Journal of the American Society for Mass Spectrometry最新文献

{"title":"Isotope-Coded Derivatization Enables Accurate LC–MS/MS Quantification of Urinary THC–COOH without Isotope-Labeled Cannabinoid Standards","authors":"Maiko Kusano,&nbsp;Shimba Kawasue,&nbsp;Yu-ki Sakamoto,&nbsp;Mahiro Yoshida,&nbsp;Taka-aki Matsuyama","doi":"10.1021/jasms.6c00110","DOIUrl":"10.1021/jasms.6c00110","url":null,"abstract":"<p>Quantitative determination of 11-nor-9-carboxy-Δ⁹-tetrahydrocannabinol (THC–COOH) in urine is the internationallyaccepted approach for verifying cannabis use in forensic toxicology.Accurate liquid chromatography–tandem mass spectrometry (LC–MS/MS)analysis typically relies on stable isotope-labeled internal standards;however, isotope-labeled cannabinoid reference materials are costly,tightly regulated, and not uniformly accessible across laboratories.We report an isotope-coded derivatization (ICD) strategy that enablesisotope-dilution–equivalent quantification of urinary THC–COOHwithout reliance on commercially available isotope-labeled cannabinoidstandards. THC–COOH was derivatized with isopropyl-piperidinecarboxylic acid hydrazide (IPPAH) and its deuterated analogue (IPPAH-<em>d</em>₆), generating a chemically matched analyte/internalstandard pair through parallel derivatization. The derivatives exhibitedstable chromatographic coelution and closely matched ionization behaviorunder positive electrospray ionization. Quantitative LC–MS/MSanalysis demonstrated linearity over 1–500 ng/mL (r² &gt; 0.999), with intra- and interday accuracy of 81.8–108.6%and precision below 10%. Internal standard–normalized matrixfactors ranged from 97–109% with minimal variability, indicatingeffective compensation for matrix effects. This compensation enabledreliable quantification without extensive sample cleanup, allowinga simplified sample preparation workflow compared with conventionalmethods. Derivatized samples remained stable for at least 72 h inthe autosampler without detectable isotopic exchange. This ICD strategyprovides a quantitatively reliable alternative to conventional isotopedilution while eliminating dependence on isotope-labeled cannabinoidstandards, thereby expanding the accessibility of high-confidenceLC–MS/MS quantification and illustrating the broader potentialof isotope-coded derivatization in forensic mass spectrometry.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 8","pages":"1840–1847"},"PeriodicalIF":2.9,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148306500","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":"Role of Ion Charge and Size in Susceptibility to Acoustic Ion Manipulation (AIM)","authors":"Julia L. Danischewski,&nbsp;Joshua S. Wiley,&nbsp;Yi You,&nbsp;Josefin Hufgard,&nbsp;Jens Riedel,&nbsp;Jacob T. Shelley","doi":"10.1021/jasms.6c00048","DOIUrl":"10.1021/jasms.6c00048","url":null,"abstract":"<p>The recent coupling of electrospray ionization (ESI)with acousticion manipulation (AIM) has expanded the range of ionic species thatcan be successfully controlled with an acoustic field. The use ofa drying tube was critical to this process to ensure sufficient desolvationand enable the strongest AIM interaction. Here, we explore how desolvationof small-molecule and protein ions impacts the AIM process in moredetail. Specifically, acoustic gating of ions from ubiquitin, cytochromec, and a standard mass calibration mixture was studied for dryingtube temperatures from 30 to 210 °C. Transmission of an ion beamtrajectory through an acoustic antinode has been previously establishedas a reliable and simple measure for the acoustic-ion interactioncross section. The transmission of different charge states of proteinions was found to be heavily temperature dependent. This unique observationenabled exploration of the potential impact of different ESI mechanismson the availability of ions for AIM interactions. The behaviors ofsingly charged and multiply charged ions traversing a standing acousticwave were compared and suggest that the electrostatic properties,as well as the resulting higher-order structure, of ions at leastpartially explain AIM behaviors. Additionally, the increased desolvationtemperature led to ion transmission values consistent with dry, plasma-producedions (i.e., less than 5%) across all species tested. The use of ahigher drying temperature ultimately further optimized ESI-AIM, aswell as highlighted the role of ion properties during the AIM phenomenon.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 8","pages":"1729–1732"},"PeriodicalIF":2.9,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148395558","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":"Special Issue in Honor of Jack Henion, Recipient of the 2025 John B. Fenn Award for Distinguished Contribution in Mass Spectrometry","authors":"Erin S. Baker,&nbsp;Richard A. J. O’Hair","doi":"10.1021/jasms.6c00290","DOIUrl":"10.1021/jasms.6c00290","url":null,"abstract":"","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 8","pages":"1685–1690"},"PeriodicalIF":2.9,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148676817","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":"Characterization of Alkane Oxidation Products in a Corona-Discharge Reactor Using Ammonia-Doped Ion Mobility–Mass Spectrometry","authors":"Priyanka Kumari,&nbsp;Younes Valadbeigi,&nbsp;Vahideh Ilbeigi,&nbsp;Štefan Matejčík","doi":"10.1021/jasms.6c00175","DOIUrl":"10.1021/jasms.6c00175","url":null,"abstract":"<p>This study examines the oxidation of C₅–C₈ alkanes in an external corona-discharge reactor. Oxidationproducts were characterized using ion mobility spectrometry (IMS)and tandem IMS–mass spectrometry (IMS-MS) with an internalcorona-discharge APCI source. This configuration enables structuralisomer resolution and provides deeper insight into the molecular compositionof the oxidation products. IMS-MS analysis showed that alkane (M)oxidation produces mainly ketones ([M+O–2H]) and diketones([M+2O–4H]), with 3-ketone isomers dominating. Under standardAPCI conditions, H⁺(H₂O)<em>_n</em> reactant ions protonated these products, generating complexIMS spectra for [M+O-2H].H⁺ and [M+2O-4H].H⁺. Introducing NH₃ as a dopant shifted the primary reactantion to NH₄⁺(H₂O)<em>_n</em>, forming [M+O–2H]. NH₄⁺ and[M+2O–4H].NH₄⁺ adducts with similar collisioncross sections. This simplified the IMS spectra to a single peak,enhanced sensitivity, and improved suitability for analytical applications.Using this approach, quantitative analysis of selected alkanes yieldeddetection limits of 0.01–0.1 ppm_v.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 8","pages":"1990–2002"},"PeriodicalIF":2.9,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148358856","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 Robotic Sample Handling Platform for Fully Automated Nanospray Desorption Electrospray Ionization Mass Spectrometry Imaging","authors":"Li-Xue Jiang,&nbsp;Emerson Hernly,&nbsp;Benjamin W. Cerjan,&nbsp;Mushfeqa Iqfath,&nbsp;Tommy Zhang,&nbsp;Julia Laskin","doi":"10.1021/jasms.6c00089","DOIUrl":"10.1021/jasms.6c00089","url":null,"abstract":"<p>Recentadvances in mass spectrometry imaging (MSI) haveenabledhigh-throughput experiments, making it possible to image multiplesamples and perform three-dimensional molecular mapping. For theseapplications, automated sample handling is critical. Here, we presentthe first fully automated nanospray desorption electrospray ionization(nano-DESI) MSI platform that integrates robotic sample handling withautomated sample recognition system. A robotic arm, controlled byour custom LabVIEW program, automatically places samples onto a sampleholder and removes them after the analysis. The sample holder, mountedon a motorized XYZ stage, is automatically transferred to a mass spectrometerfor imaging. A newly developed on-site sample region recognition systemenables on-the-fly identification of sample coordinates and transfersthem to LabVIEW, which plans and executes the imaging experiment.A microfluidic nano-DESI probe (MFP) was used due to its robustnessand high-throughput capability. Shear force feedback distance controlwas incorporated into the MFP to address height variations acrossmultiple glass slides. Using this system, five mouse brain tissuesections on two glass slides were imaged sequentially with high reproducibilityand consistency, without human intervention. These results demonstratethe feasibility and performance of a fully automated nano-DESI MSIworkflow, paving the way for multisample and three-dimensional MSIexperiments.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 8","pages":"1833–1839"},"PeriodicalIF":2.9,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148366511","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":"Manipulation of Electrospray-Produced Biomolecular Ions with Acoustic Fields at Atmospheric Pressure","authors":"Julia L. Danischewski,&nbsp;Yi You,&nbsp;Josefin Hufgard,&nbsp;Joshua S. Wiley,&nbsp;Jens Riedel,&nbsp;Jacob T. Shelley","doi":"10.1021/jasms.6c00198","DOIUrl":"10.1021/jasms.6c00198","url":null,"abstract":"<p>Thecoupling of electrospray ionization (ESI) with the newly discoveredacoustic ion manipulation (AIM) phenomenon is demonstrated for biopolymericions, including peptides, proteins, and oligonucleotides. It is shownthat large (i.e., up to ca. 29 kDa) and multiply charged ions areinfluenced by the presence of acoustic fields. Specifically, we demonstratethe ability to gate, modulate, redirect, and focus these biomolecularions with an acoustic field. To ensure effective acoustic controlof ESI-generated ions, it was necessary to desolvate the electrospraydroplets and ions prior to the AIM field through optimization of dryingtube temperature and spray gas pressure. In general, small and highlycharged ions were more readily deflected from the unstable antinoderegion toward the acoustic nodes. This trend extended to a charge-state-dependentbehavior for protein ions, where higher-charge ions of the same moleculewere redirected more easily than their lower-charge counterparts.This work lays a foundation for the implementation of AIM in the studyof biomolecules as well as other analytes introduced by ESI to ion-basedspectroscopic techniques, such as mass spectrometry and ion mobilityspectrometry.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 8","pages":"1733–1743"},"PeriodicalIF":2.9,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148395560","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":"Strategy for Simultaneous Multiomic Survey of N-Glycomic and Extracellular Matrix Proteome by Mass Spectrometry Imaging","authors":"Harrison B. Taylor,&nbsp;Jade K. Macdonald,&nbsp;Walter K. Myers,&nbsp;Noah Bonnheim,&nbsp;Anand S. Mehta,&nbsp;Richard R. Drake,&nbsp;Christopher Hernandez,&nbsp;Jeffrey C. Lotz,&nbsp;Aaron Fields,&nbsp;Bärbel Rohrer,&nbsp;Peggi M. Angel","doi":"10.1021/jasms.6c00146","DOIUrl":"10.1021/jasms.6c00146","url":null,"abstract":"<p>Recent advances in spatially resolved molecular profilinghavepositioned matrix-assisted laser desorption/ionization mass spectrometryimaging (MALDI-MSI) as a powerful platform for multiomic tissue analyses.However, conventional workflows that sequentially target distinctmolecular classes are time- and resource-intensive, requiring repeatedsequential sample preparation, imaging, and data integration. Here,we evaluate streamlined strategies for simultaneous or combined acquisitionof N-glycan and collagen-derived peptide information using PNGaseF and collagenase. In-solution studies demonstrate that simultaneousenzymatic digestion yields comparable peptide identifications andglycan profiles relative to traditional sequential workflows, withminimal impact on enzymatic specificity. On the basis of these findings,we developed and optimized MALDI-MSI protocols enabling either simultaneousenzyme application or sequential enzyme treatment with unified matrixdeposition and single-pass imaging. While direct coapplication reducedimage uniformity, a hybrid approach that used sequential enzyme depositionwith combined imaging preserved spatial fidelity and spectral qualitywhile significantly reducing processing and computational demands.Application to human tissues, including vertebral bone and ocularsamples, highlights the utility of this workflow for fragile specimensand exploratory multiomic surveys. Collectively, these results establisha framework for integrated glycomic and proteomic imaging targetingthe extracellular microenvironment, expanding multiomic MALDI-MSIanalyses.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 8","pages":"1931–1941"},"PeriodicalIF":2.9,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148403238","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":"Data-Independent Acquisition for Improved Compound Annotation in MALDI MS Imaging","authors":"Carmen Paschke,&nbsp;Kerstin Strupat,&nbsp;Carolin M. Morawietz,&nbsp;Karl-Christian Schaefer,&nbsp;Christoph Henrich,&nbsp;Bernhard Spengler","doi":"10.1021/jasms.6c00128","DOIUrl":"10.1021/jasms.6c00128","url":null,"abstract":"<p>Matrix-assisted laser desorption/ionization mass spectrometryimaging(MALDI MSI) enables spatial mapping of biomolecules within biologicaltissues, where conventional MS¹-based workflows often resultin ambiguous compound annotations. Data-dependent acquisition (DDA)can improve annotation specificity but is biased toward high-abundantions and lacks reproducibility. Here, we present a novel MALDI MSIworkflow integrating data-independent acquisition (DIA) to obtainboth spatial and fragmentation information. In this approach, MS¹ and DIA MS² spectra are acquired alternately acrossthe sample without prior knowledge of compound localization. Eachimage pixel consists of one MS¹ and several DIA MS² subpixels, providing both high spatial resolution for MS¹ data and broad <em>m</em>/<em>z</em> coverage.Using small, randomized <em>m</em>/<em>z</em> isolationwindows reduces spectral overlap and improves fragment-ion specificity.Data were processed using an extended Compound Discoverer, integratingmzCloud and LipidSearch for compound annotation. Applied to tissueof the parasitic worm <em>Fasciola hepatica</em>, this workflow produced detailed lipid maps and improved annotationconfidence by combining precursor-mass, DIA MS², and spatial-correlationinformation. Our results demonstrate that DIA offers a flexible strategyto integrate fragmentation information into MALDI MSI, expanding itscapabilities for spatial metabolomics.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 8","pages":"1890–1900"},"PeriodicalIF":2.9,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148417790","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":"Reference-Free Structure Elucidation of N–O Heterocyclic Ring Systems with Infrared Ion Spectroscopy: A Test Case of the Isoxazoline Insecticide Isocycloseram and Its MS/MS Fragment","authors":"Teun van Wieringen,&nbsp;Agisilaos Chantzis,&nbsp;Jos Oomens,&nbsp;Giel Berden,&nbsp;Mansoor Saeed,&nbsp;Simon J. Perry,&nbsp;Jonathan Martens","doi":"10.1021/jasms.6c00213","DOIUrl":"10.1021/jasms.6c00213","url":null,"abstract":"<p>Five-membered heterocyclic molecules with an N–Obond areemerging as active ingredients in the agrochemical and pharmaceuticalindustry. Characterization of these molecules in biological matricesis commonly done using liquid chromatography and mass spectrometry,which is not always diagnostic for the exact molecular structure.We demonstrate how infrared ion spectroscopy (IRIS) can be used tostructurally characterize the ions formed in mass spectrometry ona set of 12 isoxazolidinone analogues. Combining IRIS with quantum-chemicalmethods, we assign the gas-phase structure and show that most of theisoxazolidinone analogues protonate on the carbonyl oxygen. This approachis then extended to the isoxazoline insecticide isocycloseram, whichis much larger in size and possesses an IR spectrum that is more congested.In addition to “standard” harmonic frequency calculationsat the Density Functional Theory (DFT) level, we compare the experimentalspectrum to computations performed using Born–Oppenheimer moleculardynamics (BOMD), which implicitly accounts for anharmonicity and conformationaldynamics at the finite temperatures of the experiment. Collision-induceddissociation of protonated isocycloseram yields a low-intensity fragmention with the charge retained at the isoxazolinone; we assign its structureby comparing the IR spectrum of the fragment ion to the IR spectrafrom the set of small-molecule analogues.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 8","pages":"2015–2022"},"PeriodicalIF":2.9,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148547399","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":"Aziridination-Enabled Structural and Quantitative Lipidomics","authors":"Erin A. Hirtzel,&nbsp;Gopal Reddy Ramidi,&nbsp;Xin Yan","doi":"10.1021/jasms.6c00107","DOIUrl":"10.1021/jasms.6c00107","url":null,"abstract":"<p>Chemicalderivatization has long been employed to enhance the structuralcharacterization of lipids by mass spectrometry (MS). In recent years,olefin aziridination has emerged as a powerful and versatile strategyin lipidomics, driven by its ability to selectively target carbon–carbondouble bonds (C═C bonds) and to introduce nitrogen-containingfunctionalities that facilitate both structural elucidation and quantitativeanalysis. Aziridination-enabled MS approaches provide reliable C═Cbond localization through diagnostic fragmentation, while simultaneouslyimproving ionization efficiency, particularly for nonpolar lipid classes.A diverse range of aziridination chemistry has been developed, eachoffering distinct advantages for lipid analysis. In this review, wesummarize recent advances in aziridination-enabled MS methodologies,with an emphasis on reaction development and analytical performance.We further highlight applications across biological and complex samplesystems. These developments highlight aziridination-assisted MS asa powerful strategy for precision lipidomics with isomer-resolvedcapability and accurate quantification.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 8","pages":"1691–1704"},"PeriodicalIF":2.9,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148590035","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}