Analytical Chemistry最新文献

{"title":"Functionalized Polystyrene Sensor for Selective Extraction and Assay of Plutonium at Ultratrace Level in Complex Radionuclide Matrices","authors":"Amol Mhatre, Chhavi Agarwal, Reshmi Thekke Parayil, Rahul Tripathi","doi":"10.1021/acs.analchem.4c05601","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05601","url":null,"abstract":"The present study focuses on the development of a scintillation sensor specifically designed for the selective extraction and ultratrace detection of Pu in the presence of other α and β-γ emitting radionuclides. To achieve this, a polystyrene (PS) film, embedded with the fluorophore 2,5-diphenyloxazole (PPO) and the activator 1,4-bis(2-methylstyryl)benzene (MSB), has been prepared as the substrate owing to its excellent pulse height response. The Pu selective functional groups have been introduced onto the PS substrate by surface grafting of bis(2-(methacryloyloxy)ethyl) phosphate (BMEP) monomer using in situ ultraviolet (UV) polymerization. The scintillation sensor could be successfully tested for Pu detection in the presence of α (Am, Cm, U) and β-γ (Cs, Ba, and Eu) emitting radionuclides. The sensor has been successfully applied for the uptake and estimation of Pu from a legacy sample containing high activities of ¹³⁷Cs and ²⁴¹Am. In order to test the response of the Pu-loaded sensor in the most complex scenario, it has been exposed to a freshly prepared fission product solution. In this case, the uptake of fission product (⁹⁵Zr and ⁹⁵Nb) has been observed along with Pu, which introduced significant interference from β particles in the scintillation pulse height spectra of Pu. With optimization of the thickness of the PS substrate, the β contribution could be reduced and Pu could be estimated in such a complex scenario. If the Pu activity is sufficiently high, the PS film can also be subjected to α spectrometry using solid-state Si detectors for quantification of Pu. The developed sensor has been found to be sensitive, selective, and reusable and has a linear response over a wide range of Pu concentrations. Moreover, these sensors are deployable for field applications with the capability of remote monitoring, enabling low-level detection of Pu even in the presence of other interfering radionuclides.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"23 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745398","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":"Preclinical Evaluation of HSP90 Noninvasive Imaging in Colorectal Cancer Diagnosis","authors":"Lenan Zou, Qi Chang, Chengwei Chen, Ao Li, Yang Luo, Xiaohui Wang, Xue Li, Zihan Wu, Mengyao Zhou, Haoran Xu, Hui Wang, Zhihao Han, Yueqing Gu","doi":"10.1021/acs.analchem.4c05864","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05864","url":null,"abstract":"Heat shock protein 90 (HSP90) is a powerful molecular chaperone responsible for the stability and integrity of various client proteins, including various transcription factors, kinases, and steroid hormone proteins, among others. Overexpression of HSP90 is closely related to cancer, immune diseases, and neurodegenerative diseases. However, there are few effective fluorescent probes for HSP90. Therefore, we synthesized a near-infrared fluorescent probe YQHSI-MPA-1 targeting HSP90. The probe was later structurally modified to improve the targeting specificity and accuracy in vivo as YQHSI-MPA-2. Furthermore, the application values of YQHSI-MPA-2 in situ CRC, AOM-DSS-induced CRC, and various metastasis models were evaluated. The results showed that YQHSI-MPA-2 had excellent specificity and high tumor contrast. In conclusion, YQHSI-MPA-2 is an ideal tool for tumor detection and surgical navigation.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"20 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758451","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":"Does Native Capillary Zone Electrophoresis-Mass Spectrometry Maintain the Structural Topology of Protein Complexes?","authors":"William J. Moeller, Zihao Qi, Qianjie Wang, Qianyi Wang, Vicki H. Wysocki, Liangliang Sun","doi":"10.1021/acs.analchem.4c06949","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06949","url":null,"abstract":"Native capillary zone electrophoresis-mass spectrometry (nCZE-MS) is a useful analytical tool for studying protein complexes. However, the extent to which the protein complexes maintain their native structural topology in nCZE-MS compared to traditional native MS (nMS) is still not fully characterized. In this technical note, we contribute to this topic by coupling nCZE-MS with surface-induced dissociation (SID) for two well-studied protein complexes (streptavidin and human recombinant C-reactive protein). SID cleaves the weakest interface of a given complex, making it a powerful diagnostic tool for identifying perturbations of protein complex structures based on fragmentation patterns. The SID fragmentation patterns of the two protein complexes from nCZE-MS under normal and charge-reducing conditions show a high similarity index compared to those from direct infusion. Additionally, nCZE-MS shows the potential to separate different conformations or different proton distributions that have subtle differences. Although only two cases are shown, the results suggest that nCZE-MS can maintain the native-like structural topology of protein complexes.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"50 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745401","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":"Challenges in Detecting Hydroxyl Radicals Generated in Water Droplets with Mass Spectrometry","authors":"Dong Xing, Xufeng Gao, Huan Chen, Jianze Zhang, Madison E. Edwards, Chiyu Liang, Chongqin Zhu, Yifan Meng, Richard N. Zare, Yu Xia, Xinxing Zhang","doi":"10.1021/acs.analchem.5c00386","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00386","url":null,"abstract":"Water is sprayed into the air using three distinct methods: (1) nanoelectrospray ionization, (2) a vibrating membrane nebulizer, and (3) a pneumatic nebulizer. The resulting droplets are analyzed by three different mass analyzers: (a) a linear ion trap mass analyzer on an <i>LTQ-XL</i> mass spectrometer, (b) the <i>Velos Pro</i> dual-pressure linear ion trap mass analyzer on an <i>Orbitrap Elite</i> mass spectrometer, and (c) the Orbitrap mass analyzer on the same <i>Orbitrap Elite</i> system. We searched for hydroxyl radical adducts with hydronium ions (OH•–H₃O⁺) or reaction products with caffeine dissolved in water and with melatonin dissolved in water. These experiments were repeated in several different laboratories, and all results were the same. The oxidation products of caffeine and melatonin were not detected when using the Orbitrap mass analyzer having a much longer holding time in the ion trap (500 ms) but could be observed with reduced intensity at much shorter holding times (&lt;10 ms). The signal of OH•–H₃O⁺ was also significantly reduced when using the <i>Velos Pro</i> dual-pressure linear ion trap mass analyzer. These results suggest that ion signals from fragile radicals may be diminished or lost depending on the mass detection system and operating conditions employed, and there may be a risk of obtaining spurious results when using an Orbitrap mass spectrometer.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"72 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745402","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":"Rapid MALDI-MS/MS-Based Profiling of Lipid A Species from Gram-Negative Bacteria Utilizing Trapped Ion Mobility Spectrometry and mzmine","authors":"Edward Rudt, Matti Froning, Steffen Heuckeroth, Lucas Ortmann, Julia Diemand, Linus Hörnschemeyer, Alexander Pleger, Max Vinzelberg, Robin Schmid, Tomáš Pluskal, Ulrich Dobrindt, Heiko Hayen, Ansgar Korf","doi":"10.1021/acs.analchem.4c05989","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05989","url":null,"abstract":"Lipid A, a crucial component of lipopolysaccharides (LPS), plays a pivotal role in the pathogenesis of Gram-negative bacteria. Lipid A patterns are recognized by mammals and can induce immunostimulatory effects. However, the outcome of the interaction is highly dependent on the chemical composition of individual lipid A species. The diversity of potential fatty acyl and polar headgroup combinations in this complex saccharolipid presents a significant analytical challenge. Current mass spectrometry (MS)-based lipid A methods are focused on either direct matrix-assisted laser desorption/ionization (MALDI)-MS screening or comprehensive structural elucidation by tandem mass spectrometry (MS/MS) hyphenated with separation techniques. In this study, we developed an alternative workflow for rapid lipid A profiling covering the entire analysis pipeline from sample preparation to data analysis. This workflow is based on microextraction and subsequent MALDI-MS/MS analysis of uropathogenic <i>Escherichia coli</i> utilizing trapped ion mobility spectrometry (TIMS), followed by mzmine data processing. The additional TIMS dimension served for enhanced sensitivity, selectivity, and structural elucidation through mobility-resolved fragmentation via parallel accumulation-serial fragmentation (PASEF) in parallel reaction monitoring (prm)-mode. Furthermore, mzmine enabled automated MS/MS acquisition by adapting the spatial ion mobility-scheduled exhaustive fragmentation (SIMSEF) strategy for MALDI spot analysis. It also facilitated robust lipid A annotation through a newly developed extension of the rule-based lipid annotation module, allowing for the custom generation of lipid classes, including specific fragmentation rules. In this study, the first publication of lipid A species’ collision cross section (CCS) values is reported, which will enhance high-confidence lipid A annotation in future studies.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"25 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745403","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":"Precise Conformational Tuning Facilitated by Tetrahedral DNA Framework Dimers for Enhanced Biomolecular Detection","authors":"Jiankai Jin, Guoqian Qin, You Nie, Yi Wu, Jun Zhang, Xiaolei Zuo, Rongzhang Hao, Shaopeng Wang","doi":"10.1021/acs.analchem.5c00860","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00860","url":null,"abstract":"Cellular systems achieve precise biomolecular recognition through dynamic regulation of molecular conformation and spatial arrangement, a complexity that is difficult to replicate in vitro, limiting advancements in biosensing technologies. The nanoscale programmability of tetrahedral DNA frameworks (TDFs) offers a compelling solution, enabling precise control over the spatial arrangement and conformation of nucleic acid targets, making TDFs highly effective for biosensor interface engineering. In this study, we developed dimeric TDF capture probes with tunable interprobe distances (25–45 nm), allowing for the precise stretching and ultrafast detection of single-stranded DNA (ssDNA) targets. By integrating auxiliary probes to modulate local target conformation, hybridization efficiency was significantly enhanced, yielding a 2.9-fold improvement in signal intensity. This approach was successfully applied to single-nucleotide polymorphism (SNP) detection, demonstrating a 2-fold improvement in discrimination sensitivity. Furthermore, integration with a microarray fluorescence chip enabled rapid and accurate quantification of IDH1 mutant allele frequency (MAF), highlighting its potential for glioma classification, disease monitoring, and therapeutic evaluation. These findings underscore the transformative potential of TDF-based interface engineering as a platform for high-performance biosensing and diagnostic applications.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"75 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745553","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":"SiaQuant Unveils Serum α2,3/α2,6 Sialylation Heterogeneities and Predicts Neoadjuvant Chemotherapy Response in Locally Advanced Cervical Cancer","authors":"Xiaoxiao Feng, Jing Li, Chong Li, Jun Wang, Yuying Liang, Bin Fu, Zhenyu Sun, Jun Yao, Juan He, Aiying Nie, Liming Wei, Weiwei Feng, Haojie Lu","doi":"10.1021/acs.analchem.4c04952","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c04952","url":null,"abstract":"Sialylation significantly influences tumor progression, invasion, and metastasis. Accurately characterizing sialylated <i>N</i>-glycopeptides (SGPs), particularly the linkage-specific analysis of α2,3,α2,6 sialic acids, remains a challenging yet crucial task in glycoproteomics. Notably, to date, there is a notable lack of detailed studies on α2,3/α2,6 sialylation in serum. Here, we present SiaQuant, an integrated strategy that employs liquid chromatography–ion mobility–tandem mass spectrometry (LC-IM-MS/MS), capitalizing on the distinctive separation of characteristic isomeric glycan fragments in ion mobility to accurately analyze serum α2,3/α2,6 sialylation patterns. It first provides proteome-wide insights into α2,3/α2,6 sialylation in serum, revealing three-dimensional heterogeneities across <i>N</i>-glycans, <i>N</i>-glycosites, and <i>N</i>-glycoproteins. Additionally, SiaQuant identifies potential candidate biomarkers for neoadjuvant chemotherapy (NACT) response in locally advanced cervical cancer (LACC), where the elevated level of α2,3/α2,6 sialylation was found to be associated with NACT resistance. In summary, SiaQuant offers the most comprehensive site- and linkage-specific <i>N</i>-glycosylation profiling of serum and shows great potential in clinical usage.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"60 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745397","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":"The Role of Chloride in Raman Signal Enhancement by Electrochemical Silver Oxidation Revealed by Dark Field Microscopy","authors":"Sheila Hernandez, Kevin Wonner, Pouya Hosseini, Paolo Cignoni, Aranzazu Heras, Alvaro Colina, Kristina Tschulik","doi":"10.1021/acs.analchem.4c05942","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05942","url":null,"abstract":"Raman spectroscopy is a widely used technique in several contexts, including chemical analysis, materials characterization, and catalysis. However, to exploit the high capacities of this technique, signal enhancement is needed. For this purpose, several methodologies can be used, and those known as surface enhanced Raman scattering (SERS), or resonance Raman (RR) have been widely used. However, there are some new strategies, such as electrochemical surface oxidation enhanced Raman scattering (EC-SOERS), that require further understanding for optimum exploitation in diverse analytical contexts. In EC-SOERS, the enhancement of the Raman signal is observed during the electrochemical oxidation of silver in the presence of a precipitating agent, but only for specific concentrations of this agent. In this work, we use electrochemical dark-field microscopy (DFM) to explore and reveal the origin of this concentration dependency by monitoring the oxidative formation of EC-SOERS substrates in solutions of different chloride concentrations. These <i>operando</i> studies provide a complete picture of the processes taking place on the electrode surface and at the solution adjacent to it with a high time resolution, showing that the formation of the EC-SOERS substrate requires sufficient Cl^– to generate AgCl nanocrystals without blocking the surface and allowing the release of Ag⁺ cations. Thanks to the gained mechanistic insights, the selection of a suitable precipitation agent concentration can move from a trial and error selection process to a knowledge-based selection, allowing the rational design of different SOERS substrates that will facilitate the efficient application of SOERS in different research contexts","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"1 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745399","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":"Enhanced Breath Aldehyde Analysis by Dual-Membrane-Assisted Charge Tagging, Enrichment, and Onsite Elution NanoESI-MS","authors":"Beichen Zhu, Yifan Wei, Xiumei Zheng, Chengxi Tang, Xiaobo Xie, Yi Lv","doi":"10.1021/acs.analchem.5c00434","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00434","url":null,"abstract":"Aldehydes, crucial volatile organic compounds present in exhaled breath, have been established as promising biomarkers for cancer diagnosis. However, their rapid and sensitive detection through widely employed spray-based ionization mass spectrometry is still challenging. To address this, we introduce a charged “iridium isotopic signature” probe tailored for efficient capture and unambiguous identification of ubiquitous aldehydes in the gas phase. This ^191/193Ir-tagged mass spectrometric probe, equipped with a reactive amine moiety capable of interacting with aldehydes, is immobilized on the porous Nylon-6 membrane that facilitates efficient gas transport and enriches aldehydes from the complex breath matrix. Following a rapid solvent extraction, the Ir-tagging aldehyde derivatives were successfully eluted with efficient removal of excess probes by the oxidized cellulose membrane, yielding a purified sample ideally suited for direct, rapid, and ultrasensitive (with a detection limit below 0.1 ppt) nanoelectrospray ionization mass spectrometry (nanoESI-MS) analysis. By utilizing an analogous iridium complex as an internal standard, our method precisely identified and quantified 12 aldehydes in exhaled breath (EB), with several exhibiting significant elevations in esophageal cancer patients compared with healthy controls. This highlights its efficacy as a rapid and accurate tool for detecting breath aldehyde biomarkers, offering promising avenues for cancer diagnosis.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"33 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745552","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":"Examining Instrumental Factors Influencing the Performance of Data-Independent Acquisition Methods in Hydrogen/Deuterium Exchange Mass Spectrometry","authors":"Frantisek Filandr, Morgan Hepburn, Vladimir Sarpe, D. Alex Crowder, Maryam Hassannia, Stephen Coales, Yuqi Shi, Rosa Viner, Martin A. Rossotti, Joey G. Sheff, Jamshid Tanha, David C. Schriemer","doi":"10.1021/acs.analchem.5c00429","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00429","url":null,"abstract":"Hydrogen/deuterium exchange mass spectrometry (HX-MS) is a method used to study solution-phase protein structure and dynamics. Despite its many applications, HX-MS is limited in throughput because manual data analysis is still the norm. We previously developed HX-MS² technology to add a second dimension of deuteration data and promote automated data processing. Data-independent acquisition (DIA) techniques enable this approach, but we require optimized methods for best performance. Using an Orbitrap Eclipse for illustration, we show that ion optics and collision energy settings typical of a proteomics DIA experiment generate maximal peptide retrieval from the DIA library. As few as three MS² sequence ions are sufficient to generate a deuteration measurement with a precision that exceeds what is possible in traditional HX-MS. DIA window sizes are based on the chromatographic resolution of the method. An inter-scan window offset method is the recommended default configuration for most HX-DIA applications butan intra-scan overlap method can be tuned for highest performance and is recommended when maximum peptide retrieval is desired. We demonstrate the robustness of one HX-MS² configuration (consisting of Trajan HDX automation technology, an Orbitrap Eclipse mass spectrometer and AutoHX software) on an extensive time-course analysis of phosphorylase B and an epitope analysis of single-domain antibodies (V_HHs, nanobodies) specific to the receptor binding domain of SARS-CoV-2 spike protein.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"72 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745557","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}