Analytica Chimica Acta最新文献

{"title":"Functionalized toothpicks for solid-phase microextraction of drugs from oral fluids","authors":"Patricia García-Atienza ,&nbsp;Jaime Millán-Santiago ,&nbsp;Rafael Lucena ,&nbsp;Soledad Cárdenas ,&nbsp;Sergio Armenta ,&nbsp;José Manuel Herrero-Martínez ,&nbsp;Héctor Martínez-Pérez-Cejuela","doi":"10.1016/j.aca.2025.344243","DOIUrl":"10.1016/j.aca.2025.344243","url":null,"abstract":"<div><h3>Background</h3><div>Efficient extraction techniques with high selectivity and sensitivity are critical for drug analysis in biological matrices. Traditional methods often face challenges when dealing with semi-polar and ionic drugs, necessitating the development of improved sorbents. To address this issue, we propose the use of carboxymethylated wooden toothpicks (c-WTs) as a novel sorbent for solid-phase micro-extraction (SPME). This approach aims to improve drug extraction from oral fluids, offering a more effective and sustainable solution compared to conventional sorbents.</div></div><div><h3>Results</h3><div>Wooden toothpicks were modified through sodium chloroacetate oxidation under mild conditions, introducing carboxyl groups that enhance analyte-sorbent interactions via electrostatic forces. Characterization via infrared spectroscopy and scanning electron microscopy confirmed the successful derivatization, showing an increase in surface roughness compared to unmodified toothpicks. The optimized SPME method was applied to extract a range of 22 drugs, including amphetamines, opioids, benzodiazepines, and cannabinoids, from oral fluids. The validation of the method demonstrated excellent performance, with recovery rates ranging from 68 to 120 %. Precision was high, with relative standard deviations (RSD) below 10 %. The method also exhibited low limits of quantification (1–5 μg L⁻¹) when analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS), indicating its potential for reliable and sensitive drug analysis in biological matrices.</div></div><div><h3>Significance</h3><div>This study presents an innovative, sustainable approach for drug extraction using natural-based sorbents. The use of c-WTs offers a cost-effective, selective, and environmentally friendly alternative to traditional methods. This work contributes to the development of efficient SPME techniques for complex biological samples, advancing analytical methodologies in forensic and clinical applications.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1365 ","pages":"Article 344243"},"PeriodicalIF":5.7,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144130643","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":"Identification the fine structure of triacylglycerol regioisomers from localization of acyl chains by electron activated dissociation tandem mass spectrometry","authors":"Ying Wang, Dong ruizhi, Xiuqin Li, Hongtao Chu, Zhuo Man, Qinghe Zhang","doi":"10.1016/j.aca.2025.344217","DOIUrl":"https://doi.org/10.1016/j.aca.2025.344217","url":null,"abstract":"<h3>Background</h3>Triacylglycerols (TAGs) are essential components in living organisms, exhibiting a significant correlation between their structural characteristics and physiological functions. A considerable number of regioisomers can arise due to the different arrangements of fatty acyl chains attached to the glycerol backbone in glycerides. The positional differences of fatty acyl chains significantly influence the physical properties, biochemical characteristics, and nutritional value of TAGs. In current, Accurately and efficiently characterizing the TAG regioisomers still presents a considerable challenge due to the diversity of TAG structures.<h3>Results</h3>In this study, we employed electron activated dissociation (EAD) tandem mass spectrometry to systematically analyze 17 TAG isomers, including four AAA types, four AAB types, three ABA types, and six ABC types. Compared to collision induced dissociation (CID), EAD fragmentation of the [M+Na]⁺ species (13eV) from standard TAGs resulted in additional specific and informative. We propose a novel and efficient strategy for the structural characterization of TAG regioisomers based on three characteristic ions groups: 1) sodium-adducted precursor ions; 2) ions resulting from the loss of one fatty acyl chain, where the number of these ions varies depending on the isomeric position of the TAGs; and 3) ions resulting from the loss of two fatty acyl chains, with similar positional variations. By analyzing these characteristic ions, our approach allows for identification of TAG regioisomers.<h3>Significance</h3>EAD represents a relatively novel cleavage technique that effectively targets singly charged lipid ions, thereby yielding extensive structural information. A comprehensive strategy was proposed for characterizing TAG regioisomers based on three characteristic ions groups, enhancing confidence in structure elucidation. Our findings establish a foundation for the rapid qualitative identification of TAG regioisomers in complex oils and fats.","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"15 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122418","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":"Portable microfluidic-LAMP assay for rapid on-site detection of eight highly pathogenic viruses","authors":"Huan Li ,&nbsp;You Nie ,&nbsp;Yi Wu ,&nbsp;Yuanyuan Cao ,&nbsp;Wanying Liu ,&nbsp;Rongtao Zhao ,&nbsp;Xuesong Feng ,&nbsp;Rongzhang Hao","doi":"10.1016/j.aca.2025.344236","DOIUrl":"10.1016/j.aca.2025.344236","url":null,"abstract":"<div><h3>Background</h3><div>The recent global spread of highly pathogenic viruses, such as Mpox and Ebola viruses, highlights the urgent need for multiplex detection technologies. Current methods lack the capability for simultaneous identification, which hampers outbreak control in resource-limited settings and global surveillance efforts. Traditional techniques, like real-time quantitative polymerase chain reaction (qPCR), are often impractical in resource-limited areas due to laboratory dependency, and specialized personnel requirements. A portable, rapid, and cost-effective method for multiplex field detection of highly pathogenic viruses is critically needed to address the growing threat of outbreaks in resource-limited settings.</div></div><div><h3>Results</h3><div>In this study, a simple and rapid nucleic acid extraction method was performed using a paper-based dipstick, which was equipment-free and could be completed within 2 min. Subsequently, a microfluidic chip was integrated with loop-mediated isothermal amplification (LAMP) technology to develop a field-deployable, portable detection method termed the microfluidic-LAMP assay. This assay allows for the simultaneous detection of eight highly pathogenic viruses: Ebola virus (EBOV), Marburg virus (MARV), Rift Valley fever virus (RVFV), Lassa virus (LASV), yellow fever virus (YFV), Congo Basin Mpox virus (C-MPXV), West African Mpox virus (W-MPXV), and variola virus (VARV), all within a span of 70 min. The assay demonstrated a sensitivity of 7.02 × 10²-8 × 10⁴ copies/mL across different targets using simulated clinical samples. The limits of detection of this field available assay were comparable to or lower than those of the real-time quantitative PCR. The microfluidic-LAMP assay demonstrated good specificity in cross-tests with 21 pathogens, including the above 8 viruses and 13 other respiratory pathogens.</div></div><div><h3>Significance</h3><div>This study presents the first portable microfluidic-LAMP assay capable of simultaneously detecting eight highly pathogenic viruses in resource-limited settings. The assay's equipment-free nucleic acid extraction (2 min) and rapid detection (70 min) make it a practical solution for on-site detection in resource-limited regions, facilitating outbreak control and global surveillance efforts.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1365 ","pages":"Article 344236"},"PeriodicalIF":5.7,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144130644","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":"Overcoming limitations in exhaled breath aerosol analysis – Untargeted breathomics for the identification of endogenous breath biomarkers using LC-HRMS/MS","authors":"Juel Maalouli Schaar,&nbsp;Selina Hemmer,&nbsp;Sascha K. Manier,&nbsp;Lea Wagmann,&nbsp;Markus R. Meyer","doi":"10.1016/j.aca.2025.344241","DOIUrl":"10.1016/j.aca.2025.344241","url":null,"abstract":"<div><h3>Background</h3><div>Human exhaled breath (EB) aerosol is a suitable matrix for the non-invasive bioanalysis of both volatile but also non-volatile compounds. One of the key challenges in drug monitoring studies is the lack of standardization in EB sample collection. The aim of the present study was to use untargeted breathomics for identification of potential endogenous biomarkers in EB that could address these challenges.</div></div><div><h3>Results</h3><div>The Breath Explor impaction device was used to collect microparticles in EB aerosol from six healthy volunteers and six different sampling time points over a 1-h period (total number of samples = 36). Sample preparation consisted of an extraction with methanol and analysis was performed using reversed-phase and hydrophilic interaction-phase liquid chromatography coupled to high-resolution mass spectrometry. Results revealed the presence of a feature that could be reliably detected across all samples, thus representing a potential biomarker for standardizing EB aerosol sample collection. Although an annotation of this feature was not possible, it showed robustness and reproducibility in EB samples from healthy volunteers and could also be successfully detected in patient samples.</div></div><div><h3>Significance and novelty</h3><div>This study represents a step forward in overcoming the current limitation of EB analysis, the lack of standardization in sampling procedure. Nevertheless, further investigation including correlation studies and more diverse populations will be essential for the confirmation of the clinical relevance and application of this biomarker.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1365 ","pages":"Article 344241"},"PeriodicalIF":5.7,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144130618","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 of a quantitative structure-response relationships to estimate concentrations of plasticizer metabolites in urine without reference standards using non-targeted analysis with liquid chromatography high-resolution mass spectrometry","authors":"Yong-Lai Feng ,&nbsp;Jerrie Feng ,&nbsp;Anca Baesu ,&nbsp;Vanessa Martinez ,&nbsp;Yan Li","doi":"10.1016/j.aca.2025.344215","DOIUrl":"10.1016/j.aca.2025.344215","url":null,"abstract":"<div><h3>Background</h3><div>Plasticizers are characterized as endocrine disruptors, and human exposure to these chemicals can adversely affect the reproductive system. Non-targeted analysis (NTA) using liquid chromatography – high resolution mass spectrometry (LC-HRMS) is a discovery-based approach for screening and identifying hundreds of compounds and metabolites in human samples without <em>a priori</em> knowledge of the chemical species that would be present in the sample. However, while NTA methods need to be standardized in order to provide reliable and reproducible qualitative results, <strong>there is also an urgent need to develop NTA methods that can provide quantitative information for identified compounds</strong>.</div></div><div><h3>Results</h3><div>We describe a quantitative structure-response relationship (QSRR) in NTA using LC-electrospray ionization (ESI)-HRMS that was established by combining retention behavior and structural descriptors. This relationship can be used to estimate the signal response factors of chemicals and we can utilize the estimated response factors to approximate the concentrations of plasticizer metabolites without reference standards. The model consists of 12 variables, being retention time and 11 molecular descriptors, that can estimate response factors of eleven testing chemicals with an error less than 30 %. The study demonstrated that the model can be updated with routine (e.g. daily) calibration curves and estimate concentrations of unknown metabolites in urine with an error less than 50 % for most compounds. The model can be applied to two different ionization systems without having a significant impact on its prediction accuracy.</div></div><div><h3>Significance</h3><div>While NTA provides the important information on identification of unknown and new chemicals/metabolites, it is crucial to provide quantitative concentrations for these compounds identified in NTA to support exposure assessment. Our approach enables a fast and simple estimation of the concentration of unknown metabolites of phthalates and their alternative chemicals without the need for respective reference standards. More importantly, the method is applicable to routine NTA studies and can be adapted to different LC-MS systems by simply updating the model with daily calibration data.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1364 ","pages":"Article 344215"},"PeriodicalIF":5.7,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122423","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":"Electrochemical Biosensors Based on Niobium-containing Oxides: A Review","authors":"Jessica Gotardi, Adilar Gonçalves dos Santos Júnior, Simone Cristina Baggio Gnoatto, Célia de Fraga Malfatti, Diogo André Pilger","doi":"10.1016/j.aca.2025.344239","DOIUrl":"https://doi.org/10.1016/j.aca.2025.344239","url":null,"abstract":"<h3>Background</h3>The diagnosis area is an expanding field, and methodological alternatives for the traditional techniques have been sought. In this context, electrochemical biosensors have attracted attention due to their low cost per analysis, portability, and high sensitivity and specificity. Over the past two decades, niobium-containing oxides have been proposed for the construction of electrochemical biosensors due to their favorable properties, such as chemical stability, good biocompatibility, and the possibility of obtaining nanostructured morphologies. Additionally, biosensor development has other critical steps for its success, such as surface biofunctionalization and electrochemical detection strategy.<h3>Results</h3>This work provides a concise overview of niobium-containing oxides applied in developing electrochemical biosensors. From the literature, it was possible to observe that most of the works neglect the elucidation of the singular role of niobium-containing oxide and there is a lack of discussion of its advantages over other materials. However, considering the results of the reviewed works, it can be concluded that niobium-containing oxides are a suitable candidate for electrochemical biosensor construction. In addition, this review explores electrode construction and details chemical and biological surface functionalization techniques that are used to achieve electrostatic or covalent immobilization, especially emphasizing how surface morphological structures impact bioreceptor immobilization and the assembly of each type of biosensor. Electrochemical detection strategies are analyzed, focusing on their specific applications in different biosensor types. Besides, future perspectives of niobium-containing oxides applied to biosensor construction are discussed.<h3>Significance and Novelty</h3>This review article offers valuable insights for researchers working in the fields of electrochemical biosensors, nanomaterials, and diagnostics. It provides an overview, without time constraints, of the knowledge base regarding the use of niobium-containing oxides for the development of electrochemical biosensors, focusing on synthesis methods, morphology and electrode construction, surface biofunctionalization, and electrochemical detection.","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"237 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113815","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":"A rapid portable assay for Salmonella typhimurium quantitative detection based on performance-enhancing anti-matrix interference aptamer","authors":"Jingwen Wang ,&nbsp;Yuanyuan Ge ,&nbsp;Tingyu Hu ,&nbsp;Heyang Zhao ,&nbsp;Jun Wang ,&nbsp;Fuxia Zhang ,&nbsp;Hongyan Zhang ,&nbsp;Shuyuan Du","doi":"10.1016/j.aca.2025.344240","DOIUrl":"10.1016/j.aca.2025.344240","url":null,"abstract":"<div><h3>Background</h3><div><em>Salmonella typhimurium</em> (<em>S. typhimurium</em>) is a common cause of global foodborne illness, and poses a significant risk to food safety and public health. Consequently, there is a pressing need to develop a portable, rapid, quantitative and highly sensitive detection method for <em>S. typhimurium</em> to enable real-time field detection. Although aptamer-based detection methods for <em>S. typhimurium</em> have garnered increasing attention, challenges remain in improving their sensitivity, portability, and quantification accuracy. Additionally, the use of portable instruments for rapid quantitative detection is essential for successfully applying rapid testing methods in field-based quantitative analysis.</div></div><div><h3>Results</h3><div>In this study, two truncation strategies were employed to optimize the binding properties of the aptamer ROU-77 while maintaining its resistance to matrix interference. This optimization yielded a truncated aptamer, ROU-46, which exhibited a 4.2-fold increase in target affinity compared to ROU-77. Based on these findings, a novel variant probe which incorporated the aptamer and DNA bridges was designed to develop a signal amplified portable high affinity aptamer assay. The target concentration was converted into measurable glucose levels via the formation of DNA bridges, with signal amplification achieved by modulating the number of these bridges. Consequently, a portable glucose meter enabled highly sensitive, quantitative detection of <em>S. typhimurium</em>. Under optimized conditions, the assay achieved a detection limit of 295 CFU⋅mL⁻¹. In addition, the excellent specificity, reproducibility, and practical applicability of this proposed method were carefully evaluated.</div></div><div><h3>Significance</h3><div>This study successfully truncated an anti-matrix interference aptamer and enhanced its affinity without compromising matrix resistance, which provided a novel strategy for aptamer optimization. Additionally, a new on-site detection method for <em>S. typhimurium</em> was developed by integrating the truncated aptamer into a composite probe and coupling it with a portable glucose meter. The use of the portable quantification device eliminated the need for large-scale equipment, and provided an innovative approach for real-time rapid detection.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1364 ","pages":"Article 344240"},"PeriodicalIF":5.7,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122421","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":"XYOnion: a layer-based method for splitting datasets into calibration and validation subsets","authors":"Jokin Ezenarro","doi":"10.1016/j.aca.2025.344229","DOIUrl":"10.1016/j.aca.2025.344229","url":null,"abstract":"<div><h3>Background</h3><div>Chemometric models are widely used in analytical chemistry to interpret complex multivariate data. However, they rely on robust validation, which typically involves splitting the dataset into calibration and validation subsets when an independent set is missing. Dataset splitting methods such as random splitting, Kennard-Stone, SPXY, and Onion each have limitations, including biased performance estimates or unbalanced subset distributions. This study introduces XYOnion, a novel algorithm that addresses these issues by combining the strengths of SPXY and Onion in a unified framework.</div></div><div><h3>Results</h3><div>XYOnion generates representative calibration and validation subsets by combining distances in both the predictor (X) and response (y) spaces, and assigning samples in layered shells based on this combined metric. This layered structure ensures balanced coverage across the entire data space and prevents extrapolation in the validation subset, leading to more robust model assessments. The algorithm was tested on both simulated and real datasets and systematically compared against commonly used methods such as random splitting, Kennard-Stone, SPXY, and Onion. Results demonstrate that XYOnion produces more realistic and stable figures of merit, effectively avoiding the overly optimistic performance estimates that arise from unbalanced or non-representative splits. Additionally, the incorporation of the DISTSLCT algorithm improves computational efficiency by eliminating the need to compute full pairwise distance matrices, thereby enhancing scalability and making XYOnion suitable for large and high-dimensional datasets encountered in chemometric applications.</div></div><div><h3>Significance and novelty</h3><div>In conclusion, XYOnion offers a practical and reliable approach for dataset splitting in situations where independent test sets are unavailable. By integrating distance information from both predictor and response variables with a layered sampling strategy, the method ensures balanced and representative calibration and validation subsets. This leads to more realistic, reproducible, and trustworthy model evaluations.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1364 ","pages":"Article 344229"},"PeriodicalIF":5.7,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144104250","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":"Ambient ionization mass spectrometry as a tool for organic reaction tracking","authors":"Min-Zong Huang ,&nbsp;Yan-Jyun Huang ,&nbsp;Chi-Yang Lee ,&nbsp;Jingyueh Jeng ,&nbsp;Vinoth Kumar Ponnusamy ,&nbsp;Wenjian Sun ,&nbsp;Jentaie Shiea","doi":"10.1016/j.aca.2025.344226","DOIUrl":"10.1016/j.aca.2025.344226","url":null,"abstract":"<div><h3>Background</h3><div>Thermal desorption electrospray ionization mass spectrometry (TD-ESI/MS) is an ambient ionization technique that enables the rapid analysis of chemical compounds in solids or solutions. A small amount of the sample solution was placed onto a metal wire, and an electric current was applied to heat it quickly. This process triggered the formation of numerous tiny droplets and released analyte molecules from the solution. These desorbed analytes were then fed into an ESI plume, where they combined with charged solvent species to produce analyte ions.</div></div><div><h3>Results</h3><div>This study demonstrates the use of a modified TD-ESI/MS technique to monitor the different stages of ongoing chemical reactions, including condensation reaction, addition reaction, and Tröger's base formation. Samples that were collected at different time points throughout each reaction were analyzed, where reactants, intermediates, and products for each reaction were detected as each reaction progressed towards equilibrium. A heating wire was used to hold and thermally desorb samples before electrospray ionization, where the low sample volumes needed (2 μL per sample) and minimal pretreatment required allows each sample to be easily and rapidly analyzed (within 15 s). Reproducible and time-resolved mass spectra were collected that offered insights on the changing structures and reaction mechanisms of the compounds involved in different stages of each ongoing reaction.</div></div><div><h3>Significance and novelty</h3><div>The user-friendly design of the TD-ESI/MS system enhances analytical efficiency by streamlining processes, simplifying operation, and reducing the reliance on extensive laboratory resources or specialized expertise. TD- ESI/MS supports both efficiency and sustainability—fundamental principles of green chemistry—by accelerating analytical workflows through direct sampling and minimal pretreatment, lowering the required volumes of solvents and samples, and decreasing the production of hazardous chemical waste.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1364 ","pages":"Article 344226"},"PeriodicalIF":5.7,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144104249","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":"LC-MS/MS-based determination of 25-hydroxyvitamin D in dried blood spots: crucial importance of combining a robust extraction with knowledge of the hematocrit","authors":"Liesl Heughebaert, Christophe P. Stove","doi":"10.1016/j.aca.2025.344223","DOIUrl":"https://doi.org/10.1016/j.aca.2025.344223","url":null,"abstract":"<h3>Background</h3>While many liquid chromatography – tandem mass spectrometry (LC-MS/MS)-based methods exist for the determination of 25-hydroxyvitamin D (25OHD) using dried blood spots (DBS), none of these comprehensively evaluated the robustness of the employed extraction method. The latter is critical as the hematocrit (Hct) as well as DBS ageing may affect analyte recovery and, thus, the accuracy of the obtained DBS-based 25OHD result. Moreover, as the application potential of DBS for the determination of 25OHD mainly lies in the analysis of DBS collected and archived in the context of newborn screening or epidemiological studies, a large variation in Hct and ageing is to be expected.<h3>Results</h3>A Hct- and ageing-independent extraction of 25OHD from a single 6 mm DBS subpunch was obtained in the Hct range of 0.23 to 0.53 L/L, using thermoshaking in 50/50 acetonitrile/water for 1 h at 60 °C. The optimized LC-MS/MS-based method allowed fast (&lt;2 min) separation of 3-epi-25OHD3 from 25OHD3 using an inverse gradient without the need for a dedicated column. The method was successfully validated for the determination of 25OHD3 and 25OHD2 in DBS, whole blood and plasma, with lower limits of quantification of 1.97 and 2.53 ng/mL in DBS and whole blood, and 3.94 and 5.06 ng/mL in plasma for 25OHD3 and 25OHD2, respectively. For both 25OHD3 and 25OHD2, accuracy and imprecision were respectively within -14.7% to 2.3% and within 1.1% to 10.0% for all matrices. Stability studies (up until three months of storage at room temperature) as well as the evaluation of spotted blood volume did not reveal any relevant impact on the quantification of 25OHD in DBS. Finally, a proof-of-concept study indicated that, when the Hct is taken into account, comparable results can be obtained in DBS and whole blood samples and plasma concentrations can be derived from DBS, respectively.<h3>Significance and novelty</h3>The presented manuscript is the first to address in-depth one of the major remaining research gaps in the determination of 25OHD from DBS, namely the evaluation of the robustness of the employed extraction procedure. Using thermoshaking at elevated temperature, we demonstrated Hct- and ageing-independent recovery of 25OHD3 and 25OHD2, confirming the method’s suitability for large-scale applications such as newborn screening and epidemiological studies.","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"45 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144097267","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}