Analytical Chemistry最新文献

{"title":"Multiplexed Detection of Pancreatic-Specific Nucleic Acids and Protein Biomarkers Using a Logic Nanofluidic Platform.","authors":"Lina Wang,Yixin Jia,Jin Wang,Xing-Hua Xia,Chen Wang","doi":"10.1021/acs.analchem.5c01978","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c01978","url":null,"abstract":"Early detection of pancreatic cancer is vital for patient survival. However, current diagnostic approaches remain constrained by insufficient precision and specificity inherent to single-biomarker detection strategies. Herein, we develop a nanochannel biosensing platform implementing cooperative dual-signal detection of pancreatic-specific biomarkers CA19-9 and miRNA-196a. Using liquid-liquid interface self-assembly, we constructed anodic aluminum oxide (AAO)-Au hybrid nanochannels integrated with a surface-modified double-key DNA nanolock (DDN). The conformational switch of DDN logic gating triggered by miRNA-196a exposes the CA19-9-aptamer, enabling specific target recognition and consequent ion current signal attenuation. Simultaneously, released miRNA-196a is quantified by catalytic hairpin assembly and hybridization chain reaction-mediated cascade amplification. Experiments show that the present DDN-based logic nanofluidic platform could achieve an ultralow detection limit of 0.000027 U·mL-1 for CA19-9 and 4.74 aM for miRNA-196a, which is 2-3 orders of magnitude higher than traditional ELISA/qPCR methods. Finally, clinical sample analysis confirms the high specificity of this platform in distinguishing pancreatic cancer and acute pancreatitis from healthy individuals. This DDN-functionalized nanofluidic biosensor provides valuable insights into designing precision detection platforms for pancreatic cancer, highlighting its significant potential for clinical diagnostics.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"17 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087761","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":"Detection of Protein Polysulfidation Using a β-(4-Hydroxyphenyl)ethyl Iodoacetamide-Derived Biotin Tag HPB.","authors":"Yuping Xin,Xinyue Zhang,Qingda Wang,Longyang Dian,Yongzhen Xia,Luying Xun,Huaiwei Liu","doi":"10.1021/acs.analchem.5c00712","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00712","url":null,"abstract":"Protein polysulfidation (Pr-SnH, n ≥ 2) is a type of post-translational modification that plays multiple physiological functions. Detecting Pr-SnH remains challenging due to the high reactivity of -SnH groups and their similarity to other thiol-based modifications. Here, we report the development of a new biotinylated tag, HPB, which is derived from β-(4-hydroxyphenyl)ethyl iodoacetamide (HPE-IAM). HPB demonstrates superior performance over the traditional iodoacetamide (IAM)-derived biotin tag IAB, especially in minimizing off-target alkylation and preserving polysulfide chains. After protocol optimization, we achieved a 73.3% accuracy rate in proteomic scale Pr-SnH detection. Further, we found that polysulfides can modify other amino acids besides cysteine, including histidine, phenylalanine, and tryptophan, by introducing -SH or -SSH groups into their heterocyclic/phenyl rings. This leads to the detection accuracy rate of all current methods being less than 100%. Nonetheless, this study provides a reliable tool for detecting protein polysulfidation from complex cellular backgrounds.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"53 89 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087763","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemiluminescence Biosensor Based on an Efficient Antifouling Cell Membrane Hydrogel for the Direct Detection of Alkaline Phosphatase in Human Serum and Cell Lysate.","authors":"Qiongwei Wu,Zhengjun Dong,Fan Geng,Jia Wang,Xianzhen Song,Caifeng Ding","doi":"10.1021/acs.analchem.5c00432","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00432","url":null,"abstract":"Electrochemiluminescence (ECL) biosensors are an ideal choice for the real-time and sensitive detection of biomarkers. However, there are many interfering biomolecules in human serum or cell lysate that can affect the ECL signal through nonspecific interface adsorption. To solve this issue, an efficient ECL antifouling biosensor based on a red blood cell membrane (RBCM) hydrogel was developed for the direct detection of alkaline phosphatase (ALP) in human serum and cell lysate. Among them, the RBCM hydrogel was prepared by embedding the purified RBCM vesicles into [1,2-distearoyl-sn-glycerol-3-phosphoethanolamine]-[polyethylene]-[acrylamide] (DSPE-PEG-AM), which endowed the antifouling interface with high stability and biocompatibility. Meanwhile, compared to RBCM, the constructed RBCM hydrogel improved the electron transfer rate of the antifouling interface. Furthermore, luminescent copper nanosheets (Cu NSs) and quencher MnO2 NSs were encapsulated in the RBCM hydrogel, which greatly reduced the distance between Cu NSs and MnO2 NSs, thereby effectively improving the signal quenching efficiency. In the presence of ALP, l-ascorbic acid 2-phosphate trisodium salt was hydrolyzed to ascorbic acid, thus disrupting the structure of MnO2 NSs to restore the ECL signal. Based on the above sensing strategies, the constructed ECL biosensor achieved an ultrasensitive detection of ALP with a wide linear range (10-5 to 104 U·L-1) and a detection limit as low as 3.4 × 10-6 U·L-1 (3δ/k), demonstrating potential application value in clinical diagnosis.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"8 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087764","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":"Quantitative Trace Analysis of Dilute Mixtures Using a Benchtop NMR System with SABRE Hyperpolarization.","authors":"Bono O Jimmink,Mattia Negroni,Thom B Posthumus,Arno P M Kentgens,Marco Tessari","doi":"10.1021/acs.analchem.5c01026","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c01026","url":null,"abstract":"Despite their modest sensitivity, benchtop NMR spectrometers have recently attracted a great deal of attention, because of their low cost, high portability, and robustness. A solution to the sensitivity limitation of benchtop spectrometers is offered by nuclear spin hyperpolarization, by which large NMR signal enhancements can be realized. Signal Amplification By Reversible Exchange (SABRE) is one-such hyperpolarization technique, which utilizes hydrogen enriched in the para spin-isomer (pH2). However, the application of SABRE with benchtop NMR has so far largely been restricted to sample concentrations in the millimolar range. In this work, we present SABRE hyperpolarization of a mixture at micromolar concentrations, measured on a 1 T benchtop spectrometer. The observed linear dependence between hyperpolarized signals and concentration demonstrates the stability of our approach, which allows quantification in the micromolar range.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"128 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087791","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":"Sequential Labeling-Assisted Precise and Multitarget Analysis of Surface Proteins on Extracellular Vesicles.","authors":"Xiaomeng Yu,Ya Cao,Jianan Xia,Kai Zhang,Zihan Zou,Jie Yang,Zhaoyin Wang,Jing Zhao","doi":"10.1021/acs.analchem.5c00326","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00326","url":null,"abstract":"Analysis of multiple surface proteins on extracellular vesicles (EVs) can reveal biological characteristics and potential therapeutic targets of cancer, particularly in highly heterogeneous breast cancer. However, due to the limited surface area of EVs, spatial hindrance remains a challenge for multiprotein assessment. Here, we present a sequential labeling-assisted electrochemical method for the precise and multitarget analysis of surface proteins on EVs, using breast cancer-related epidermal growth factor receptor and programmed death ligand-1 as examples. This sequential labeling is achieved through the use of a pair of aptamer probes functionalized with electroactive nanoparticles and an oxidative cleavage process facilitated by the bleomycin-Fe2+ complex. The results demonstrate that sequential labeling efficiently avoids the adverse effects of spatial hindrance, enabling accurate analysis of target surface proteins on as low as 341 particles/mL of standard EVs derived from triple-negative breast cancer (TNBC) cells. Moreover, this sequential labeling-assisted method is successfully applied to clinical blood samples from healthy individuals and TNBC patients, highlighting its potential utility in early diagnosis and disease-course monitoring of breast cancer. Therefore, this work offers a feasible tool for the precise identification and analysis of multiple surface proteins on individual EVs, providing valuable information at the protein level for the accurate diagnosis and personalized treatment of breast cancer.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"131 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087760","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":"Phosphorescent Naphthalene-Doped Carbon Nitride Quantum Dots for Selective Detection of Polyamide Microplastics","authors":"Qiaocheng Feng, Xiaoyan Hu, Jingru Chen, Liangqia Guo","doi":"10.1021/acs.analchem.5c00290","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00290","url":null,"abstract":"Fluorescent dye labeling is a visual method for the detection of microplastics (MPs). However, the interference from the background fluorescence in complex environmental samples results in overestimation of the MP number, and the nonspecific fluorescent dye cannot selectively detect a single type of MPs. Herein, phosphorescent naphthalene-doped carbon nitride quantum dots (NDCNQDs) were prepared via incomplete condensation of urea with 1,5-diaminonaphthalene at 250 °C and used as a specific dye to stain polyamide (PA) MPs via hydrogen bonding. A phosphorescence imaging method for the selective detection of PA MPs was proposed. Benefitting from the long lifetime of phosphorescence, the interference from the background fluorescence in environmental samples was avoided. The recoveries for PA MPs in pond water samples and pond mud samples were 91.2–108.4%. PA MPs in environmental samples (e.g., streamwater, sediment, house dust) were analyzed without complicated pretreatment. This work provides a strategy for the specific detection of PA MPs in environmental samples.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"14 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144067088","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":"Microfluidics-Based High-Throughput Single-Cell Analysis of Reactive Oxygen Species and T Cell Exhaustion","authors":"Ruotong Rao, Rui Cao, Wenjun Wang, Tao Li, Heng Zhou, Yin Zhao, Jiang Zhu, Yunhuang Yang, Rui Hu, Fuling Zhou, Ying Li","doi":"10.1021/acs.analchem.5c01485","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c01485","url":null,"abstract":"Reactive oxygen species (ROS) play a significant role in cellular signaling and oxidative stress, with elevated levels often linked to T cell exhaustion in various pathological conditions, including cancer. However, the relationship between ROS and T cell exhaustion in acute myeloid leukemia (AML) remains unexplored. To address this, we developed a high-throughput single-cell platform─T cell exhaustion and reactive oxygen species analyzer (TEROSA). The system achieved a single-cell capture efficiency of up to 80% with a throughput of 2400 cells and enabled dynamic monitoring of triple molecules, including the intracellular mitochondrial superoxide, on-membrane T cell exhaustion marker PD-1, and secreted extracellular H₂O₂. Our study evaluated the device’s performance across multiple cell lines and demonstrated its capability to assess ROS production at the single-cell level. In particular, we analyzed T cells from AML patients and found significantly elevated ROS levels and increased PD-1 expression compared to healthy donors, suggesting a potential link between ROS and T cell exhaustion in AML. These findings highlight the utility of TEROSA in advancing our understanding of T cell behavior in leukemia and underscore its potential for broader applications in single-cell analysis.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"9 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144067089","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":"Coupling Immunoprecipitation with Multiplexed Digital PCR for Cell-Free DNA Methylation Detection in Small Plasma Volumes of Early-Onset Colorectal Cancer","authors":"Truong T. Truong, Klara Mikloska, Judith Sum, Martina Oberländer, Nikolas von Bubnoff, Lea Christiansen, Sebastian Tornow, Stefanie Derer, Florian Janke, Holger Sültmann, Sebastian Zeissig, Michael Linnebacher, Clemens Schafmayer, Michael Lehnert, Tobias Hutzenlaub, Nils Paust, Peter Juelg","doi":"10.1021/acs.analchem.5c01361","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c01361","url":null,"abstract":"Colorectal cancer (CRC) remains a major global health challenge, with an increasing incidence of early-onset cases among young adults. Targeted analysis of cell-free DNA (cfDNA) methylation in blood has emerged as a promising minimally invasive diagnostic approach. While digital PCR (dPCR) offers high sensitivity and low turnaround times, conventional bisulfite-based dPCR assays require large plasma volumes due to cfDNA degradation, limiting clinical feasibility. To overcome this limitation, we developed a bisulfite-free, low-plasma-volume assay by coupling cell-free methylated DNA immunoprecipitation (cfMeDIP) with multiplexed dPCR for methylation detection. Assays were designed for CRC targets based on publicly available bisulfite-based plasma data and optimized for native, bisulfite-untreated cfDNA. The cfMeDIP-dPCR assays were first developed and optimized on circulating tumor DNA surrogates derived from HCT116 cells and subsequently validated in a pilot study, including 32 early-onset CRC (EO-CRC) patients and 29 non-CRC individuals. Methylation ratios, defined as the proportion of methylated to total cfDNA copies per marker, served as a diagnostic indicator. Three out of four selected markers (<i>SEPT9</i>, <i>KCNQ5</i>, and <i>C9orf50</i>) were successfully adapted, with significantly higher methylation ratios (<i>p</i> ≤ 0.001) in the EO-CRC cohort. <i>KCNQ5</i> demonstrated the highest diagnostic performance, achieving an 85% sensitivity at a 90% specificity, with methylation ratios correlating with the tumor stage. This study presents the first cfMeDIP-dPCR approach, demonstrating its potential as a sensitive liquid biopsy assay. Requiring only 0.5 mL of plasma, i.e., more than 20 times less than a sensitivity-matched bisulfite-based assay, cfMeDIP-dPCR facilitates clinical implementation for CRC and other diseases with epigenetic signatures.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"35 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066970","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":"Deep Learning-Assisted Sensor Array Based on Host–Guest Chemistry for Accurate Fluorescent Visual Identification of Multiple Explosives","authors":"Wenxing Gao, Zhibin Wang, Qiang Li, Wenfeng Liu, Hao Guo, Li Shang","doi":"10.1021/acs.analchem.5c01326","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c01326","url":null,"abstract":"Accurate and rapid discrimination of multiple explosives with high precision is of paramount importance for national security, ecological protection, and human health yet remains a significant challenge with conventional analytical techniques. Herein, we present an innovative deep learning-assisted artificial vision platform based on cyclodextrin-protected multicolor fluorescent gold nanoclusters (CD-AuNCs) with four distinct emission wavelengths, enabling the highly accurate discrimination of seven explosives. The sensor array leverages the host–guest interactions between the cyclodextrin ligands on the AuNCs’ surface and the target explosives, generating unique fluorescence fingerprint patterns. Mechanistic studies reveal that the fluorescence enhancement of CD-AuNCs is attributed to ligand rigidification, while fluorescence quenching is primarily caused by photoinduced electron transfer between CD-AuNCs and explosives. The multicolor fluorescence responses are captured by using a smartphone, and the corresponding RGB values are simultaneously extracted. To enhance the recognition accuracy, a dense convolutional network (DenseNet) algorithm with advanced image recognition capability is integrated with the fluorescence sensor array. This platform achieves remarkable 100% recognition accuracy at a concentration of 200 μM, enabling the rapid and precise visual classification of explosives. The proposed strategy not only provides a powerful tool for on-site explosive monitoring but also offers a versatile platform for the intelligent detection of diverse analytes, demonstrating significant potential for real-world applications in environmental and security monitoring.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"83 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144067000","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":"Recognition Site Density Regulation of Schiff Base Organic Porous Polymers for Ultrasensitive and Specific Fluorescence Sensing toward Gaseous DCP.","authors":"Huazangnaowu Bai,Ruiqi Qiao,Fang Xiao,Jiawen Li,Baiyi Zu,Zhenzhen Cai","doi":"10.1021/acs.analchem.5c01087","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c01087","url":null,"abstract":"Due to the severe interference from analogues such as hydrochloric acid, it is of great significance to establish a highly reliable technique to enhance the discrimination ability toward diethyl chlorophosphate (DCP). Here, based on the electrophilicity of DCP, a series of zero-background fluorescence Schiff base materials with different densities of C═N bonds as recognition sites were designed and synthesized by modulating the chain length. It is found that the increase of the C═N bond density and the specific surface area could improve the collision efficiency with DCP, thereby improving the response speed. When the density of C═N bonds is 3.86 × 1021/cm3 and the specific surface area is 128.5 m2/g, DFDBA-POP demonstrated a more superior sensing performance toward the target analyte, including the ability to detect gaseous DCP, a rapid response (1 s), and superior selectivity even in the presence of 15 kinds of interferents including the very similar hydrochloric acid. Moreover, the practicality of DFDBA-POP was further verified by a DFDBA-POP solid-state sensor, which is capable of specifically identifying gaseous DCP. The present nonfluorescent Schiff base materials design and modulation strategy would open up a new gate for the rational design of high-performance fluorescent materials to detect and discriminate trace hazardous substances with similar structures and properties.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"15 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144065786","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}