Analytical Methods最新文献

{"title":"Considerations for deconvolution of oligonucleotide mass spectra in quality control.","authors":"Michael Rühl","doi":"10.1039/d5ay01223f","DOIUrl":"https://doi.org/10.1039/d5ay01223f","url":null,"abstract":"<p><p>Oligonucleotide therapeutics and mass spectrometry are evolving fields in both research and pharmaceutical development. A proper data evaluation needs to be ensured, especially in a regulated environment. Deconvolution is often applied to derive the intact mass from electrospray ionization (ESI) mass spectra. The type of deconvolution algorithm applied as well as the used parameters can affect the outcome of the analysis. This study aims to show differences in the deconvolution algorithm in terms of mass accuracy and how the input mass range affects the mass accuracy and the detected abasic impurities and adducts for polydeoxythymidine (poly-dT) samples with 20, 48, 100 and 200 nucleotides (nts). While Bayesian deconvolution is more suitable for analytes up to ∼15 000 Da in terms of mass accuracy, maximum entropy deconvolution fits best for larger oligonucleotides, with a mass accuracy of 1.6 ppm for a 100 (nts) poly-dT sample. The input mass range is the second important parameter to be tested, as low charge states tend to show more adducts and higher charge states tend to be prone for depurination and depyrimidation, leading to an overrepresentation of the impurity mass in the deconvoluted spectrum. This manuscript also highlights how the findings can be translated to a short DNA-based adjuvant and a sample single guide RNA.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":2.6,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145111437","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Determination of animal species origin of blood in artworks by LC-MS/MS","authors":"Stepanka Kuckova, Tadeas Matecha, Jiri Santrucek, Alena Meledina, David Straka, Katarina Harcarikova, Tomas Dostal, Ludek Dvorak, Vaclav Pitthard and Silvia Miklin-Kniefacz","doi":"10.1039/D5AY01156F","DOIUrl":"10.1039/D5AY01156F","url":null,"abstract":"<p >This study introduces an innovative approach to the long-standing challenge of determining the animal origin of blood used in artworks – an issue of central relevance to art historians aiming to understand historical techniques, symbolic meanings, and the cultural traditions associated with artistic materials. Using LC-MS/MS analysis, species-specific peptide sequences of blood proteins were identified, allowing for the discrimination of seven animal species (cat, cow, dog, goose, hen, human, and pig). This analytical approach was successfully applied to a series of model samples containing blood, confirming both the proteinaceous composition and the animal origin of the blood. Furthermore, the method enabled the identification of pig blood in historical samples taken from Japanese and Chinese lacquer artefacts dating from the 18th and 19th centuries. The novelty of this work lies in a new strategy for data evaluation that facilitates the creation of custom peptide databases tailored to distinguish specific animal species. This approach overcomes a major limitation in proteomic studies – namely, the lack of complete sequence data for many animals – by incorporating homologous sequences from closely related species. The strategy demonstrates a high degree of effectiveness when implemented within a clearly defined group of animal species, such as those historically utilised in the production of blood-based artistic materials. This approach offers a novel pathway for the molecular identification of animal origin in cultural heritage contexts and establishes a robust foundation for future interdisciplinary investigations bridging art history, conservation science, and molecular biology.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 38","pages":" 7755-7763"},"PeriodicalIF":2.6,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ay/d5ay01156f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145111490","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rapid gas chromatography – mass spectrometry profiling of small organic molecules in biomass pyrolysis: a simple and industry-ready approach for process optimisation","authors":"Sanathri Alwis, Leo Lebanov, Estrella Sanz Rodriguez, Noel W. Davies, Desmond E. Richardson and Brett Paull","doi":"10.1039/D5AY01053E","DOIUrl":"10.1039/D5AY01053E","url":null,"abstract":"<p >Biomass pyrolysis is a sustainable process that converts organic matter into valuable products including biochar, bio-oil, and syngas. Depending on the type of biomass, its age, moisture content, and the process conditions, the composition of the resulting mixture can vary significantly. Quantifying compositional changes during pyrolysis is essential for improving product quality, ensuring process efficiency and recovering by-products for conversion into value-added products, thus enhancing sustainability. This study presents a novel gas chromatography-mass spectrometry (GC-MS) method to identify and quantify volatile organic compounds released during pyrolysis, namely formaldehyde, methanol, acetic acid, and formic acid. The method features simple sample preparation and achieves baseline separation of target analytes using a DB-WAX-UI column in under 15 minutes. Data acquisition was conducted in both selected ion monitoring (SIM) mode to obtain high sensitivity for targeted analytes and full scan mode to facilitate untargeted monitoring. Achieved instrumental LODs were 0.09, 0.04, 0.02, and 0.03 μg mL<small>⁻¹</small> for formaldehyde, methanol, acetic acid, and formic acid, respectively. Intra- and inter-day repeatability was always better than 5% and 12%, respectively. The method was applied for the analysis of 141 samples collected from two sampling points at a local biomass pyrolysis facility over a period of 7 months, providing insights into the changes in the analyte profile during this period. The results demonstrate that this GC-MS method is a simple, fast, industry ready method, able to provide additional valuable insights into product quality for the purpose of process monitoring and optimisation.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 38","pages":" 7732-7742"},"PeriodicalIF":2.6,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084517","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Novel multitarget-labeled molecular networking for exploring pharmacodynamic compounds of traditional Chinese medicine formulae: a case study of Zhu-Ling decoction","authors":"Xianxian Li, Jiamu Ma, Yuan Zheng, Xueyang Ren, Wanzhu Wang, Yun Zhang, Shufan Yao, Jianling Yao, Feng Zhang, Yu Cao, Yongqi Yang, Yuqing Yang, Letian Ying, Yan Zhang, Qingqing Song and Gaimei She","doi":"10.1039/D5AY00772K","DOIUrl":"10.1039/D5AY00772K","url":null,"abstract":"<p >Traditional Chinese Medicine (TCM) formulae exert therapeutic effects through the synergistic actions of multiple compounds. The interaction between compounds of TCM and their biological targets can be pivotal in revealing the pharmacodynamic material basis and compatibility mechanisms. Here, a novel strategy named multitarget-labeled molecular networking (MLMN), which combines feature-based molecular networking (FBMN) and -CDOCKER interaction energy (-CIE) calculated from molecular docking, was presented to discover the pharmacodynamic compounds and implemented in a case study of Zhu-Ling Decoction (ZLD), a well-known TCM formula for kidney diseases. First, VOSviewer and Carrot2 were employed to focus on the clinical disease of ZLD, known as chronic glomerulonephritis (CGN) and its five core targets (TGF-β, Smad3, TLR4, IL-6 and Nrf2) for further study. Subsequently, 98 compounds were identified using HPLC-Q-Exactive MS in combination with FBMN. These compounds were then docked with the five core targets as ligands and receptors. The results showed that TGF-β, Smad3, and IL-6 had stronger binding affinities with various chemical compounds in ZLD. Finally, MLMN analysis was proposed to visually and comprehensively display the interactions between compounds in ZLD and multiple targets. Compounds in ZLD, such as poricoic acid A and polyporusterone A, demonstrated good binding affinities with all five targets, suggesting that they are key pharmacodynamic compounds contributing to the efficacy of ZLD against CGN. Finally, the effects of alisol B 23-acetate, poricoic acid A and polyporusterone A in regulating mRNA expression levels of core targets were verified based on a zebrafish model of kidney injury. This study provides a novel strategy for the rapid exploration of the pharmacodynamic material basis of TCM efficacy through a “multi-compounds to multi-targets” standpoint.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 38","pages":" 7704-7721"},"PeriodicalIF":2.6,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084564","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Determination of amide herbicides in food by salting-out vortex-assisted dispersive liquid–liquid microextraction coupled with gas chromatography-tandem mass spectrometry","authors":"Baoqing Bai, Xiaojie Li, Siyuan Meng, Ying Zhang, Tao Bo, Jinhua Zhang and Yukun Yang","doi":"10.1039/D5AY01089F","DOIUrl":"10.1039/D5AY01089F","url":null,"abstract":"<p >A new method, salting-out vortex-assisted dispersive liquid–liquid microextraction (SO-VA-DLLME), was developed for extracting amide herbicides (AHs) from food samples. Quantitative analysis of AHs was performed using gas chromatography-tandem mass spectrometry (GC-MS/MS). One-variable-at-a-time testing was used to investigate the impact of the experimental parameters on extraction efficiency. Based on the results of our previous research, this study analyzed the impact of various extraction factors on AH extraction efficiency and improved pre-treatment conditions using response surface methodology (RSM) and a back propagation-genetic algorithm (BP-GA) neural network model. Specifically, the BP-GA neural network exhibited exceptional stability during AH extraction, facilitating comprehensive optimization. The method demonstrated excellent linearity (<em>R</em><small>²</small> ≥ 0.992) within the 2.00–2000 ng kg<small>⁻¹</small> range. The detection limits (LODs) were estimated to be 0.060–1.20 ng kg<small>⁻¹</small>, and quantitation limits (LOQs) were 0.200–2.00 ng kg<small>⁻¹</small> at S/N ratios of 3 and 10, respectively. Extraction recoveries ranged from 87% to 98%, with enrichment factors of 3480 to 3920, indicating effectiveness. Intra-day and inter-day relative standard deviations (RSDs) were below 9.60%, ensuring reliability. In line with the white analytical chemistry principles, the method confirmed environmental safety. Overall, this rapid, cost-effective method efficiently detected amide herbicides in food samples.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 38","pages":" 7743-7754"},"PeriodicalIF":2.6,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084527","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structural analysis of synthetic opioids using travelling wave ion mobility-mass spectrometry (TWIM-MS)†","authors":"Karen Abigail Reyes Monroy, Daillin L. Perez, Rebecca Demmelash, Lilly T. Ngo, Ariana M. Mancilla Rodriguez, Haley A. Castro, Noah R. Wiese, Wilbert A. Murillo, Dr. Teresa D. Golden and Dr. Guido F. Verbeck","doi":"10.1039/D4AY02263G","DOIUrl":"10.1039/D4AY02263G","url":null,"abstract":"<p >Traveling wave ion mobility-mass spectrometry (TWIM-MS) has emerged as a powerful tool for the identification of synthetic opioids, such as fentanyl and its analogs. However, due to its novelty, only a few fentanyl analogs have been studied using this technology and alternative drift gases, apart from the commonly employed nitrogen gas. Here we introduce the largest compendium of measured <small>^TW</small>CCS<small>_{N<small>₂</small>}</small>, <small>^TW</small>CCS<small>_He</small>, and <small>^TW</small>CCS<small>_{CO<small>₂</small>}</small> values for fentanyl-related compounds. This compendium of mobility-derived CCS molecular descriptors for precursor [M + H]<small>⁺</small> ions can be used to assign fentanyl identities. Here, we report collision-cross section (CCS) values for precursor [M + H]<small>⁺</small> ions of 110 fentanyl analogs, 7 fentanyl precursors, and 31 non-fentanyl related synthetic opioids measured using three mobility gases; nitrogen, helium, and carbon dioxide. Measured <small>^TW</small>CCS<small>_{N<small>₂</small>}</small> values show high agreement with previously published collision cross-section values obtained <em>via</em> drift-tube ion mobility (DTIM) MS, with differences ranging from −0.1 to 1.3%. Additionally, computationally derived CCS values for each fentanyl analyte were calculated using MobCross, with a difference range of ±3–15% between theoretical and experimental values.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 38","pages":" 7692-7703"},"PeriodicalIF":2.6,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ay/d4ay02263g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145079220","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An electrochemiluminescence biosensor based on Ag–Ag2S as an efficient emitter and Zr-MOG as the co-reaction promoter for the ultrasensitive detection of CYFRA21-1","authors":"Yun Wang, Fengdi Li, Xianpeng Liao, Kailong Liu, Lihua Hu, Hongmin Ma, Dan Wu and Qin Wei","doi":"10.1039/D5AY00896D","DOIUrl":"10.1039/D5AY00896D","url":null,"abstract":"<p >In this work, a highly sensitive electrochemiluminescence (ECL) biosensor was successfully developed for the detection of CYFRA21-1, in which a metal–organic gel (Zr-MOG) was introduced as a novel co-reaction promoter for amplifying the ECL signal of the silver nanoparticle-modified silver sulfide/potassium persulfate (Ag–Ag<small>₂</small>S/K<small>₂</small>S<small>₂</small>O<small>₈</small>) system. Specifically, the incorporation of Ag nanoparticles narrowed the bandgap and enhanced the ECL signals of the composites. As a co-reaction promoter, Zr-MOG accelerated the reduction of S<small>₂</small>O<small>₈</small><small>²⁻</small> to produce abundant sulfate radicals (SO<small>₄</small>˙<small>⁻</small>) while increasing the electrode active surface area, which led to a significant enhancement of the Ag–Ag<small>₂</small>S ECL emission. The biosensor constructed based on the dual-signal amplification strategy demonstrated excellent sensitivity, selectivity, and stability, with a wide linear detection range of 0.00005–100 ng mL<small>⁻¹</small> and a detection limit as low as 17.66 fg mL<small>⁻¹</small> (S/N = 3).</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 38","pages":" 7635-7642"},"PeriodicalIF":2.6,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145079192","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Microfade testing in cultural heritage","authors":"Analytical Methods Committee, AMCTB No. 119","doi":"10.1039/D5AY90120K","DOIUrl":"10.1039/D5AY90120K","url":null,"abstract":"<p >Microfade testing (MFT) is an accelerated aging technique used to test the lightfastness of a material or object directly rather than relying on generalisations or models; it was developed specifically for the cultural heritage sector, unlike many other analytical methods currently used in museums and cultural institutions. Since its development in the 1990s, MFT has helped to guide museums’ lighting policies and the responsible display and loan of cultural heritage objects. MFT is considered to be minimally invasive and is frequently used to test materials that are suspected to be highly light-sensitive, including textiles, works on paper and more complex three-dimensional objects. Tests are conducted directly on the object, allowing the user to observe changes as the test is performed – despite the name of the technique, MFT can be used to detect any colour change, not just fading.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 37","pages":" 7570-7573"},"PeriodicalIF":2.6,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145074379","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A UPLC-MS/MS method for the determination of 2-nitro-1,3-propanediol, a metabolite of Bronopol, in human urine","authors":"Isabell Schönrath, Christoph Schmidtkunz, Katja Küpper, Edgar Leibold and Gabriele Leng","doi":"10.1039/D5AY00960J","DOIUrl":"10.1039/D5AY00960J","url":null,"abstract":"<p >Bronopol is a preservative with applications in various industrial fields; thus, the general population may be exposed to this substance. For the development of an analytical method for human biomonitoring (HBM) in urine, 2-nitro-1,3-propanediol was postulated as a suitable biomarker according to findings in animal studies. The herein described UPLC-MS/MS method enables the quantification of 2-nitro-1,3-propanediol in a concentration range from 0.5 μg l<small>⁻¹</small> (LOQ) to 5000 μg l<small>⁻¹</small>. The sample preparation is based on a liquid–liquid extraction with ethyl acetate. Analyte losses are compensated by the authentic, isotope-labelled internal standard 2-nitro-1,3-propanediol-<small>¹³</small>C<small>₃</small>. The method fulfils all reliability criteria: intra- and interday coefficients of variation (CVs) were determined in spiked pooled urine samples at 1, 10 and 100 μg l<small>⁻¹</small> and did not exceed 5%. The corresponding accuracies were between 104 and 105%. In individual urine samples (robustness, <em>n</em> = 10) spiked at the same levels, CVs were &lt;8% and accuracies ranged between 98 and 104%. Applying different hydrolysis protocols, we could rule out any phase II metabolites of 2-nitro-1,3-propanediol from being excreted in urine. Thanks to samples from a human metabolism study involving oral intake of Bronopol, we were able to confirm the postulated metabolite. In representative specimens, the analyte could be quantified in large amounts, demonstrating the applicability of the method both for high concentrations in metabolism studies and occupational medicine, and at lower levels, for example, in field studies to assess the burden of the general population.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 38","pages":" 7670-7677"},"PeriodicalIF":2.6,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145074343","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Machine learning-powered plasmonic pattern recognition: etch-suppressed gold nanorods for multiplex urinary analysis of catecholamine neurotransmitters","authors":"Mahsa Daneshmandi, Afsaneh Orouji and Mohammad Reza Hormozi-Nezhad","doi":"10.1039/D5AY00976F","DOIUrl":"10.1039/D5AY00976F","url":null,"abstract":"<p >Simultaneous monitoring of catecholamine neurotransmitters (CNTs)—including epinephrine (Epi), norepinephrine (NE), levodopa (L-DOPA), and dopamine (DA)—is essential for the accurate diagnosis and effective management of various neurological disorders. However, most existing sensing platforms face challenges such as limited multiplexing capabilities and potential cytotoxicity of the sensing components. In this work, we introduce a sensitive, non-toxic, and non-invasive single-component multicolorimetric probe capable of detecting and distinguishing low concentrations of Epi, NE, L-DOPA, and DA, along with their binary, ternary, and quaternary mixtures. The sensing mechanism relies on the controlled inhibition of gold nanorod (AuNR) etching in the presence of varying concentrations of <em>N</em>-bromosuccinimide (NBS), a mild oxidizing agent, under ambient conditions. To enable robust analyte identification and quantification, the spectral responses were processed using machine learning algorithms—specifically, linear discriminant analysis (LDA) for classification and partial least squares regression (PLSR) for concentration prediction. Under the optimized conditions, the assay demonstrated excellent linearity across a broad concentration range for each analyte, Epi (1.8–20 μmol L<small>⁻¹</small>), NE (1.4–25 μmol L<small>⁻¹</small>), L-DOPA (1.5–25 μmol L<small>⁻¹</small>), and DA (2.8–50 μmol L<small>⁻¹</small>), with corresponding detection limits of 0.62, 0.47, 0.49, and 0.92 μmol L<small>⁻¹</small>. The practical utility of the platform was validated through successful application to human urine samples, confirming its potential as a powerful tool for point-of-care diagnostics and clinical neurochemical analysis.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 37","pages":" 7390-7401"},"PeriodicalIF":2.6,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145062928","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}