Journal of the American Society for Mass Spectrometry最新文献

{"title":"Direct Analysis of Basic Dyes and Photodegradation Products in Blue Ballpoint Inks via Desorption Electrospray Ionization Mass Spectrometry","authors":"Morgan L. Demmler,&nbsp;Hannah S. Soltiz,&nbsp;Nelson R. Vinueza","doi":"10.1021/jasms.6c00158","DOIUrl":"https://doi.org/10.1021/jasms.6c00158","url":null,"abstract":"<p>Desorption electrospray ionization mass spectrometry(DESI-MS)is a useful ambient ionization technique for ink analysis, offeringrapid characterization of dyes with minimal sample destruction─acritical requirement for forensic evidence. While DESI-MS preservessamples in their native state, its utility in monitoring ink degradationduring accelerated weathering has remained largely unexplored. Inthis study, written samples from six blue ballpoint pens were subjectedto accelerated weathering using the AATCC TM169-2025 to simulate exposureto semitropical and semiarid outdoor climates and were analyzed viaDESI-MS. Five primary dyes─Basic Violet 1, 3, and 4 and BasicBlue 7 and 26─were identified along with their respective photodegradationproducts. The results demonstrate that most dyes follow a linear degradationtrend over time, establishing DESI-MS as a viable tool for the temporalprofiling of questioned documents.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 10","pages":"2357–2367"},"PeriodicalIF":2.9,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149093563","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 Personal Perspective on the Technological and Commercial Development of Nanospray and Nanobore LC-MS","authors":"Gary A. Valaskovic","doi":"10.1021/jasms.6c00124","DOIUrl":"https://doi.org/10.1021/jasms.6c00124","url":null,"abstract":"<p>Flow-rate-minimized electrospray ionization, commonlyreferredto as nanoelectrospray or, more simply, nanospray, has evolved intoan essential foundational technology in the development and proliferationof mass spectrometric-based proteomic analysis. Historically, nanospraywas an offline technique, termed herein as static nanospray. Staticnanospray paired well with the leading protein purification methodof the day: two-dimensional polyacrylamide gel electrophoresis (PAGE).The demands of analyzing ever more complex samples have evolved rapidlywith the introduction of LC-based methodologies. The introductionof shotgun proteomics technology, taking inspiration from the developmentof shotgun-based genomic sequencing, enabled the analysis of whole-cellprotein digests in a single LC-MS run. As mass spectrometry continuedto improve in both sensitivity and speed over the decades, concomitantadvances in nanobore LC column technology and emitter performancehave occurred. Over the past 30 years, we have been fortunate to seesensitivity gains progress from isolated PAGE gel bands to single-cellproteomics. Here, I offer a personal perspective on the evolutionof nanospray and nanobore LC-MS technology and on the journey of bringingthese tools from the bench to the global scientific community throughcommercialization.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 10","pages":"2261–2272"},"PeriodicalIF":2.9,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124642","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":"Correction to “Fluorinated Phenyl Sulfate Derivatives as Advanced Thermometer Anions for Electrospray Ionization Tandem Mass Spectrometry”","authors":"Daiki Asakawa","doi":"10.1021/jasms.6c00349","DOIUrl":"https://doi.org/10.1021/jasms.6c00349","url":null,"abstract":"","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 10","pages":"2638–2639"},"PeriodicalIF":2.9,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124832","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":"δ13C Determination of Benzoic Acid by High-Resolution Orbitrap MS: How Sample Introduction Strategy Governs Accuracy and Precision","authors":"Giovanni B. Bevilaqua,&nbsp;Hugo G. Machado,&nbsp;Júlio C. O. Ribeiro,&nbsp;Nerilson Marques Lima,&nbsp;Alexandre A. Ferreira,&nbsp;Ygor S. Rocha,&nbsp;Gabriel F. dos Santos,&nbsp;Boniek Gontijo","doi":"10.1021/jasms.6c00221","DOIUrl":"https://doi.org/10.1021/jasms.6c00221","url":null,"abstract":"<p>Stablecarbon isotope ratio measurements (δ¹³C)are traditionally performed by isotope ratio mass spectrometry (IRMS),but recent advances in high-resolution Orbitrap mass spectrometry(Orbitrap MS) enable molecular-level isotope ratio analyses withoutconversion to simple gases. Here, we systematically evaluate and comparethree sample-introduction strategies for Orbitrap-MS-based δ¹³C determination of benzoic acid─dual-inlet (DI), single-inlet(SI), and automated HPLC flow-injection (column-free mode)─assessinghow each governs measurement accuracy and precision. Analyses wereperformed using paired injections of an isotopically certified benzoicacid reference (IAEA-601) and a benzoic acid sample previously characterizedby elemental analysis–IRMS (EA-IRMS), following a seven-blockbracketing sequence (Ref-Smp-Ref-Smp-Ref-Smp-Ref) to minimize temporaldrift and to generate within-run triplicates. Across all configurations,high analytical precision was achieved, within-block relative standarderror (σ_RSE) consistently below approximately 0.6‰.Under DI conditions, replicate means closely approached the EA-IRMSbenchmark (−27.77‰), with residuals of −0.40to +0.50‰ on the Exploris 240 and −0.58 to −2.73‰on the Q Exactive. SI analysis enabled the acquisition of a highernumber of individual scans per block, contributing to lower σ_RSE (approximately 0.50–0.65‰) but exhibitedlarger accuracy offsets (residuals up to approximately 1–3‰),indicating greater susceptibility to systematic bias. Automated HPLCinjection on the Exploris 240, optimized for concentration and AGC(50 μmol L^–1 and 2.5 × 10⁵, respectively), delivered δ¹³C values of 28.1‰,−27.19‰, and −27.79‰ (residuals of approximately0.20–0.45‰) with no significant differences among replicatemeans (ANOVA/Tukey, 95% confidence level). Collectively, these findingsconfirm Orbitrap-MS as a reliable alternative to IRMS for δ¹³C analysis of benzoic acid, and reveal that the choice ofinjection strategy is the primary determinant of the accuracy–precision–throughputbalance achievable with this platform.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 10","pages":"2472–2482"},"PeriodicalIF":2.9,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124650","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":"Inline HIC-HRPF Enables Conformer-Specific Structural Analysis of Apo and Holomyoglobin","authors":"Godson I. Orachor,&nbsp;Ajay Sharma,&nbsp;Sandeep K. Misra,&nbsp;Joshua S. Sharp","doi":"10.1021/jasms.6c00291","DOIUrl":"https://doi.org/10.1021/jasms.6c00291","url":null,"abstract":"<p>Hydroxylradical protein footprinting (HRPF) is a method for proteinhigher-order structure analysis that oxidizes solvent-accessible sidechains of amino acids. One major limitation of HRPF is that resultsrepresent an ensemble average of all conformers in solution, preventingresolution of conformationally heterogeneous systems. Here, we establishedan inline hydrophobic interaction chromatography (HIC)-HRPF workflowthat enables conformer-specific labeling while correcting for gradient-dependentdifferences in radical scavenging. Significant radical scavengingdisparity exists between ammonium sulfate and phosphate buffers, andwe compensated for this with 7 mM HEPES supplementation, restoringeffective radical dose parity across the gradient. Using apo and holomyoglobinas a benchmark, we achieved baseline chromatographic separation ofconformers. Multi-dose HRPF revealed conformer-specific oxidationpatterns: apomyoglobin displayed enhanced labeling in peptide 81–97,specifically residue H83, consistent with destabilization of the F-helixand opening of the heme pocket, while holomyoglobin exhibited increasedoxidation in peptide 120–154 corresponding to M132, E137, andL138, suggesting hinge-like rearrangements in the H-helix upon hemeincorporation. These results validate inline HIC-HRPF as a robust,conformer-specific probe of higher-order structure and highlight thenecessity of scavenging parity across the gradient for reliable structuralinterpretation. The method establishes a framework for extending HRPFto dynamic conformationally heterogeneous systems resolvable by HIC.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 10","pages":"2542–2551"},"PeriodicalIF":2.9,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149093531","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":"Cross-Platform Consistency of FAIMS Compensation Voltage Optimization in Modern Orbitrap Mass Spectrometers","authors":"Siwen Zhang,&nbsp;Joao A. Paulo","doi":"10.1021/jasms.6c00307","DOIUrl":"https://doi.org/10.1021/jasms.6c00307","url":null,"abstract":"<p>High-Field Asymmetric Waveform Ion Mobility Spectrometry(FAIMS)enhances peptide identification in LC-MS proteomics, but whether optimalcompensation voltages (CVs) are transferable between mass spectrometryplatforms remains unclear. To address this gap, we used the PiercePeptide Retention Time Calibration (PRTC) mixture comprised of 15synthetic peptides and analyzed the CV transmission profiles acrossa wide voltage range (−85 to −25 V). We systematicallyevaluated FAIMS CV profiles across three modern Orbitrap mass spectrometers(Astral, Ascend, and Exploris 480), each equipped with different ionizationsources and chromatographic systems. Across the three platforms, optimalCVs were conserved within a narrow tolerance (typically ≤5V), supporting CV portability for routine method transfer under theconditions evaluated. Additionally, we observed that interplatformCV variability was greatest for peptides with strongly negative optimalCVs, consistent with the greater conformational sensitivity of highercharge-density ions under high-field FAIMS conditions. Together, theseresults suggest that FAIMS CV requirements are predominantly peptide-intrinsicproperties under typical bottom-up proteomics conditions and supportthe use of the PRTC mixture as a practical standard for routine FAIMScalibration and cross-platform quality control in proteomics laboratories.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 10","pages":"2577–2584"},"PeriodicalIF":2.9,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149093564","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":"Nanobubbles in Bulk Solution and Electrosprayed Microdroplets Accelerate Chemical Reactions","authors":"Bincy Binny,&nbsp;George Joseph,&nbsp;Andre R. Venter","doi":"10.1021/jasms.6c00359","DOIUrl":"https://doi.org/10.1021/jasms.6c00359","url":null,"abstract":"<p>Bulknanobubbles (NBs) are metastable gas-filled voids in solution,with diameters of nearly 200 nm that exhibit long lifetimes and largesurface-to-volume ratios. Recent studies have shown that chemicalreactions are significantly accelerated within sprayed microdropletsduring electrospray ionization mass spectrometry (ESI-MS). Althoughseveral factors, such as partial solvation of reagents, electric fields,ordered orientation, and pH, have been implicated in the accelerationin microdroplets, the primary governing factor remains unclear anddependent on the system. Similar processes occur on the nanobubble–liquidinterface, leading to enhanced reaction rates when they are presentin bulk solution. We demonstrate reaction rate acceleration by deliberatelyadding NBs to the bulk solution and microdroplets by considering twomodel systems: the Katritzky transamination reaction and the reactionbetween CO₂ and <em>N</em>,<em>N</em>-dibutyl-1,3-propanediamine (DBPA). N₂ and CO₂ nanobubbles weregenerated using sonication, pressure cycling (PC), or the Tesla valve(TV) and delivered as bulk or spray solvents. The Katritzky reactionin bulk solution with NB-enriched solvent systems was examined bymass spectrometry under nonaccelerating electrospray conditions. Theacceleration factor (AF) for the reaction doubled compared with thecontrol. On the other hand, the microdroplet accelerated the Katritzkyreaction, with N₂ NB producing a further six-fold accelerationcompared to the microdroplet control. For the reaction of the diamineDBPA with N₂ nebulization, CO₂ reagent deliveryby NB resulted in acceleration factors between 2 and 50 compared tothe microdroplet reaction control, depending on the solvent fraction,wherein bubbles were generated. With CO₂, nebulizationwhere ample reagent is already present, the addition of NBs produceda further two-to-five-fold acceleration factor depending on the solventfraction in which NBs were generated, indicating a NB catalytic effect.Our findings show that NBs improve reaction kinetics by acting bothas improved reagent delivery vehicles and/or as catalysts. Catalyticactivity is a consequence of increased liquid–air interfacialsurface area and improved reagent transport in bulk solution and withinmicrodroplets.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 10","pages":"2609–2617"},"PeriodicalIF":2.9,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149093567","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":"Deep Ultraviolet Laser Ablation Surface Sampling for Native Mass Spectrometry","authors":"Neda Feizi,&nbsp;Kadeem O. Hayes,&nbsp;Kelcey B. Hines,&nbsp;Raul A. Villacob,&nbsp;Kermit K. Murray,&nbsp;Touradj Solouki","doi":"10.1021/jasms.6c00185","DOIUrl":"https://doi.org/10.1021/jasms.6c00185","url":null,"abstract":"<p>A pulsed 193 nm deep ultraviolet (DUV) laser was usedto ablateproteins and a noncovalently bound protein assembly deposited on surfaces.DUV laser ablation has been used for ablation of proteins from surfaceswithout fragmentation; however, DUV ablation of native proteins fromsurfaces without the loss of higher-order structure of proteins hasnot been demonstrated. Here, protein charge state distribution (CSD)and collision-induced unfolding (CIU) were used to probe the structureof DUV laser-ablated native proteins. Standard solutions containingnative bovine serum albumin (BSA), jack-bean concanavalin A (ConA),and bovine carbonic anhydrase (CA) were deposited on a quartz microscopeslide, laser-ablated, and captured for ion mobility-mass spectrometry(IM-MS) analysis. Observed CSD from native MS of conventionally extractedand DUV laser-ablated proteins were comparable. CIU plots for allcharge states of laser-ablated proteins exhibited the same ion mobilityfeatures and comparable transition voltages (CIU50) as the extractedsamples. These results suggest that DUV laser ablation can yield intactproteins with conserved higher-order structures.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 10","pages":"2388–2395"},"PeriodicalIF":2.9,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149093677","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":"Setting the STORI Straight: Improved Signal Processing for Charge Detection Mass Spectrometry","authors":"Michael P. Goodwin,&nbsp;Dmitry Grinfeld,&nbsp;Ping Yip,&nbsp;Kyle P. Bowen,&nbsp;Liangxuan Fu,&nbsp;Jared O. Kafader,&nbsp;Neil L. Kelleher,&nbsp;Michael W. Senko","doi":"10.1021/jasms.6c00256","DOIUrl":"https://doi.org/10.1021/jasms.6c00256","url":null,"abstract":"<p>Charge detection mass spectrometrydepends on the accurate measurementof both the <em>m</em>/<em>z</em> and charge of individualions. While the selective temporal overview of resonant ions (STORI)approach is a powerful tool for determining ion charges, its originalimplementation lacked the ability to account for errors or shiftsin an ion’s frequency during measurement. The misSTORI algorithmwas developed as an extension of STORI, providing significant improvementsto charge determination in a variety of scenarios. The algorithm ofmisSTORI is presented here in more detail, demonstrating how smallchunks of the frequency domain around a signal of interest can beutilized to extract a given ion’s charge and any relevant informationabout its appearance, disappearance or mass shifting during its acquisition.Various examples are provided which demonstrate the power of misSTORIin both improving the accuracy of charge measurements and revealinginteresting properties of ion behavior inside the mass spectrometer.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 10","pages":"2497–2510"},"PeriodicalIF":2.9,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149093655","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":"Modeling Energy Transfer Efficiency in Collision-Induced Dissociation and Unfolding Using Molecular Dynamics Simulations","authors":"Austin W. Green,&nbsp;James S. Prell","doi":"10.1021/jasms.6c00292","DOIUrl":"https://doi.org/10.1021/jasms.6c00292","url":null,"abstract":"<p>Collisional activation is available ubiquitously in commercialmass spectrometers, but, due to differences in instrumentation, itcan be difficult to “translate” instrument settingsfrom one instrument in a collisional activation experiment to anotherinstrument to achieve quantitatively predictable results. With thegoal of a more universal understanding and translatability of collision-induceddissociation and unfolding (CID/U) experiments, we recently introducedsoftware (“IonSPA”) for simulating ion heating, cooling,and kinetic energy damping during collisional activation. A key parameterin IonSPA is the “pseudo-atom mass”, which controlsthe efficiency of energy transfer between an ion’s vibrationalmodes and the gas particle on a collision-by-collision basis. Here,we use molecular dynamic (MD) simulations to study energy transferefficiency for native charge states of three different protein ions.Energy transfer efficiency is found to depend primarily on the collisiongas type, relative speed of the collision, and total vibrational energyof the ion. Efficiency trends toward unity (completely inelastic andthermalizing) at zero collision speed, decreases to a minimum at amoderate collision speed, and increases again toward highly inelasticat high collision speeds. Dependence on collision geometry and therole of the centrifugal barrier and interaction potential are alsoexplored. A pseudo-atom mass function based on gas type, ion vibrationaltemperature, and collision speed is derived from these MD simulationsand implemented into IonSPA to calculate thermochemical barrier valuesin CID and CIU.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"37 10","pages":"2552–2564"},"PeriodicalIF":2.9,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149093610","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}