Analytical and Bioanalytical Chemistry最新文献

{"title":"Quantification of deoxythioguanosine in human DNA with LC-MS/MS, a marker for thiopurine therapy optimisation.","authors":"Björn Carlsson, Louise Karlsson, Andreas Ärlemalm, Sophie Sund, Malin Lindqvist Appell","doi":"10.1007/s00216-024-05581-6","DOIUrl":"10.1007/s00216-024-05581-6","url":null,"abstract":"<p><p>In the treatment of diseases such as acute childhood leukaemia (ALL) and inflammatory bowel disease (IBD), the thiopurines azathioprine, 6-mercaptopurine, and 6-thioguanine are used. Thiopurines are antimetabolites and immunomodulators used to maintain remission in patients. They are all prodrugs and must be converted into the competing antimetabolites thioguanosine triphosphate and deoxythioguanosine triphosphate for final incorporation into RNA or DNA. The current therapeutic drug monitoring (TDM) method measures the sum of the formed metabolites in the sample, after acidic hydrolysis at high temperature. In this work, the goal is to measure these drugs closer to their pharmacological endpoints, once incorporated into DNA. After extracting DNA from whole blood, followed by DNA hydrolysis, 2'-deoxythioguanosine (dTG) and the complementary natural nucleobase 2'-deoxycytidine (dC) were measured. Chromatographic separation on a HSS T3 column followed by mass spectrometric detection was performed in multi-reaction monitoring (MRM) mode on a Xevo TQ-XS with ESI in positive mode, within 5 min. The concentration range for dTG was 0.04-5 nmol/L, and for dC, 0.1-12.5 µmol/L. The lower limit of detection was determined to a concentration of 0.003 nmol/L for dTG and 0.019 µmol/L for dC. The intra- and inter-assay imprecision for the quality controls ranged between 3.0 and 5.1% and between 8.4 and 10.9%, respectively. Sample stability for up to 4 years is shown. In summary, a sensitive method to quantify the thiopurines incorporated into DNA as dTG has been developed and will be used in further clinical studies for a better understanding of the mode of action of the thiopurines and the use of this method in TDM.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"6711-6723"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11579148/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142455211","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Simple and robust high-throughput serum proteomics workflow with low-microflow LC-MS/MS.","authors":"Yoondam Seo, Inseon Kang, Hyeon-Jeong Lee, Jiin Hwang, Soo Heon Kwak, Min-Kyu Oh, Hyunbeom Lee, Hophil Min","doi":"10.1007/s00216-024-05603-3","DOIUrl":"10.1007/s00216-024-05603-3","url":null,"abstract":"<p><p>Clinical proteomics has substantially advanced in identifying and quantifying proteins from biofluids, such as blood, contributing to the discovery of biomarkers. The throughput and reproducibility of serum proteomics for large-scale clinical sample analyses require improvements. High-throughput analysis typically relies on automated equipment, which can be costly and has limited accessibility. In this study, we present a rapid, high-throughput workflow low-microflow LC-MS/MS method without automation. This workflow was optimized to minimize the preparation time and costs by omitting the depletion and desalting steps. The developed method was applied to data-independent acquisition (DIA) analysis of 235 samples, and it consistently yielded approximately 6000 peptides and 600 protein groups, including 33 FDA-approved biomarkers. Our results demonstrate that an 18-min DIA high-throughput workflow, assessed through intermittently collected quality control samples, ensures reproducibility and stability even with 2 µL of serum. It was successfully used to analyze serum samples from patients with diabetes having chronic kidney disease (CKD), and could identify five dysregulated proteins across various CKD stages.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"7007-7018"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11579186/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142455216","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Forty years of advances in optical biosensors-are \"autonomous\" biosensors in our future?","authors":"Frances S Ligler, George T Ligler","doi":"10.1007/s00216-024-05338-1","DOIUrl":"10.1007/s00216-024-05338-1","url":null,"abstract":"<p><p>Optical biosensors have employed at least three distinct system architectures over the last 40 years, moving from \"sample in-answer out\" systems to completely embedding the optical biosensor into the sample to embedding the recognition module in the sample and optically interrogating the recognition module from outside of the sample. This trends article provides an overview of the evolution of these three system architectures and discusses how each architecture has been applied to solve the measurement challenges of a wide variety of applications. A fourth biosensor system architecture, that of an \"autonomous\" biosensor which \"takes the user out of the loop\" while both detecting target analytes and responding to that measurement, is currently under development for applications initially including environmental cleanup and \"smart therapeutics.\" As is the case in many other areas of technology, it will be profoundly interesting to observe the further development and application of elegant, simpler (optical) biosensor systems to address tomorrow's measurement needs.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"7199-7203"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11584417/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141174594","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Facile biotic/abiotic sandwich detection system for the highly sensitive detection of human serum albumin and glycated albumin.","authors":"Hirobumi Sunayama, Chehasan Cheubong, Eri Takano, Toshifumi Takeuchi","doi":"10.1007/s00216-024-05403-9","DOIUrl":"10.1007/s00216-024-05403-9","url":null,"abstract":"<p><p>Quantifying glycated albumin (GA) levels in the blood is crucial for diagnosing diabetes because they strongly correlate with blood glucose concentration. In this study, a biotic/abiotic sandwich assay was developed for the facile, rapid, and susceptible detection of human serum albumin (HSA) and GA. The proposed sandwich detection system was assembled using a combination of two synthetic polymer receptors and natural antibodies. Molecularly imprinted polymer nanogels (MIP-NGs) for HSA (HSA-MIP-NGs) were used to mimic capture antibodies, whereas antibodies for HSA or GA were used as primary antibodies and fluorescent signaling MIP-NGs for the Fc domain of IgG (F-Fc-MIP-NGs) were used as a secondary antibody mimic to indicate the binding events. The HSA/anti-HSA/F-Fc-MIP-NGs complex, formed by incubating HSA and anti-HSA antibodies with F-Fc-MIP-NGs, was captured by HSA-MIP-NGs immobilized on the chips for fluorescence measurements. The analysis time was less than 30 min, and the limit of detection was 15 pM. After changing the anti-HSA to anti-GA (monoclonal antibody), the fluorescence response toward GA exceeded that of HSA, indicating successful GA detection using the proposed sandwich detection system. Therefore, the proposed system could change the detection property by changing a primary antibody, indicating that this system can be applied to various target proteins and, especially, be a powerful approach for facile and rapid analysis methods for proteins with structural similarity.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"7337-7345"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11584489/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141615514","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Influence of on-site sampling conditions on the representativeness of the sample for the analysis of trace VOCs in raw renewable gases.","authors":"A Legendre, S Bsaibes, C Paijens, J Dugay, Y Courtois, L Cuccia, D Ballestas Castro, D Thiebaut, J Vial","doi":"10.1007/s00216-024-05604-2","DOIUrl":"10.1007/s00216-024-05604-2","url":null,"abstract":"<p><p>In the context of the energy transition and in order to fully manage the integration of renewable and/or low-carbon gases into the gas mix, these new renewable gases need to be characterized, including volatile organic compounds (VOCs) at trace levels that may have an impact on different stages of the gas chain event at low concentrations. This study focuses on sampling because it is the first step in any method for analyzing trace VOCs and its careful execution is essential to ensure reliable results even if the on-site conditions can be variable, such as the external temperature. The stabilization time, the effect of external temperature, and the impact of using an intermediate sample cylinder prior to transfer to tubes were hence studied in the laboratory using a standard gas mixture representative of renewable gases. The latter was also studied using a real sample. To perform this study, VOCs were sampled in Tenax® TA tubes and then analyzed by thermal desorption hyphenated to comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry. The results showed that 45 min were required to stabilize the sampling system and that external temperature had little influence, limited to the heaviest compounds. Finally, the use of a cylinder to temporarily collect gas prior to transfer to tubes led to a loss of compounds, particularly when the cylinder was stored before the transfer.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"7019-7029"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142455204","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":"Visualizing the transdermal delivery of berberine loaded within chitosan microneedles using mass spectrometry imaging.","authors":"Xiaoqing Cui, Haoyuan Geng, Huanying Guo, Lei Wang, Zihan Zhu, Yaqi Zhang, Panpan Chen, Xiao Wang, Chenglong Sun","doi":"10.1007/s00216-024-05584-3","DOIUrl":"10.1007/s00216-024-05584-3","url":null,"abstract":"<p><p>Berberine (BR), an alkaloid isolated from the Chinese traditional medicine Coptidis rhizoma, exhibits therapeutic effects on several diseases including bacterial infections, diabetes, and hyperlipidemia, but the oral availability is poor. In this work, we prepared the chitosan microneedle array-loaded BR (BR-CS MNAs) to transdermally deliver BR, and the spatial distribution of BR in heterogeneous skin tissues was analyzed and imaged by matrix-assisted laser desorption ionization mass spectrometry imaging (MALDI-MSI). Some endogenous phospholipids with specific spatial distribution were used to differentiate the epidermis and dermis regions of the skin. The results showed that BR was effectively delivered and could permeate to both epidermis and dermis regions of the skin. This demonstrated the feasibility of MALDI-MSI to evaluate the transdermal delivery efficiency of microneedle arrays and suggested BR could be transdermally delivered by CS MNAs.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"6869-6877"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142455222","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":"Core-shell structures assembled from magnetic covalent organic frameworks as a Ti⁴⁺-fixed affinity substrate for the identification of phosphopeptides in colorectal cancer serum.","authors":"Jiakai Chen, Xinyue Zhou, Zhenzhen Cao, Bing Wang, Chuan-Fan Ding, Yinghua Yan","doi":"10.1007/s00216-024-05620-2","DOIUrl":"10.1007/s00216-024-05620-2","url":null,"abstract":"<p><p>When it comes to the early detection of colorectal cancer (CRC), the study of protein phosphorylation is crucial. This work used magnetic covalent organic framework (COF) materials as substrates. The magCOF@PM-Ti⁴⁺ composites were obtained by constructing the three-dimensional cross-linked structures and chelating them with Ti⁴⁺ in a green and economical way, which was utilized to identify the phosphopeptides. This material possesses magnetic properties that facilitate simplified experimental manipulation, has superior sensitivity (0.2 fmol), excellent selectivity (1000:1), and good reusability (10 cycles), and achieves outstanding recovery rates (103.4 ± 1.2%). In addition, magCOF@PM-Ti⁴⁺ was utilized to identify phosphopeptides in human serum. One hundred phosphopeptides were identified from three normal control serums, whereas 98 phosphopeptides were identified from three CRC serums. The results demonstrated that magCOF@PM-Ti⁴⁺ has great potential in efficiently identifying low-abundance phosphopeptides.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"7151-7159"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142520644","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":"Illustrate the metabolic regulatory mechanism of Taohong Siwu decoction in ischemic stroke by mass spectrometry imaging.","authors":"Xiaoqun Wang, Xueting Zhang, Jiayu Zhang, Hanxue Yang, Zhuqing Liu, Daiyin Peng, Lan Han","doi":"10.1007/s00216-024-05591-4","DOIUrl":"10.1007/s00216-024-05591-4","url":null,"abstract":"<p><p>Metabolic dysregulation in the ischemic region has been increasingly recognized as a contributing factor to ischemic stroke pathogenesis. Taohong Siwu decoction (THSWD), a traditional Chinese medicine preparation used to enhance blood circulation, is frequently employed in treating ischemic stroke. However, the metabolic regulatory mechanism underlying the therapeutic effects of THSWD in ischemic stroke remains largely unexplored. In this study, we employed desorption electrospray ionization mass spectrometry imaging (DESI-MSI) to investigate the metabolic changes in the brain tissue of ischemic stroke rat model. Our investigation revealed that 30 metabolites exhibited significant dysregulation in the ischemic brain regions, specifically the cortex and striatum, following ischemic injury. Following the treatment of THSWD, almost all the dysregulated metabolites got different degrees of callback. Further pathway analysis indicated that THSWD might exert its therapeutic effects by restoring energy metabolism, improving neurotransmitter metabolism, recovering polyamine metabolism, and so on. DESI-MSI offers a favorable methodology for investigating the alterations in the spatial distribution and level within the ischemic brain region following treatment with THSWD in ischemic stroke. These findings provide a novel perspective on the underlying mechanisms of the efficacy of THSWD in ischemic stroke treatment.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"6931-6944"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142520645","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":"Perfluoroalkyl acid precursor or weakly fluorinated organic compound? A proof of concept for oxidative fractionation of PFAS and organofluorines.","authors":"Jonathan Zweigle, Apollonia Schmidt, Boris Bugsel, Christian Vogel, Fabian Simon, Christian Zwiener","doi":"10.1007/s00216-024-05590-5","DOIUrl":"10.1007/s00216-024-05590-5","url":null,"abstract":"<p><p>Organofluorine mass balance approaches are increasingly applied to investigate the occurrence of per- and polyfluoroalkyl substances (PFAS) and other organofluorines in environmental samples more comprehensively. Usually, complex samples prevent the identification and quantification of every fluorine-containing molecule. Consequently, large unidentified fractions between fluorine sum parameters such as extractable organic fluorine (EOF) and the sum of quantified analytes are frequently reported. We propose using oxidative conversion to separate (unidentified) weakly fluorinated compounds (e.g., pesticides, pharmaceuticals) from PFAA-precursors (perfluoroalkyl chain lengths ≥ C₆). We show with three organofluorine model substances (flufenamic acid, diflufenican, pantoprazole) that CF₃-groups or aromatic fluorine can be quantitatively converted to inorganic fluoride and trifluoroacetic acid (TFA) by applying PhotoTOP oxidation (UV/TiO₂). The principle of fluorine separation in mixtures is demonstrated by the oxidation of the three weakly fluorinated compounds together with the PFAA-precursor 6:2/6:2 fluorotelomer mercaptoalkyl phosphate diester (FTMAP). After oxidation, the products F^- and TFA were separated from PFCAs (> C₄) by SPE, and the fractions were analyzed individually. Closed mass balances both with and without the addition of organic matrix were achieved. Eventually, the fluorine balance was verified by total fluorine measurements with combustion ion chromatography (CIC). The proposed methods should be considered a proof of concept to potentially explain unidentified fractions of the EOF, especially if compounds with low fluorine content such as pesticides, pharmaceuticals, and their transformation products contribute largely to the EOF. Future studies are needed to show the applicability to the complexity of environmental samples.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"6799-6808"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11579176/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405874","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Early developments toward HbA_1c determination in whole blood by high-speed sample preparation and LC-MS/MS analysis.","authors":"Indranil Mitra, Andreas Leinenbach, Andrea Geistanger, Andreas Huber, Thomas Dülffer, Susanne Adam, Lars Hillringhaus, Martin Silvestre, Holger Busskamp, Sven Vopel","doi":"10.1007/s00216-024-05601-5","DOIUrl":"10.1007/s00216-024-05601-5","url":null,"abstract":"<p><p>We report a method to determine HbA_1c (glycated hemoglobin) where whole blood samples are prepared by fast hemolysis (dilution with deionized water and vortex mixing), digestion with 0.6 mg/mL endoproteinase Glu C (Glu C) in 30 mM ammonium acetate buffer (pH 4.3) at 37 °C for 45 min, and termination of the digestion by diluting with 0.1% formic acid in water, and then analysis by a gradient liquid chromatography-tandem mass spectrometry (LC-MS/MS) method with a run time of 36 s. The method is linear between 0 and 200 HbA_1c/mol Hb (IFCC) with a correlation coefficient of 0.999, providing an inter-day reproducibility between 1.3 and 2.3% CV, and comparable with results from analysis of the same samples on the Roche Cobas® c 513 clinical analyzer with a correlation coefficient of 0.998. In two alternative detection workflows that were not characterized in detail, the same digested samples were purified by a magnetic bead-based solid-phase extraction (SPE) method requiring about 10 min and then analyzed using either an isocratic LC-MS/MS method or a flow injection analysis (FIA)-MS/MS method with run times of 12 s and 18 s, respectively. Our work demonstrates the feasibility of LC-MS-based methods for HbA_1c determination that minimize the time required for sample preparation and measurement while preserving analytical performance and are thereby more suitable for routine clinical settings compared to traditional methods which require up to 25 h and 23 min, respectively, to prepare and measure samples.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":"6735-6744"},"PeriodicalIF":3.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11579156/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142492487","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}