{"title":"Sensitive determination of volatile nitrosamines with ambient pressure ammonium-adduct ionization mass spectrometry.","authors":"Lian Duan, Cheng Wang, Yuwei Li, Binwang Yang, Xiuqing Zheng, Jiaxu Liu, Guoxing Jing, Wenjie Liu, Jianna Yu","doi":"10.1007/s00216-024-05580-7","DOIUrl":"10.1007/s00216-024-05580-7","url":null,"abstract":"<p><p>In recent years, the control of volatile N-nitrosamines (NAs) has been of interest in the pharmaceutical and food industries, as many of these compounds are probable human carcinogens. Thus, rapid and trace-level quantitative determination methods are in urgent demand. In this work, ambient pressure ammonium-adduct ionization mass spectrometry was proposed for the sensitive detection of volatile nitrosamines in various pharmaceutical headspaces. The ammonium ions produced through electrospray ionization acted as reactant ions for NAs to generate ammonium-NA adduct ions and underwent in-source collision-induced dissociation to produce protonated NAs, which were detected by mass spectrometry. The ionization selectivity and sensitivity for various volatile NAs were improved significantly using the developed method, which was demonstrated by the limit of quantification (LOQ) below 52 ng L<sup>-1</sup> for all NAs, and the quantitative performance was consequently improved. Different NAs exhibited almost equimolar response using NH<sub>4</sub><sup>+</sup> as the reactant ion, with at least a twofold enhancement in intensity for the individual compounds relative to when using H<sup>+</sup> as the reactant ion. The proposed method is a rapid, sensitive, and environmentally economical approach that uses few reagents.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"6839-6847"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142455215","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}
Qingshan Zhong, Lei Shao, Yudong Yao, Shuo Chen, Xiuyi Lv, Zhihan Liu, Shanshan Zhu, Zejun Yan
{"title":"Urine-based SERS and multivariate statistical analysis for identification of non-muscle-invasive bladder cancer and muscle-invasive bladder cancer.","authors":"Qingshan Zhong, Lei Shao, Yudong Yao, Shuo Chen, Xiuyi Lv, Zhihan Liu, Shanshan Zhu, Zejun Yan","doi":"10.1007/s00216-024-05595-0","DOIUrl":"10.1007/s00216-024-05595-0","url":null,"abstract":"<p><p>Bladder cancer (BC) is an epidemiological urologic malignancy that continues to increase each year. Early diagnosis and prognosis monitoring is always significant in clinical practice, especially in distinguishing non-muscle-invasive bladder cancer (NMIBC) from muscle-invasive bladder cancer (MIBC), due to the various depths of tumor invasion related to different therapeutic schedules and recurrence rates. Common diagnostic approaches are too invasive or generally inefficient in accuracy and specificity. In this work, a totally non-invasive and cost-effective method is established by investigating urine samples using surface-enhanced Raman spectroscopy (SERS) and multivariate statistical analysis. The comparison of urine SERS spectra shows the intensities of characteristic peaks for DNA/RNA, hypoxanthine, albumin, D-( +)-galactosamine, fatty acids, and some amino acids are distinguishable in BC occurrence and invasion progression. A PLS-LDA-based two-step binary classification scheme is performed on urine SERS spectra and the diagnostic accuracies were 97.7% and 96.3% for healthy individuals versus BC patients and NMIBC versus MIBC patients, respectively. Moreover, the impact of urine SERS spectral lengths in reaching high-precision recognition of BC is investigated. The results show that the Raman peaks at 803, 893, 1139, 1375, and 1466 cm<sup>-1</sup> play an essential role in correctly categorizing healthy control, NMIBC, and MIBC patients, and SERS spectra ranges from 400 to 1600 cm<sup>-1</sup> are enough for this identification task. These findings provide a sensitive, label-free, rapid, and totally non-invasive way for assessment of invasion depth of BC to its early diagnosis and prognosis monitoring, as well as valuable insights for selecting reasonable spectral range to enhance the measurement efficiency especially in large-scale sample datasets.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"6973-6984"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142455221","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}
Wen-Ya Liu, Di Xu, Hui-Hui Meng, Cheng-Yao Wang, Xin Feng, Jun-Song Wang
{"title":"Metabolic fate of the natural anticancer agent cucurbitacin B: an LC-MS/MS-enabled profiling of its major phase I and II conjugates in vivo.","authors":"Wen-Ya Liu, Di Xu, Hui-Hui Meng, Cheng-Yao Wang, Xin Feng, Jun-Song Wang","doi":"10.1007/s00216-024-05608-y","DOIUrl":"10.1007/s00216-024-05608-y","url":null,"abstract":"<p><p>Cucurbitacin B (CuB) is a natural triterpenoid with diverse pharmacological effects including potent anticancer activity. However, its oral bioavailability is hampered by limited metabolism in vivo. We characterized CuB's in vivo metabolism in rats to uncover bioactive metabolites retaining therapeutic potential, using a robust UHPLC-Q-TOF-MS/MS workflow. This workflow combined molecular networking, fragmentation filtering, and mass defect filtering to identify CuB metabolites in rat urine, plasma, and feces following oral administration. Thirteen metabolites were identified and seven were confirmed. Major phase I transformations involved hydrolysis, reduction, epoxidation, and amination. Phase II conjugation included cysteine, glutathione, glucuronide, and gluconic acid conjugates. Notably, one of the main metabolites formed was the cysteine conjugate CuB-Cys. CuB-Cys maintained similar in vitro antiproliferative activity to CuB on HepG2, MCF-7, and PANC-1 cancer cell lines. However, it demonstrated lower cytotoxicity towards non-cancerous L02 cells, highlighting improved therapeutic selectivity. Mechanistically, CuB-Cys induced greater apoptotic signaling in HepG2 cells than CuB via enhanced caspase activation and disrupted BAX-Bcl-2 balance. This represents the first systematic characterization of CuB's in vivo metabolic pathway. The identification and confirmation of CuB-Cys provide insight for drug development efforts aiming to maintain therapeutic efficacy while reducing toxicity, via metabolite-based approaches. Our findings shed light on strategies for improving CuB's clinical potential.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"7043-7062"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142492489","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}
Andaravaas Patabadige Jude P Vaas, Raymond B Yu, Joselito P Quirino
{"title":"Stacking in electrophoresis by electroosmotic flow-assisted admicelle to solvent microextraction.","authors":"Andaravaas Patabadige Jude P Vaas, Raymond B Yu, Joselito P Quirino","doi":"10.1007/s00216-024-05554-9","DOIUrl":"10.1007/s00216-024-05554-9","url":null,"abstract":"<p><p>An in-line sample concentration method for capillary electrophoresis called admicelle to solvent microextraction was proposed. In this technique, analytes were trapped in the cetyltrimethylammonium bromide admicelles formed in situ on the negatively charged capillary surface. A solvent plug was then partially injected hydrodynamically to collapse the admicelles, which liberated and focused the analytes at the solvent front. Voltage was applied across the capillary, completing the stacking process. Various solvents, namely, methanol, ethanol, and acetonitrile, were investigated. The optimal solvent for solvent to admicelle microextraction was 30% acetonitrile in 24 mM sodium tetraborate (pH 9.2). Sample injection time and solvent to sample injection ratio were also optimised. For this demonstration, the optimum sample injection time and solvent to sample injection ratio were 320 s and 1:2, respectively. Using the optimum conditions, UV detection sensitivity was enhanced 132-176-fold for the model anions. The LOQ, %intra-/inter-day (n = 6/n = 12, 2 days) repeatability, and linearity (R<sup>2</sup>) of admicelle to solvent microextraction were 0.08-2 µg/mL, 1.9-3.9%, 2.8-4.9%, and 0.992, respectively. Admicelle to solvent microextraction was applied to the analysis of various fortified water samples, with good repeatability (%RSD = 0.5-3.6%), and no matrix interferences.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"6789-6798"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142363899","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}
Haojie Hu, Chen He, Di Zhu, Weilai Zhang, Xiaocun Zhuo, Yuguo Li, Quan Shi
{"title":"Revealing the backbone structures of land-based fulvic acids derived from river and soil through n-butylsilane reduction.","authors":"Haojie Hu, Chen He, Di Zhu, Weilai Zhang, Xiaocun Zhuo, Yuguo Li, Quan Shi","doi":"10.1007/s00216-024-05589-y","DOIUrl":"10.1007/s00216-024-05589-y","url":null,"abstract":"<p><p>While ultra-high-resolution mass spectrometry has enabled the identification of the molecular composition of dissolved organic matter (DOM), elucidating its molecular structure remains a challenging endeavor. Here, two fulvic acids (FAs), one from river and the other from forest soil, were subjected to reduction using an optimized n-butylsilane (n-BS) reduction method. The reduction products were purified through a combination of liquid-liquid extraction and silica gel column chromatography, resulting in the separation into saturates, aromatics, and polar products. The polar products were analyzed by high-resolution mass spectrometry (HRMS), and the saturates and aromatics were analyzed using gas chromatography-mass spectrometry (GC-MS). HRMS results showed that the number of oxygen atoms and double-bond equivalent (DBE) values of FA decreased after reduction. GC-MS results revealed that a total of 270 hydrocarbon monomers were identified from the reduction products of a single sample, with the highest carbon number of cycloalkanes reaching C<sub>33</sub>. For the first time, steranes and hopanes were detected in the reduction products, potentially serving as evidence for the existence of carboxyl-rich alicyclic molecule (CRAM) precursors. Additionally, a significant number of polycyclic aromatic hydrocarbons were identified, and the potential sources of various compounds were preliminarily inferred based on their isomers. This study extends the knowledge of the possible backbone structure of the DOM and provides a new potential tool for investigating the origin and transformation mechanisms of DOM.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"6919-6929"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398950","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}
Luisa Speicher, Hao Song, Norman Ahlmann, Daniel Foest, Simon Höving, Sebastian Brandt, Guanghui Niu, Joachim Franzke, Caiyan Tian
{"title":"Correction to: Soft ionization mechanisms in flexible μ‑tube plasma-from FμTP to closed μ‑tube plasma.","authors":"Luisa Speicher, Hao Song, Norman Ahlmann, Daniel Foest, Simon Höving, Sebastian Brandt, Guanghui Niu, Joachim Franzke, Caiyan Tian","doi":"10.1007/s00216-024-05621-1","DOIUrl":"10.1007/s00216-024-05621-1","url":null,"abstract":"","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"7191"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142492485","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":"Development and application of a dual isotopic labeling method for enhanced detection and quantification of stimulants in urine samples using high-resolution mass spectrometry.","authors":"Yang Wang, Wanli Li, Xiaojun Deng","doi":"10.1007/s00216-024-05612-2","DOIUrl":"10.1007/s00216-024-05612-2","url":null,"abstract":"<p><p>Given the critical nature of anti-doping efforts, the detection of stimulant substances is shifting from accurate qualitative analysis to precise quantitative analysis. Additionally, the use of liquid chromatography-high-resolution mass spectrometry (LC-HRMS) in detecting stimulants is becoming more widespread. However, the lack of isotope-labeled internal standards is causing increasing issues with quantitative accuracy. Furthermore, challenges such as the mass spectrometric response of small molecules and the separation of isomers present additional difficulties. We have developed a quantitative method for stimulant substances containing amine or phenol hydroxyl groups, using a dual-label derivatization system. This method offers a new perspective for analyzing and detecting low molecular weight substances, isomers, or those with poor LC-MS response, and proposes a solution to the problem of missing isotope-labeled internal standards. Methodological validation has shown that this approach has promising application potential.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"7073-7084"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142492486","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}
Qiaofang Yan, Fei Huang, Chuyang Wang, Min Zhan, Qiaoxuan Zhang, Di Huang, Jun Yan, Haibiao Lin, Xianzhang Huang, Liqiao Han
{"title":"Clinical application of an optimized reference measurement procedure for serum digoxin using bracketing calibration method by ID-LC-MS/MS.","authors":"Qiaofang Yan, Fei Huang, Chuyang Wang, Min Zhan, Qiaoxuan Zhang, Di Huang, Jun Yan, Haibiao Lin, Xianzhang Huang, Liqiao Han","doi":"10.1007/s00216-024-05587-0","DOIUrl":"10.1007/s00216-024-05587-0","url":null,"abstract":"<p><p>Digoxin, a cardiac glycoside, is widely used in the treatment of cardiovascular diseases. Due to its narrow therapeutic range, precise monitoring of its blood concentration is essential. A reference measurement procedure (RMP) is pivotal for ensuring result accuracy and comparability. The RMP for serum digoxin by ID-LC-MS/MS was optimized with sample pre-treatment and detection processes, and the bracketing calibration method was used, which facilitates more accurate measurement, especially for extreme concentrations. The performance of this optimized RMP was thoroughly evaluated. The limit of detection (LoD) was 0.05 ng/mL (0.06 nmol/L) and the lowest limit of quantification (LLoQ) was 0.10 ng/mL (0.13 nmol/L). The intra- and inter-assay imprecisions were 2.24%, 2.51%, 1.40% and 1.72%, 1.65%, 0.97% at 0.5, 2.0, 5.0 ng/mL, respectively. Recoveries were 99.63 to 101.42% and the linear response ranged from 0.1 to 10.0 ng/mL. The relative bias was 0.41% and 2.00% of our results compared with the median of all participating reference laboratories for IFCC-RELA (External Quality Assessment Scheme for Reference Laboratories in Laboratory Medicine) 2023A and 2023B. The uncertainty, calibration and measurement capability (CMC) of this method were also evaluated. The optimized RMP was applied in the Trueness Verification Plan of Southern China, which indicates significant differences among clinical systems, highlighting the need for standardization efforts. In addition, two commonly used clinical systems which employed immunoassay methods were compared with this optimized RMP, and 26 individual serum samples were analyzed. The good correlations indicate the feasibility of standardization for serum digoxin. The optimized RMP serves as an accurate reference baseline for routine methods, aiming to enhance the accuracy and precision of measurements in clinical laboratories.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"6909-6918"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142387028","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":"Enzyme-free immunoassay for rapid, sensitive, and selective detection of C-reactive protein.","authors":"Sathishkumar Munusamy, Haiyan Zheng, Rana Jahani, Shuo Zhou, Jun Chen, Juanhua Kong, Xiyun Guan","doi":"10.1007/s00216-024-05598-x","DOIUrl":"10.1007/s00216-024-05598-x","url":null,"abstract":"<p><p>C-reactive protein (CRP) is a protein made by the liver, which is released into the bloodstream in response to inflammation. Furthermore, CRP is a potential risk factor for heart disease. Hence, it is of great importance to develop a rapid, sensitive, accurate, and cost-effective method for CRP detection. Herein, we report an enzyme-free fluorescent assay for the rapid and ultra-sensitive detection of CRP with a limit of detection (LOD) reaching as low as 3.08 pg/mL (i.e., ~ 27 fM). The high sensitivity of our method was simply achieved via dual-functionalized gold nanoparticles (AuNPs). By regulating the molar ratio of DNA to CRP antibody immobilized on the AuNP surface, hundreds to thousands-fold amplification in the analyte signal could be instantly accomplished. Furthermore, our sensor was selective: non-target proteins such as interleukin-6, interleukin-1β, procalcitonin, bovine serum albumin, and human serum albumin did not interfere with the target CRP detection. Moreover, simulated serum samples were successfully analyzed. Given the excellent sensitivity, selectivity, and high resistance to complicated matrices, the enzyme-free CRP detection strategy developed in this work can be used as a generic platform to construct sensors for a wide variety of protein biomarkers and hence offers potential as a tool for rapid, accurate, and low-cost medical diagnosis.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"6985-6994"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142455201","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}
Claire Davison, Jordan Pascoe, Melanie Bailey, Dany J V Beste, Mónica Felipe-Sotelo
{"title":"Single cell-inductively coupled plasma-mass spectrometry (SC-ICP-MS) reveals metallic heterogeneity in a macrophage model of infectious diseases.","authors":"Claire Davison, Jordan Pascoe, Melanie Bailey, Dany J V Beste, Mónica Felipe-Sotelo","doi":"10.1007/s00216-024-05592-3","DOIUrl":"10.1007/s00216-024-05592-3","url":null,"abstract":"<p><p>Single cell-inductively coupled plasma-mass spectrometry (SC-ICP-MS) offers an attractive option for rapidly measuring trace metal heterogeneity at the single cell level. Chemical fixation has been previously applied to mammalian cells prior to sample introduction so that they can be resuspended in a solution suitable for SC-ICP-MS. However, the effect of fixation on the elemental composition of suspended cells is unknown, and robust methodologies are urgently needed so that the community can measure the effects of intracellular pathogens on elemental composition of their host cells. We demonstrate that different fixatives impact measured cell elemental composition. We have compared suspensions treated using different fixatives (methanol 60-100% in H<sub>2</sub>O and 4% paraformaldehyde in phosphate-buffered saline solution), and the number of distinguishable single cell events, keeping a constant particle number concentration. Significantly more single cell events (n = 3, P ≤ 0.05) were observed for Ca and Mg when cells were fixed in 4% paraformaldehyde than for the methanol-based fixatives, confirming the hypothesis that methanol fixatives cause leaching of these elements from the cells. The impact of fixation on Mn and Zn was less pronounced. Microbial and viral infection of eukaryotic cells can have profound effects on their elemental composition, but chemical fixation is necessary to render infected cells safe before analysis. We have successfully applied our methodology to a macrophage model of tuberculosis demonstrating utility in understanding metal homeostasis during microbial infection of mammalian cells.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"6945-6955"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142455218","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}