali Qiao","doi":"10.1021/acs.analchem.5c03576","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c03576","url":null,"abstract":"Effective control of carbon dot (CD) self-assembly into larger nanoclusters in the liquid state for ultrasensitive detection is challenging and still in its infancy. For the first time, a europium(III) coordination-mediated strategy for self-assembly of N-doped carbon dots into large nanoclusters (N, Eu<sup>3+</sup>-CD nanoclusters) in aqueous solution was developed. It was found that the sizes and photoluminescence (PL) properties of nanoclusters could be effectively tuned by adjusting the Eu<sup>3+</sup> content. The larger clusters with relatively longer fluorescence lifetimes were obtained by increasing the Eu<sup>3+</sup> content. The simultaneous coordination of multi-CD particles with a Eu<sup>3+</sup> and a dot particle with multiple Eu<sup>3+</sup> was the key to inducing the self-assembly of CDs and regulating their optical properties. Furthermore, a dual-emitting N, Eu<sup>3+</sup>-CD nanocluster-based probe was constructed for the fluorescence ratiometric detection of tetracycline (TC). Once introducing TC, the blue emission of CDs was quenched through an IFE effect, but red emission of Eu<sup>3+</sup> was significantly sensitized through an AE effect. Taking advantage of aggregation of CDs in aqueous solution, the N, Eu<sup>3+</sup>-CD nanocluster possessed a high sensitivity for detection of TC due to the spatial proximity of a large number of sensing units in the aggregated nanocluster assembly. The detection limit for TC was low to 35 nM. This work will provide a new insight into tuning the self-assembly of CDs and to regulate the photoluminescence and sensing performance of CDs.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"77 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241630","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}
Jiyuan Su, Dengke Xiang, Wan Zhong, Yizhuo Fu, Ruiting Diao, Xueqian Chen, Chao Lu
{"title":"Electrochemiluminescence Monitoring of the Ligand Exchange Process of Gold Nanoclusters","authors":"Jiyuan Su, Dengke Xiang, Wan Zhong, Yizhuo Fu, Ruiting Diao, Xueqian Chen, Chao Lu","doi":"10.1021/acs.analchem.5c04409","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04409","url":null,"abstract":"Ligand exchange reaction (LER) plays an important role in the synthesis and postmodification of metal nanoclusters (MNCs). However, due to the challenges in the analysis of the metal–ligand interface, the approaches of revealing the ligand exchange process of MNCs still lag behind. In this work, a detailed ligand exchange process of MNCs was revealed by monitoring their electrochemiluminescence (ECL) signals. Taking tetrakis(hydroxymethyl) phosphonium chloride (THPC)–gold nanoclusters (AuNCs) as a model for the existing nanocluster and 8-mercaptooctanoic acid (MOA) as a model for the incoming ligand, the ECL intensities of THPC/MOA-AuNCs first increased and then decreased before ultimately reaching a stable plateau. Further investigation confirmed that the initial increase in ECL corresponded to ligand replacement on the surface of AuNCs, while the subsequent ECL decrease was attributed to ligand rearrangement. Both the ligand replacement and ligand shell reconstruction processes modulated interligand interactions and ligand-to-metal charge transfer (LMCT) properties, thereby altering the electronic band of AuNCs and ultimately tuning their ECL emission performances. The developed ECL-based approach for monitoring LER also exhibited universal applicability, which can successfully extend to the other AuNCs with different ligand pairs. This work not only provides deep insight into the correlation between the ECL intensity and surface dynamics of MNCs but also offers a convenient approach to monitor the ligand exchange process of MNCs.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"33 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241631","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}