Analytical and Bioanalytical Chemistry最新文献

{"title":"Sterol analysis in cancer cells using atmospheric pressure ionization techniques.","authors":"Pia Wittenhofer, Juan F Ayala-Cabrera, Laila Orell, Florian Uteschil, Sven W Meckelmann, Oliver J Schmitz","doi":"10.1007/s00216-025-06126-1","DOIUrl":"https://doi.org/10.1007/s00216-025-06126-1","url":null,"abstract":"<p><p>The analysis of sterol biosynthesis poses analytical challenges such as vast concentration differences between precursor molecules and cholesterol as well as the substantial interferences between the sterols and the matrix, resulting in strong ion suppression. LC-MS and 2D-LC-MS may address some of these challenges, but for sensitive and robust detection, ionization plays a key role. Electrospray ionization (ESI) stands out for its capability to generate ions from polar and nonpolar compounds, rendering it suitable for a broad spectrum of analytes, including sterols. Atmospheric pressure chemical ionization (APCI) demonstrates efficacy for compounds exhibiting moderate to low polarity, thereby facilitating efficient ionization of sterols. Tube plasma ionization (TPI) is a relatively new technique that promises sensitive ionization across a wide polarity range, indicating its potential utility for sterol analysis. Here, a new tube plasma ion source for LC-MS was developed and compared with established ion sources (ESI and APCI) for sterol analysis. The TPI source showed comparable LOQs to APCI and clearly outperformed ESI in terms of sensitivity. Both TPI and APCI provided stable signals during extended measurement series, while ESI suffered from pronounced ion suppression. Application to human plasma, HepG2 cells, and liver tissue demonstrated that TPI provided results in close agreement with APCI, highlighting its robustness for sterol quantification in complex biological matrices.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145205266","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Next-generation protein sequencing and individual ion mass spectrometry enable complementary analysis of interleukin-6.","authors":"Kenneth A Skinner, Troy D Fisher, Andrew Lee, Taojunfeng Su, Eleonora Forte, Aniel Sanchez, Michael A Caldwell, Neil L Kelleher","doi":"10.1007/s00216-025-06120-7","DOIUrl":"https://doi.org/10.1007/s00216-025-06120-7","url":null,"abstract":"<p><p>The vast complexity of the proteome currently overwhelms any single analytical technology in capturing the full spectrum of proteoform diversity. In this study, we evaluated the complementarity of two cutting-edge proteomic technologies-single-molecule protein sequencing and individual ion mass spectrometry-for analyzing recombinant human IL-6 (rhIL-6) at the amino acid, peptide, and intact proteoform levels. For single-molecule protein sequencing, we employed the recently released Platinum instrument. Next-generation protein sequencing (NGPS) on Platinum utilizes cycles of N-terminal amino acid recognizer binding and aminopeptidase cleavage to enable parallelized sequencing of single peptide molecules. We found that NGPS produces single amino acid coverage of multiple key regions of IL-6, including two peptides within helices A and C, which harbor residues that reportedly impact IL-6 function. For top-down proteoform evaluation, we used individual ion mass spectrometry (I²MS), a highly parallelized Orbitrap-based charge detection MS platform. Single ion detection of gas-phase fragmentation products (I²MS²) gives significant sequence coverage in key regions of IL-6, including two regions within helices B and D that are involved in IL-6 signaling. Together, these complementary technologies delivered a combined 52% sequence coverage, offering a more complete view of IL-6 structural and functional diversity than either technology alone. This study highlights the complementarity of these protein detection methods to cover protein segments relevant to biological interactions more comprehensively.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145197753","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Glycoproteomics analysis of colorectal cancer reveals differential alterations of glycoproteins and glycans.","authors":"Wenqi Zhang, Xiaotong Wang, Shengye Wen, Wei Ge, Jianbo Deng, Zeyang Zhou, Junhong Jiang, Xiaodong Yang, Yan Wang, Shuang Yang","doi":"10.1007/s00216-025-06108-3","DOIUrl":"https://doi.org/10.1007/s00216-025-06108-3","url":null,"abstract":"<p><p>Colorectal cancer (CRC) remains a global health concern, with an urgent need for better early detection and targeted therapies. Our glycoproteomics analysis comparing CRC to paracancerous (PCA) tissue revealed significant alterations. Global proteomic analysis showed more unique proteins in CRC, with differential expression across CRC stages, especially in protein synthesis, translation, and degradation pathways. Despite overall proteomic differences, intact glycopeptide analysis showed high glycosylation similarity between CRC and PCA, with 722 shared glycosites, 2102 shared glycopeptides, and 435 shared glycoproteins. However, a significant shift in CRC's N-glycan composition was observed: an upregulation of high-mannose N-glycans and a decrease in complex N-glycans, including sialoglycans and fucosylated sialoglycans. While glycosylation motif analysis showed conserved peptide sequences, the attached N-glycan types differed remarkably. KEGG pathway analysis suggested that extracellular matrix and lysosomal glycoproteins like COL1A1 and LAMP1 might modulate the PI3K/Akt signaling pathway via TGFβ1-mediated mechanisms, potentially contributing to tumor progression. These findings suggest that while global protein expression changes significantly in CRC, subtle but crucial changes in N-glycan composition, specifically the increase of high-mannose N-glycans and the decrease of complex N-glycans, may play a significant role in tumor progression and metastasis, potentially through modulation of key signaling pathways.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145197733","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tetracycline detection via carbon dots-Fe coordination from Chromolaena odorata using a portable device.","authors":"Nguyen Huynh Dang Khoa, Nguyen Ngoc Nghia, Bui The Huy, Dang Thanh Cong Minh, Tran Nguyen Cam Nhung, Tran Dang Khoa, Hoang Cao Nguyen, Huynh Anh Khoa, Nguyen Tran Nhat Trung, Nguyen Thi Kim Phuong, Nguyen Huu Hieu","doi":"10.1007/s00216-025-06125-2","DOIUrl":"https://doi.org/10.1007/s00216-025-06125-2","url":null,"abstract":"<p><p>Tetracycline residues in aquatic ecosystems, resulting from widespread antibiotic use, pose significant risks by fostering antibiotic resistance and threatening ecological and human health. Addressing the need for rapid, sensitive, and portable tetracycline detection, this study presents a novel device utilizing iron-coordinated carbon dots (CDs-Fe) derived from Chromolaena odorata as a peroxidase-mimic nanozyme. Synthesized via a one-step hydrothermal method, the CDs-Fe nanozyme exhibits enhanced catalytic activity, enabling a colorimetric assay with 3,3',5,5'-tetramethylbenzidine (TMB) and hydrogen peroxide (H₂O₂). Tetracycline detection relies on the nanozyme's peroxidase-like activity, where tetracycline competitively inhibits TMB oxidation, reducing the absorbance at 652 nm due to surface adhesion and substrate competition. The assay achieves a detection limit of 1.34 μM and a linear range of 17 to 67 μM. A portable Arduino-based device, fabricated via 3D printing with smartphone-enabled Bluetooth data reading, was developed for on-site tetracycline monitoring in real water samples, showing recoveries of 95 to 102% and high selectivity against other antibiotics. Validated against UV-vis spectrophotometry, this green-synthesized, cost-effective system offers a sustainable and field-deployable solution for environmental water quality assessment.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145197738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Resolving agrochemical penetration in wheat leaves with secondary ion mass spectrometry imaging and depth profiling.","authors":"Akhila Ajith, Sadia Sheraz, Aline Xavier de Souza, Drupad K Trivedi, Jean-Yves Mugnier, Giles N Johnson, Phillip J Milnes, Nicholas P Lockyer","doi":"10.1007/s00216-025-06134-1","DOIUrl":"https://doi.org/10.1007/s00216-025-06134-1","url":null,"abstract":"<p><p>The foliar application of an agrochemical is first encountered by the hydrophobic cuticle and then the hydrophilic epidermis of the leaf. Understanding the movement and distribution of pesticides through these layers is vital in the research and development process of agrochemicals. Currently, no technique provides conclusive answers on active ingredient penetration through the leaf surface layers without chemical or physical treatment of the leaves. The advancements in modern time-of-flight secondary ion mass spectrometry (ToF-SIMS) technologies provide the necessary depth, spatial, and mass resolution to probe this complex area of interest with precision and relatively simple sample preparation. In this work, we describe a systematic ToF-SIMS workflow to comprehensively understand the foliar movement of an applied agrochemical through the surface waxes and in the bulk of the leaf. A combination of depth profiling experiments along with cross-section imaging of agrochemical-applied wheat leaves was used to better understand the mobility of a fungicide, azoxystrobin, in young wheat leaves. Extensive testing was done to optimise the analytical conditions and sample preparation strategies best suited for the experiments described in this work. A gas cluster ion beam composed of water clusters was selected for analysis. Freeze-dried leaves were used for depth profile experiments, while tape-sectioned leaf cross-sections were used for imaging. Parallel leaf sections to those taken for ToF-SIMS were also imaged with matrix-assisted laser desorption ionisation mass spectrometry imaging (MALDI-MSI). When applied, azoxystrobin moved rapidly across the leaf cross-section, being observed in the leaves as early as 24 h after application and persisting for 1 week. When comparing the intensity in the mesophyll region to that of the vascular bundle, more azoxystrobin content was observed in the mesophyll at both time points, with greater disparity observed at 1 week. The results obtained were corroborated with the MALDI study done on similar samples and with pre-existing literature.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145197736","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Correction to: Development and validation of an isotope dilution-liquid chromatography-tandem mass spectrometry (ID-LC-MS/MS)-based candidate reference measurement procedure for total 3,3',5-Triiodothyronine in human serum.","authors":"Wenya Li, Bingling Gao, Tao Yang, Liping Tang, Dan Song, Hongmei Li, Keqi Sun, Peng Xiao","doi":"10.1007/s00216-025-06142-1","DOIUrl":"https://doi.org/10.1007/s00216-025-06142-1","url":null,"abstract":"","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145184503","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Demonstrating voxel-by-voxel (V × V) single-point calibration in liver tissue by IR-MALDESI quantitative MSI.","authors":"Emily R Bruce, Russell R Kibbe, Logan J Opperman, David C Muddiman","doi":"10.1007/s00216-025-06138-x","DOIUrl":"https://doi.org/10.1007/s00216-025-06138-x","url":null,"abstract":"<p><p>Quantitative mass spectrometry imaging (qMSI) provides information regarding the colocalization, relative abundance, and concentration of a target analyte in a tissue without homogenization. Ionization sources, including IR-MALDESI, commonly utilize an on-tissue spatial calibration curve approach; however, this approach has several limitations including tedious sample preparation, and this approach does not account for local matrix effects. To compensate for these two limitations, we developed voxel-by-voxel (V × V) quantification to provide an internal standard calibration point for every voxel which requires a simple sample preparation and accounts for local matrix effects. In this work, we evaluate the performance of V × V quantification against the spatial calibration curve to assess the quantitative capacity of this newly developed method. Quantification of glutathione (GSH) on a per-voxel basis involves homogenously spraying a known amount of stable isotope-labeled glutathione (SIL-GSH) on a microscope slide. Next, we mount liver sections on top of the coated slides and image them using IR-MALDESI MSI. Statistical analysis demonstrated high precision for V × V quantification over a wide concentration range; however, the method's accuracy is currently limited due to the sprayer's configuration. Results support the feasibility of V × V quantification as evidenced by concentration heatmaps. Additionally, V × V quantification allows for parallel reaction monitoring (PRM) imaging which provides high specificity. Combined with relativity, straightforward sample preparation, and promising initial statistics, the V × V method offers significant advantages over spatial calibration curves.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145184469","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Anti-interference labeled SERS lateral flow immunoassay based on Prussian blue for ultra-sensitive quantitative detection of bloodstains in forensic field.","authors":"Long Chen, Feng Wang, Ziwen Guo, Tianyu Qiu, Feng Chen, Yue Cao","doi":"10.1007/s00216-025-06128-z","DOIUrl":"https://doi.org/10.1007/s00216-025-06128-z","url":null,"abstract":"<p><p>In the field investigation of criminal cases, the tracking of blood evidence is very important. However, post-crime bloodstains are often cleaned up or covered up, making residual traces difficult to detect. Consequently, the creation of expeditious, exceptionally precise, and selective analytical techniques for human bloodstain recognition is imperative. Prussian blue (PB) served as a surface-enhanced Raman scattering (SERS) tag in this research, characterized by an intense monochromatic signal in the biological silent region (1800-2800 cm^-1), while endogenous biomolecules had no Raman signal in this region. This feature allows the PB signal to be completely separated from the biological background, without the need for complex spectral analysis, and perfectly adapts to complex forensic field requirements. Based on this, we constructed a Prussian blue-modified anti-interference SERS lateral flow immunoassay strip (SERS-LFIA) for highly sensitive and rapid detection of blood evidence. The visual detection Limit of the test strip for human hemoglobin was 100 ng/mL (equivalent to the commercially available colloidal gold test strip), showing a good Linear response in the range of 1.00 ng/mL to 100 μg/mL (R² = 0.950), and the SERS detection threshold was as low as 1.00 ng/mL. The results suggest that Au@PB nanoparticles (Au@PB NPs) SERS-LFIA can be used as an effective detection method for on-site bloodstains, and is suitable for long-term preservation and traceability analysis of physical evidence.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145184477","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Characterization of rare trifucosylated human milk oligosaccharides by cryogenic infrared ion spectroscopy (CIRIS).","authors":"Ali H Abikhodr, Stephan Warnke, Ahmed Ben Faleh, Thomas R Rizzo, Sibel Goeraler, John Gonsalves, Bernd Stahl, Marko Mank","doi":"10.1007/s00216-025-06114-5","DOIUrl":"https://doi.org/10.1007/s00216-025-06114-5","url":null,"abstract":"<p><p>While approximately 200 human milk oligosaccharide structures (HMOs) have been completely characterized, the precise isomeric structures of even more HMOs remain ambiguous. To address this analytical challenge, we employ tandem mass spectrometry (i.e., MS/MS) coupled with cryogenic infrared ion spectroscopy (CIRIS) to characterize and identify novel fucosylated HMOs isolated from pooled human milk. In this approach, the precise structure of isomeric precursor molecules purified by liquid chromatography (LC) is identified by IR fingerprinting their fragments. Using this technique, we have identified four novel isomers of trifucosylated oligosaccharides (i.e., trifucosyl-lacto-N-heptaoses and trifucosyl-lacto-N-neoheptaoses), some of which could not have been produced by previously known biosynthetic pathways for HMO synthesis in the mammary gland.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145147405","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dual-organelle localizing fluorescent probe for selective hydrogen sulfide imaging in mitochondria and lysosomes.","authors":"Wen-Yu Lu, Ming-Yang Zhang, Xi-Xi Wu, Xing-Yuan Bing, Hui-Jing Li, Yan-Chao Wu","doi":"10.1007/s00216-025-06121-6","DOIUrl":"https://doi.org/10.1007/s00216-025-06121-6","url":null,"abstract":"<p><p>Hydrogen sulfide (H₂S) is a crucial gaseous signaling molecule implicated in a wide range of physiological and pathological processes. Accordingly, a fluorescent probe (INS) has been designed and synthesized for selective detection of H₂S in living cells. Notably, H₂S triggers a specific nucleophilic reaction with INS, distinguishing it from other potential interfering analytes and conferring exceptional selectivity. The probe exhibits a pronounced fluorescence enhancement upon reaction with H₂S. Owing to its remarkable properties-including full water solubility, a low detection limit of 30.1 nM, excellent specificity, a large Stokes shift of 130 nm, a strong linear fluorescence response, and stable emission over a broad pH range (pH 5-12)-INS is ideally suited for the detection of H₂S in complex biological samples. Cellular imaging experiments further demonstrate that INS possesses high-contrast imaging capabilities and excellent membrane permeability, enabling effective visualization of intracellular H₂S. Moreover, INS displays organelle-targeting properties, with the ability to localize selectively to both lysosomes and mitochondria. Taken together, these outstanding features position INS as a promising and versatile fluorescent probe for sensitive and selective detection of H₂S in living cells.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145136013","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}