Rapid Communications in Mass Spectrometry最新文献

{"title":"Identification and Structural Characterization of Degradation Products of Tivozanib Using LC-Q-TOF-MS/MS and NMR: An In Silico Approach for Degradation and Toxicity Prediction","authors":"Nadeem Shaikh,&nbsp;Sowmya Chaganti,&nbsp;Rahul Khemchandani,&nbsp;Dharipally Harini,&nbsp;H. M. Chandra Mouli,&nbsp;Gananadhamu Samanthula","doi":"10.1002/rcm.10167","DOIUrl":"10.1002/rcm.10167","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>The present study investigated the degradation behaviour of tivozanib (TVZ), a potent tyrosine kinase inhibitor, under various stress conditions, including hydrolytic (acid, base, and neutral), oxidative, thermal, and photolytic (UV and visible light) conditions. The resulting degradation products (DPs) were characterized by LC-Q-TOF-MS/MS and NMR. Additionally, in silico toxicity assessment and mutagenicity studies were accomplished by using DEREK Nexus and SARAH Nexus for TVZ and its DPs.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>The in silico degradation profile of TVZ was predicted using Zeneth software. Separation of the DPs was executed by RP-HPLC with gradient elution mode using Shim-pack Solar C18 column (250 × 4.6 mm, 5 μm). The mobile phase consists of solvent A as 10 mM ammonium acetate buffer (pH 3.8) and solvent B as a mixture of acetonitrile:methanol (70%:30% v/v). Structural characterization was performed for TVZ and its DPs using LC-Q-TOF-MS/MS and NMR spectroscopy.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>TVZ was sensitive to hydrolytic (acid, base, and neutral), oxidative, and photolytic (UV light) degradation conditions, wherein seven DPs were observed and separated by RP-HPLC. A plausible degradation pathway of TVZ was proposed based on mass spectrometry data. The preparative HPLC was used to isolate DP-III, DP-IV, and DP-VI, and the structures were confirmed by NMR spectroscopy. Furthermore, the 2D NMR data helped to differentiate the chemical structure of DP-IV, which had the same molecular mass as TVZ.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusion</h3>\u0000 \u0000 <p>Forced degradation studies were conducted in accordance with ICH Q1A (R2) and Q1B guidelines. Totally, seven DPs were observed in various stress conditions. DP-IV, a structural isomer of TVZ, was detected in basic hydrolytic conditions. The developed RP-HPLC method was validated following the ICH Q2(R1). This study helps in the stability testing and routine quality control analysis during the formulation development of TVZ.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"40 3","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145534019","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":"Optimization and Application of Automatic Cryogenic Vacuum Distillation System for Fruit Water Extraction for Isotope Analysis","authors":"Lianrong He,&nbsp;Yanjun Ju,&nbsp;Hongjie Qiao,&nbsp;Jie Zhao,&nbsp;Meng Wang,&nbsp;Duoyong Zhao,&nbsp;An Li","doi":"10.1002/rcm.10175","DOIUrl":"10.1002/rcm.10175","url":null,"abstract":"<div>\u0000 \u0000 <p>Stable hydrogen (δ²H) and oxygen (δ¹⁸O) isotopes in plant tissue water provide effective indicators for tracing fruit origin. This study optimized automatic cryogenic vacuum distillation (ACVD) system parameters (temperature, extraction time, and sample volume) to achieve a near-complete water recovery and high analytical accuracy. Systematic deviations of isotopic values between the original water and the water extracted from the spiked strawberry samples (Δδ²H: 4.56‰; Δδ¹⁸O: 1.14‰) were observed, likely due to matrix effects during extraction. Nevertheless, the optimized ACVD protocol enabled clear discrimination of the geographical origins of strawberries, apples, and kiwifruits based on their δ²H and δ¹⁸O values. These results indicate that, despite extraction-induced isotopic fractionation, tissue water isotopes remain reliable markers for fruit provenance when ACVD parameters are carefully controlled.</p>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"40 3","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145538154","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":"Enhancing Chimeric Fragmentation Spectra Deconvolution Using Direct Infusion–Tandem Mass Spectrometry Across High-Resolution Mass Spectrometric Platforms","authors":"Arina Ivanova,&nbsp;Wei Tang,&nbsp;Carsten Simon,&nbsp;Kai Dührkop,&nbsp;Sebastian Böcker,&nbsp;Gerd Gleixner","doi":"10.1002/rcm.10170","DOIUrl":"10.1002/rcm.10170","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>Direct infusion mass spectrometry (DI-MS) is a rapid analytical technique widely used in omics research and other fields. However, the complexity of DI-MS spectra frequently leads to co-fragmentation of analytes with similar <i>m/z</i>, resulting in chimeric fragmentation spectra that complicate compound identification. A DI-based tandem mass spectrometric method (DI-MS2), which modulates the intensity of precursors and fragments by the stepwise movement of the quadrupole isolation window, has been shown to successfully deconvolute chimeric fragmentation spectra. Yet, its applicability to different instruments and optimisation has not been evaluated.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Method</h3>\u0000 \u0000 <p>We evaluate the performance of DI-MS2 on two high-resolution instruments: a linear ion trap-Orbitrap (LIT-Orbitrap) and a quadrupole-Orbitrap (Q-Orbitrap). We examined the impact of six instrumental settings, including mass resolving power, isolation window width, step size between MS2 scans, number of microscans, collision energy and automatic gain control (AGC) target, on the analysis of isobaric mixtures with varying <i>m/z</i> differences.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>The LIT-Orbitrap consistently achieved high-quality chimeric spectra deconvolution with an average similarity score of 0.98 despite unexpected intensity modulation patterns. The Q-Orbitrap provided four times faster measurements but showed more variable results: It achieved a similarity score of 0.96 for isobars with a <i>m/z</i> difference larger than 0.02, but only 0.56 for <i>m/z</i> differences of 0.006.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>These findings indicate that the DI-MS2 is a robust and flexible method applicable across different MS platforms, though the Q-Orbitrap may be less suited for highly complex samples with multiple peaks per nominal mass. This highlights the potential of the DI-MS2 for structural elucidation of complex biological mixtures. Additionally, we provide initial setting optimisation guidelines to improve spectra deconvolution and measurement speed.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"40 3","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12620602/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145534000","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":"Editorial-In Memory of Jean-François Muller.","authors":"Laurence Charles, Frédéric Aubriet","doi":"10.1002/rcm.10168","DOIUrl":"https://doi.org/10.1002/rcm.10168","url":null,"abstract":"","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":" ","pages":"e10168"},"PeriodicalIF":1.7,"publicationDate":"2025-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145476516","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":"Direct Identification and Quantification of Flavonoids and Their Structural Isomers Using Ambient Ionization Tandem Mass Spectrometry","authors":"Yanqiu Wang,&nbsp;Liping Xu,&nbsp;Tiange Gu,&nbsp;Hongli Li,&nbsp;David Da Yong Chen","doi":"10.1002/rcm.10169","DOIUrl":"https://doi.org/10.1002/rcm.10169","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>Flavonoids are phenolic compounds with many health-benefiting properties. However, differentiating different types of flavonoids and their isomers is challenging due to their highly similar structures of various subtypes and different numbers and sites of substituents. Timely quality evaluation of flavonoid-based products is currently almost impossible.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>An ambient ionization method of direct analysis in real time (DART) ion source and tandem mass spectrometry (MS) was used to characterize the fine structures of flavonoids. Different flavonoid subtypes and their isomers with varied numbers and sites of substituents were subjected to DART ionization and collision-induced fragmentation MS analysis.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>Seven classes of flavonoids, including methoxy-substituted compounds, exhibited distinctive fragmentation pathways such as retro-Diels-Alder reactions, cross-ring cleavages, and neutral losses. Many flavonoid isomers produced diagnostic MS² and MS³ fragments through DART-tandem MS, enabling direct identification of various isomers within mixtures. An identification workflow was developed, culminating in the creation of a computational tool called FlavoFinder, which automatically determines flavonoid aglycone subtypes and their isomeric structures.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>The method and the structural elucidation program were successfully used for the qualitative and quantitative analysis of different flavonoid isomers from real samples. The analysis procedure is high-throughput and is capable of characterizing complex flavonoid structures without extensive sample pretreatment and front-end chromatographic separations.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"40 3","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/epdf/10.1002/rcm.10169","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145470192","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":"Integration of Multiple Mass Spectrometry Techniques and Molecular Network Analysis With Bioinformatics Approaches Revealed the Mechanism of Jiuwei Xifeng Granules in the Treatment of Tourette's Syndrome","authors":"Chenning Zhang,&nbsp;Pengfei Zhao,&nbsp;Limin Xing,&nbsp;Ruiqi Zhu,&nbsp;Zhiyan Liu,&nbsp;Ying Li,&nbsp;Shuang Li,&nbsp;Chun Bao,&nbsp;Mo Sun,&nbsp;Zhenzhong Wang,&nbsp;Wei Xiao","doi":"10.1002/rcm.10156","DOIUrl":"10.1002/rcm.10156","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>Jiuwei Xifeng Granules, a Chinese patent medicine developed based on renowned traditional Chinese medicine, has shown significant clinical efficacy in treating Tourette's syndrome. However, there is limited research on its pharmacological compounds and mechanism of action.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>In this study, high-resolution mass spectrometry (HRMS) was employed to analyze the natural organic small molecules in the herbal ingredients of Jiuwei Xifeng Granules and the drug-derived components in the serum, liver, and brain tissues of mice following long-term administration, as well as the protein components in the animal drugs. Meanwhile, inorganic trace elements are also widely assessed in Jiuwei Xifeng Granules. Molecular network analysis is utilized to further analyze the natural organic small molecules. Finally, network pharmacology and molecular docking techniques were employed to investigate the mechanisms of action of the main active ingredients.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>In total, 51 natural organic small molecules were identified in the five herbal medicines of Jiuwei Xifeng Granules, and the main active components included Gastrodin, Gentiopicroside, and Geissoschizine methyl ether. A total of 22 drug-derived components were identified in the blood of mice, 18 components were detected in the liver, and 8 were found in the brain tissue. Molecular network analysis further expanded the range of identified natural small molecule organic compounds. Thirty-six proteins were identified from two animal drugs in Jiuwei Xifeng Granules, and 68 trace elements were identified from two mineral medicines in Jiuwei Xifeng Granules. The results of the systems pharmacology analysis confirm that the pharmacological action pathways include serotonergic synapse, neuroactive ligand-receptor interaction, dopaminergic synapse, and cAMP signaling pathway. The main targets included DRD2, SLC6A4, HTR1A, DRD1, and KCNH2.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusion</h3>\u0000 \u0000 <p>This study employed a multi-omics approach to comprehensively analyze the active compounds in Jiuwei Xifeng Granules, providing a chemical foundation for elucidating its mechanism of action in treating Tourette's syndrome.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"40 2","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145399181","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":"Differentiation of α2–3- and α2–6-Linked Sialic Acid Linkages Using Esterification/Amidation Reactions and Tandem Mass Spectrometry","authors":"Wei-Chien Weng,&nbsp;Hsien-Wei Tseng,&nbsp;Chin-Yu Liang,&nbsp;Hsin-Kai Tseng,&nbsp;Ching-Ching Yu,&nbsp;Chun-Cheng Lin,&nbsp;Chi-Kung Ni","doi":"10.1002/rcm.10165","DOIUrl":"https://doi.org/10.1002/rcm.10165","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rational</h3>\u0000 \u0000 <p>Among various oligosaccharides, sialylated oligosaccharides play crucial roles in both physiological and pathological processes, and sialic acid residues within these structures are often used as biomarkers. Mass spectrometry is a widely utilized tool for glycan structural analysis. However, sialic acid is prone to elimination during the sample preparation and the activation process in tandem mass spectra, resulting in a loss of information on sialylation. Consequently, the identification of sialic acid linkages presents a significant analytical challenge. One established method for differentiating α2 → 3- and α2 → 6-linked sialic acids involves esterification followed by ammonia treatment. In this process, the carboxyl group of α2 → 3-linked sialic acids is converted into an amide, while α2 → 6-linked sialic acids are transformed into esters, resulting in distinguishable molecular weights. However, partial conversion of α2 → 6-linked sialic acids to amides and α2 → 3-linked sialic acids to esters has been observed, which reduces the reliability of this differentiation approach.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>A simple tandem mass spectrometry, based on the dissociation mechanisms of hexose and <i>N</i>-acetylhexosamine, is proposed to differentiate α2 → 3 and α2 → 6 sialic acid linkages after esterification and amidation.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>Various oligosaccharides consisting of sialic acid with α2 → 3 or α2 → 6 linkages were studied. For some oligosaccharides, the amidation for α2 → 3 linked sialic acid and esterification for α2 → 6 linked sialic acid are nearly complete, while partial amidation for α2 → 6 linked sialic acid and partial esterification for α2 → 3 linked sialic acid for other oligosaccharides was found, suggesting differentiation cannot be solely dependent on the amidation and esterification (or molecular weights). We showed that the α2 → 3 and α2 → 6 linked sialic acids after esterification/amidation can be distinguished by a simple tandem mass spectrometry.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>The proposed tandem mass spectrometry enables accurate differentiation of α2 → 3 and α2 → 6 sialic acid linkages, even when both of them undergo amidation or esterification.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"40 3","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145385198","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":"In Vitro Metabolite Profiling of 4,4-Diaminodiphenylmethane Using Human Liver S9 Fractions and LC-Orbitrap HRMS: In Silico Toxicity Studies of Its Metabolites","authors":"Sridhar Chinthakindi,&nbsp;Radhika Kawathe,&nbsp;Leela Sairam Andhela","doi":"10.1002/rcm.10164","DOIUrl":"https://doi.org/10.1002/rcm.10164","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>4,4-Diaminodiphenylmethane (MDA) is an aromatic amine classified as a Group 2B carcinogen. MDA is widely used as a key ingredient in industrial and consumer products such as epoxy resins, polyurethanes, and dyes. Given its widespread use and potential for occupational and environmental exposure, understanding its hepatic metabolism is crucial in elucidating the toxicological profiles of MDA in humans. However, a limited number of metabolites have been reported in the literature. To address this gap, we conducted a comprehensive metabolite profiling study to identify and characterize all possible in vitro metabolites of MDA.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methodology</h3>\u0000 \u0000 <p>In vitro hepatic metabolism studies were conducted using pooled human liver S9 fractions to stimulate the metabolism of MDA in humans. An untargeted metabolite profiling approach was employed using an LC-Orbitrap-HRMS. Data processing and identification of metabolites were performed using the Compound Discoverer software. A targeted LC–MS/MS method was employed to find the relative abundances of metabolites at various incubation times. In silico toxicity prediction of MDA-derived metabolites was conducted using the ProTox 3.0 online tool.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>A total of twelve MDA-derived metabolites were successfully identified, reflecting both Phase I (hydroxylation, desaturation, oxidative deamination) and Phase II (acetylation, sulfation, glucoside conjugation) biotransformation pathways. Among these, N-acetylated and desaturation intermediate-related metabolites were the most abundant. Based on these findings, an in silico toxicological report for the metabolites was proposed.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>The Orbitrap LC-HRMS platform enabled comprehensive identification and characterization of in vitro hepatic metabolic profiles of MDA. The predicted toxicological profiles and the discovery of additional metabolite formation beyond the known acetylation pathway provided new insights that can enhance toxicological risk assessment of MDA.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"40 3","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145385199","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":"Integrative Approach Based on DI-MS and LC–MS/MS Analysis for Comprehensive Characterization of Flavonoid Glycoside Isomers From Onychopetalum periquino (Annonaceae)","authors":"Ana Paula A. Castro,&nbsp;Bruna R. de Lima,&nbsp;Rebeca dos S. França,&nbsp;Brenda R. C. Leocadio,&nbsp;Francinaldo A. da Silva-Filho,&nbsp;Carromberth C. Fernandes,&nbsp;Afonso D. L. de Souza,&nbsp;Hector H. F. Koolen,&nbsp;Maria L. B. Pinheiro,&nbsp;Felipe M. A. da Silva","doi":"10.1002/rcm.10163","DOIUrl":"10.1002/rcm.10163","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>Currently, mass spectrometry–based approaches constitute the primary strategy for the dereplication of flavonoid glycosides; however, strategies focused on the dereplication of their isomers are still scarce. On the other hand, although flavonoid glycosides frequently occur in the leaves of the Annonaceae family, some species, such as <i>Onychopetalum periquino</i>, remain understudied on this topic.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>The aqueous extract from the leaves of <i>O. periquino</i> was filtered through celite and eluted with methanol. The methanol fraction was analyzed by DI-MS in data-dependent acquisition (DDA) mode with neutral loss scans for flavonoid glycosides recognition. Finally, a set of presumable flavonoid glycosides isomers was analyzed by LC–MS/MS and dereplicated through manual interpretation of MS/MS spectra.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>DI-MS analysis revealed the presence of flavonoid glycoside isomers, primarily derived from apigenin, luteolin, and quercetin, which were duly dereplicated through LC–MS/MS analysis as follows: vitexin (<b>1</b>), isovitexin (<b>2</b>), apigenin 7-<i>O</i>-glucoside (<b>3</b>), luteolin 6-<i>C</i>-glucoside (<b>4</b>), luteolin 8-<i>C</i>-glucoside (<b>5</b>), luteolin 7-<i>O</i>-glucoside (<b>6</b>), isoscoparin (<b>7</b>), chrysoeriol 7-<i>O</i>-glucoside (<b>8</b>), diosmetin 7-<i>O</i>-glucoside (<b>9</b>), apigenin 8-<i>C</i>-neohesperidoside (<b>10</b>), apigenin 6-<i>C</i>-neohesperidoside (<b>11</b>), apigenin 7-<i>O</i>-rutinoside (<b>12</b>), quercetin 3-<i>O</i>-glucoside-7-<i>O</i>-rhamnoside (<b>13</b>), and quercetin 3-<i>O</i>-rutinoside (<b>14</b>).</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusion</h3>\u0000 \u0000 <p>This study demonstrated the efficacy of the proposed strategy in identifying and differentiating flavonoid glycoside isomers in <i>O. periquino</i> leaves. Therefore, this workflow is an effective approach for the comprehensive characterization of flavonoid glycoside isomers in future dereplication works. Additionally, it showed how structural differences, such as the type of linkage and position of sugars, influence their fragmentation patterns.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"40 2","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145375398","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":"An Efficient Solid Phase Extraction Method for Purification and Analysis of Compound-Specific Plant Sugar Stable Hydrogen Isotope Values","authors":"Selina Hugger,&nbsp;Meisha Holloway-Phillips,&nbsp;Ansgar Kahmen,&nbsp;Daniel B. Nelson","doi":"10.1002/rcm.10161","DOIUrl":"10.1002/rcm.10161","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>The stable hydrogen isotope composition (<i>δ</i>²H) of plant compounds can serve as environmental or metabolic proxies, but interpretations are hindered by insufficient mechanistic understanding. This can be improved by analyzing the <i>δ</i>²H values of metabolic intermediates, such as sucrose, which is the direct substrate of cellulose and a main transport sugar. However, current preparation methods for carbohydrates in general and sucrose in particular are not time-efficient.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>We evaluated methods that use acetylation of soluble carbohydrate plant extracts to aid in purification as well as isotopic analysis of plant sugars such as sucrose. Extracts were obtained using either hot water or hot 80% ethanol. Acetylated extracts were then purified using an established liquid–liquid separation (LL) method or a new solid phase extraction (SPE) method that we developed. We also evaluated glucose produced from starch after enzymatic digestion. Method performance was evaluated based on quantified yields and the impact on measured <i>δ</i>²H values.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>Acetylated sucrose and starch-derived glucose were sufficiently resolved for gas chromatography in all cases. No isotopic biasing was detected for any method. Acetylated sucrose yields differed among methods, with 80% ethanol resulting in approximately threefold higher extraction yield compared to water, and SPE giving smaller but still sufficient yields compared to LL. Sample throughput was doubled with the SPE method compared to the LL method, which allows for larger batch sizes compared to LL.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>We developed an efficient method to analyze compound-specific plant carbohydrate <i>δ</i>²H values using gas chromatography-isotope ratio mass spectrometry (GC-IRMS). This can be applied in experiments aimed at investigating the processes that shape cellulose <i>δ</i>²H values, including deconvoluting the metabolic and hydro-climatic sources of isotopic variation.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"40 2","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12560618/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145375430","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}