Analytical Chemistry最新文献

{"title":"Cancellation of Spectral and Spatial Crosstalk in Spectral Imaging for High-Dynamic-Range Electrophoretic Analysis of STR-PCR Products","authors":"Takashi Anazawa, Ryo Imai, Sayaka Tezuka","doi":"10.1021/acs.analchem.4c06970","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06970","url":null,"abstract":"In spectral imaging, an optical system generates two mutually dependent kinds of crosstalk on an image sensor: spectral crosstalk (i.e., spectral mixing) between fluorescences of different dyes and spatial crosstalk (i.e., image artifacts) between fluorescences from different emission points in the field of view of the sensor. Therefore, an algorithm to cancel both kinds of crosstalk simultaneously (i.e., simultaneous spectral unmixing and image-artifact reduction) is proposed. The algorithm is based on the assumption that a crosstalk matrix (i.e., point-spread functions, PSFs) consisting of all crosstalk ratios is constant regardless of the causes of both kinds of crosstalk. By applying the algorithm to a nine-wavelength-band measurement of four-capillary electrophoretic separation of STR-PCR (short tandem repeat-polymerase chain reaction) products labeled with six dyes, true peaks of each of the dyes were obtained, while false peaks due to spatial crosstalk were reduced below the lower limit of detection in electropherograms. As a result, effective sensitivity and effective dynamic range were improved by 2 orders of magnitude. Moreover, it became possible to perform robust human identification of on-site-collected trace samples containing template DNA at any concentration in a 3-order concentration range by a single STR-PCR and a single electrophoretic separation.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"19 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143789630","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":"Single-Molecule Liquid Biopsy Detects Low- and High-Abundance Protein Markers Simultaneously for Pancreatic Cancer Diagnosis","authors":"Xinjian Wang, Yudong Che, Songlin Liu, Bochen Ma, Yijun Liu, Jiao Lei, Liang Yuan, Yiwen Zhou, Jieer Ying, Yimin Zhang, Chen Tian, Tao Zhu, Lubin Qi, Yifei Jiang, Xiaohong Fang","doi":"10.1021/acs.analchem.4c07031","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c07031","url":null,"abstract":"Simultaneous analysis of multiple biomarkers can typically improve the sensitivity and specificity of a disease diagnosis. Low-abundance serum proteins have recently emerged as a novel class of biomarkers for diseases. Due to the low concentration, the low-abundance protein analysis relies on single-molecule immunoassay, which has a very limited dynamic range. As a result, simultaneous analysis of low- and high-abundance protein markers requires multiple instruments, which demands larger sample volumes and is cost-/labor-consuming. To overcome these limitations, we developed a single-molecule imaging technique that can detect low- and high-abundance protein markers simultaneously in one chip. By employing a hybrid biomarker capture strategy that involves both glass surface and bead immobilization, our method greatly extended the detection range of the single-molecule assay. We used the method for pancreatic cancer diagnosis and analyzed three serum biomarkers of different abundances, including LIF, CA19-9, and CA125. Combined analysis of the three biomarkers yielded exceptional sensitivity and specificity (AUC = 0.996), which is better than using any of the markers alone, including CA19-9 that is used in clinical practice (AUC = 0.804). Overall, we demonstrated a simple and cost-effective method that greatly extended the dynamic range of single-molecule imaging while maintaining the sensitivity, which has great potential in various clinical applications.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"183 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798272","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":"High-Performance Biosensing Platforms Based on Enzyme-Linked Nucleic Acid Amplification Regulated by Synergistic Allosteric Hairpin Catalysis of Bimetallic Nanozymes and Its Mechanisms","authors":"Yunzhi Ma, Chenchen Jin, Feiyan Yan, Yeyu Wu, Jun Yan, Ke-Jing Huang, Yu Ya, Xuecai Tan","doi":"10.1021/acs.analchem.4c06042","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06042","url":null,"abstract":"Sugar cane smut disease can greatly decrease both the production and quality of sugar cane, and its early diagnosis is an effective strategy to ensure the quality and increase the income of sugar cane. Therefore, developing high-precision detection methods has major implications for the actual production of sugar cane. Herein, we synthesize bimetallic nanozymes Fe₃O₄@AuNPs with excellent glucose oxidase-like activity and nitrogen-doped graphdiyne (N-GDY) with excellent conductivity and interfacial loading capacity, which are used as catalysts for biofuel cells and flexible electrode substrates, respectively. An allosteric hairpin-regulated enzymatic cascade nucleic acid amplification strategy is employed to construct a novel biosensing platform for precise and highly sensitive analysis of the pathogen causing sugar cane smut disease, and the catalytic mechanism of the nanozymes is studied. The sugar cane smut pathogen can specifically cause the complementary region of the allosteric hairpin to migrate to form a new functional hairpin. Under the promotion of enzymes, a dual nucleic acid amplification occurs using the new functional hairpin as a template and outputs a large amount of double-stranded products, which are captured by the RCA long chain on the biocathode. At the cathode, DNA double strands are capable of holding a large quantity of Ru[(NH₃)₆]³⁺ through electrostatic attraction. The nanozymes on the anode can catalyze the oxidation of glucose to produce electrons, and AuNPs/N-GDY can efficiently transfer electrons to the cathode to obtain a strong open-circuit voltage signal, which exhibits a strong linear correlation to the pathogen in the range of 0.0001–10000 pM, with a detection limit of 53.29 aM (<i>S</i>/<i>N</i> = 3). The sensing platform offers a reliable method that allows highly precise and accurate detection of sugar cane smut disease and has great application and development potential for early identification of smut and on-site rapid detection.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"34 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143789631","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":"Scanning Electrochemical Microscopy: An Evolving Toolbox for Revealing the Chemistry within Electrochemical Processes.","authors":"Seth T Putnam, Armando Santiago-Carboney, Peisen Qian, Joaquín Rodríguez-López","doi":"10.1021/acs.analchem.4c06996","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06996","url":null,"abstract":"","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":" ","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143794035","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":"Single-Atom Iron Boosts Counter Electrode Electrochemiluminescence for Biosensing","authors":"Hongkun Li, Qianqian Cai, Zhikang Li, Guifen Jie, Hong Zhou","doi":"10.1021/acs.analchem.5c00181","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00181","url":null,"abstract":"Traditional electrochemiluminescence (ECL) detection makes it difficult to realize the spatial separation of the sensing and reporting sides, which inevitably causes mutual interference between the target and the luminescent substance. By studying the relationship between the luminol luminescence position and electrode potential in a three-electrode system, this work realized spatial separation of the sensing and reporting sides for the first time. Experimental investigations showed that luminol only emitted ECL signals at electrodes with positive polarity, regardless of whether a positive or negative voltage was applied. Inspired by this, we introduced a carbon vacancy-modified iron single-atom catalyst (V_C–Fe–N-C SAC) with excellent oxygen reduction reaction (ORR) activity into the working electrode, which can catalyze the reduction of dissolved O₂ to produce abundant reactive oxygen species (ROS). ROS diffused to the surface of the counter electrode to oxidize luminol and produce a high-intensity ECL signal at an ultralow trigger potential. As a proof-of-concept application, a sensitive ECL biosensor with spatial separation of the sensing and reporting sides was first constructed for microcystin-LR (MC-LR) detection. This work solved the interference between the target and luminescent substance in the traditional three-electrode ECL system and improved the detection accuracy and sensitivity. Furthermore, the introduction of single-atom catalysts (SAC) avoided the use of the coreactant H₂O₂ and the tedious electrochemical oxidation process of luminol, which broadened the application of ECL biosensors.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"1 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143789632","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":"Separation and Analysis of Rare Tumor Cells in Various Body Fluids Based on Microfluidic Technology for Clinical Applications","authors":"Chang Xu, Dexin Du, Zhaojun Han, Haibin Si, Wei Li, Lu Li, Bo Tang","doi":"10.1021/acs.analchem.4c06925","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06925","url":null,"abstract":"This article has not yet been cited by other publications.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"23 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782999","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":"Miniaturized Supercritical Fluid Chromatography Coupled with Ion Mobility Spectrometry: A Chip-Based Platform for Rapid Chiral and Complex Mixture Analysis","authors":"Julius Schwieger, Klaus Welters, Christian Thoben, Alexander Nitschke, Stefan Zimmermann, Detlev Belder","doi":"10.1021/acs.analchem.5c00227","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00227","url":null,"abstract":"This study presents the first coupling of miniaturized chip-based supercritical fluid chromatography (SFC) with ion mobility spectrometry (IMS) enabling rapid two-dimensional analysis of moderately polar compounds. For the first time, ionization and analyte transfer at the SFC-IMS interface are achieved solely through eluent decompression in conjunction with a shifted electric IMS inlet potential. This straightforward approach significantly reduces instrumentation complexity and size, promoting system compactness and robustness. The integration of chip-based SFC with IMS enables high-speed separations of complex samples, drastically reducing analysis time while utilizing a detector capable of delivering structural information at a rapid acquisition rate and low cost. Evaluation of the SFC-IMS system as demonstrated through the chiral separation of Tröger’s base revealed exceptional repeatability and sensitivity. Short columns and high flow rates resulted in record-speed SFC-IMS analysis in just six seconds. The system was successfully used to analyze a complex mixture containing five isomers, including naloxone and 6-monoacetylmorphine, in just 30 s.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"8 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782902","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":"Better Together: Synergistic Enhancement of AuNPs and Bifunctional Monomers in a Dual-Channel Molecularly Imprinting Electrochemical Sensor for Simultaneous Detection of Diuron and Thidiazuron","authors":"Yi He, Chunyuan Tang, Yue Ren, Bingzheng Yuan, Libo Li, Tianyan You, Xuegeng Chen","doi":"10.1021/acs.analchem.4c06793","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06793","url":null,"abstract":"The combination of diuron (DU) and thidiazuron (TDZ) is commonly used in cotton production for its excellent adaptability to low temperatures, which may lead to increased crop and soil pollution. The simultaneous detection of DU and TDZ poses significant challenges due to their weak and overlapping signals, along with an unclear electrochemical detection mechanism for TDZ. This study developed a dual-channel multifunctional molecularly imprinted electrochemical (MMIP-EC) sensing platform by optimizing the substrate material and MIP layer for high performance. First, amino-functionalized graphene-based poly(pyrrole)-poly(3,4-ethylenedioxythiophene) (NH₂-rGO/PPy-PEDOT) with high conductivity was synthesized as the substrate. Subsequently, MMIPs were prepared in one step using electropolymerization by introducing chloroauric acid (HAuCl₄) and bifunctional monomers (dopamine and thiophene). This method not only enhanced specific binding capacity of the MMIP layer but also amplified the signal through the synergistic effect of reduced AuNPs and bifunctional monomers. Furthermore, two independent modules (MMIP-DU and MMIP-TDZ) were integrated into a dual-channel EC platform for simultaneous transmission of DU and TDZ responses to separate windows. Finally, based on high-performance liquid chromatography–mass spectrometry (HPLC-MS) and electrochemical kinetics studies, it was speculated that the electrochemical oxidation of TDZ via the carbonylation of a secondary amine under strongly acidic conditions, followed by hydrolysis to form a carboxyl group, reveals the electrochemical oxidation mechanism of TDZ. The developed sensor exhibited excellent performance in selectivity and sensitivity, with low detection limits of 26.6 pg/mL (DU) and 39.2 pg/mL (TDZ). In conclusion, this sensing platform presents a novel perspective for the cost-effective and highly efficient detection of diverse environmental pollutants.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"23 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782998","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":"Data-Independent Acquisition Coupled with Electron-Activated Dissociation for In-Depth Structure Elucidation of the Fatty Acid Ester of Hydroxy Fatty Acids","authors":"Yuto Kurizaki, Yuki Matsuzawa, Mikiko Takahashi, Hiroaki Takeda, Mayu Hasegawa, Makoto Arita, Junki Miyamoto, Hiroshi Tsugawa","doi":"10.1021/acs.analchem.4c06736","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06736","url":null,"abstract":"Fatty acid esters of hydroxy fatty acid (FAHFAs) are a biologically important class of lipids known for their anti-inflammatory and antidiabetic effects in animals. The physiological activity of FAHFAs varies depending on the length of the carbon chain, number and position of double bonds (DBs), and position of the hydroxyl (OH) group. Moreover, gut bacteria produce FAHFAs with more diverse structures than those produced by the host, which necessitates a FAHFA-lipidomics approach grasping their diverse structures to fully understand the physiological and metabolic significance of FAHFAs. In this study, we developed a methodology for the in-depth structural elucidation of FAHFAs. First, FAHFAs were enriched by using a solid-phase extraction (SPE) system coated with titanium and zirconium dioxide, which separated these analytes from neutral lipids and phospholipids. The fractionated metabolites were then derivatized using <i>N,N</i>-dimethylethylenediamine (DMED) to facilitate FAHFA detection in the positive ion mode of a liquid chromatography-tandem mass spectrometry (LC-MS/MS) system. A data-independent acquisition technique known as sequential window acquisition of all theoretical mass spectra (SWATH-DIA) was used to collect sequential MS/MS spectra of the DMED-derivatized fatty acid metabolites. Structural elucidation was based on fragment ions generated by electron-activated dissociation (EAD). DMED-FAHFAs were annotated using the newly updated MS-DIAL program, and FAHFA isomers were quantified using the MRMPROBS program, which quantifies lipids based on SWATH-MS/MS chromatograms. This procedure was applied to profile the FAHFAs present in mouse fecal samples, characterizing seven structures at the molecular species level, 63 structures at the OH-position-resolved level, and 15 structures at both the DB- and OH-position-resolved levels, using the MS-DIAL program. In the MRMPROBS analysis, 2OH and 3OH hydroxy fatty acids with more than 20 carbon atoms were predominantly expressed, while 5OH–13OH hydroxy fatty acids with 16 or 18 carbon atoms were the major components, abundant at positions 5, 7, 9, and 10. Furthermore, age-related changes in FAHFA isomers were also observed, where FAHFA 4:0/2O(FA 26:0) and FAHFA 16:0/10O(FA 16:0) significantly increased with age. In conclusion, our study offers a novel LC-SWATH-EAD-MS/MS technique with the update of computational MS to facilitate in-depth structural lipidomics of FAHFAs.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"58 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775741","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":"Conversion Reaction of Stable-Isotope Oxygen Labeling of Carboxylic Acids for Accurate Screening LC-MS/MS Assay: Application of Behavioral Changes of Short-Chain Fatty Acids in Sports Athletes under Exercise Loading","authors":"Aoi Ichikawa, Takahiro Takayama, Chihiro Kojima, Shumpei Fujie, Motoyuki Iemitsu, Koichi Inoue","doi":"10.1021/acs.analchem.4c05872","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05872","url":null,"abstract":"Short-chain fatty acids (SCFAs) have attracted considerable interest as potential biomarkers, therapeutic targets, and nutritional factors in athletic training. SCFAs are typically produced by the intestinal microbiome and exhibit various structural forms, including linear- and branched-chain types. In particular, branched-chain SCFAs have been associated with muscle metabolism during exercise loading. Consequently, accurate and efficient analytical methods are essential for identifying these biomarkers. Liquid chromatography–tandem mass spectrometry is a suitable and accurate technique for SCFA analysis; however, stable isotope calibrations are required for all analytes. Because of technological limitations, the available species are restricted to certain types of SCFAs. To address this issue, this study performed a simple conversion reaction involving the incorporation of ¹⁸O into the carboxyl group. Specifically, oxygen atoms in the carboxyl groups were substituted with ¹⁸O sourced from commercially available H₂¹⁸O. An SCFA mixture standard solution was successfully labeled under optimized conditions, and the SIL purity and amount were sufficient for isotope dilution (95.2–96.9%, 250 assays using 10 μL of H₂¹⁸O). Moreover, no reversion to ¹⁶O was observed during storage or analysis. Analytical validation was performed in human serum using the substituted isotopic standard mixture, achieving good accuracy (90–110%) and precision (&lt;10% relative standard deviation) across three concentration levels. Finally, changes in SCFA patterns were examined in athletes during exercise loading.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"23 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776141","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}