Dapeng Chen, Wayne A. Bryden, Michael McLoughlin, Scott A. Ecelberger, Timothy J. Cornish, Lara P. Moore, Kyle M. Regan
{"title":"digitalMALDI: A Single-Particle–Based Mass Spectrometric Detection System for Biomolecules","authors":"Dapeng Chen, Wayne A. Bryden, Michael McLoughlin, Scott A. Ecelberger, Timothy J. Cornish, Lara P. Moore, Kyle M. Regan","doi":"10.1002/jms.5110","DOIUrl":"10.1002/jms.5110","url":null,"abstract":"<div>\u0000 \u0000 <p>The development of a real-time system for characterizing individual biomolecule-containing aerosol particles presents a transformative opportunity to monitor respiratory conditions, including infections and lung diseases. Existing molecular assay technologies, although effective, rely on costly reagents, are relatively slow, and face challenges in multiplexing, limiting their use for real-time applications. To overcome these challenges, we developed digitalMALDI, a laser-based mass spectrometry system designed for single-particle characterization. digitalMALDI operates as a near real-time platform that directly samples aerosols, bypassing the need for complex and time-consuming sample preparation. To demonstrate the feasibility of this approach, intact insulin protein was used as a representative target. Results showed that digitalMALDI is capable of detecting 1 pg of insulin protein in single aerosol particles, suggesting that the system has a broad application for disease diagnosis, environmental monitoring, and biosecurity management.</p>\u0000 </div>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"60 2","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143006511","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}
Allen Martin, Alena N. Joignant, Matt Farrell, Antonio Planchart, David C. Muddiman
{"title":"Feasibility of IR-MALDESI Mass Spectrometry Imaging of PFAS","authors":"Allen Martin, Alena N. Joignant, Matt Farrell, Antonio Planchart, David C. Muddiman","doi":"10.1002/jms.5112","DOIUrl":"10.1002/jms.5112","url":null,"abstract":"<div>\u0000 \u0000 <p>Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are a class of emerging contaminants that have been in use industrially since the 1940s. Their long-term and extensive commercial use has led to their ubiquitous presence in the environment. The ability to measure the bioconcentration and distribution of PFAS in the tissue of aquatic organisms helps elucidate the persistence of PFAS as well as environmental impacts. Traditional analysis by LC–MS/MS can measure total PFAS concentrations within an organism but cannot provide comprehensive spatial information regarding PFAS concentrations within the organism. In the current study, we used infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) to determine the limit of detection (LOD) of several PFAS utilizing a commercial standard mix spotted on mouse liver tissue. The traditional ice matrix and an alternative matrix, 1,8-bis (tetramethylguanidino)naphthalene (TMGN), were explored when determining the limits of detection for various PFAS by IR-MALDESI. The ice matrix alone resulted in a higher response than the combination of TMGN and ice. The resulting LOD for perfluorooctane sulfonic acid (PFOS) on a per voxel basis was 0.16 fmol/voxel. For comparison, zebrafish that were exposed to perfluorooctanoic acid (PFOA), PFOS, and perfluorohexanesulfonic acid (PFHxS) at different concentrations were homogenized, and PFAS were extracted by solid–liquid extraction, purified by solid phase extraction, and analyzed by LC–MS/MS to determine the level of bioaccumulation in the zebrafish. PFOS resulted in the highest level of bioaccumulation (731.9 μg/kg, or 234.2 fg/voxel). A zebrafish that had been exposed to a PFAS mixture of PFOA (250 ng/L), PFOS (250 ng/L), and PFHxS (125 ng/L) was cryosectioned and analyzed by IR-MALDESI. Images could not be generated as the accumulation of PFAS in the sectioned tissue was below detection limit of the technique.</p>\u0000 </div>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"60 2","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142978896","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}
Long-Hua Zhou, Xing-Chen Lin, Li-Li Suo, Li-Fang Ma, Gui-Xiang Hu, Xiang Xia, Ming Li, Wei-Hua Huang, Yong-Jiu Jin
{"title":"Application of Online Multi-Internal Standard Calibration for Determination of Iodine by ICP-MS","authors":"Long-Hua Zhou, Xing-Chen Lin, Li-Li Suo, Li-Fang Ma, Gui-Xiang Hu, Xiang Xia, Ming Li, Wei-Hua Huang, Yong-Jiu Jin","doi":"10.1002/jms.5109","DOIUrl":"10.1002/jms.5109","url":null,"abstract":"<div>\u0000 \u0000 <p>This study presents a comprehensive evaluation of the application of online multi-internal standard calibration (M.ISC) in determining iodine concentrations through inductively coupled plasma mass spectrometry (ICP-MS). Notably, M.ISC streamlines the calibration process by requiring only a single standard solution, thereby enhancing sample throughput and minimizing liquid waste. In addition, unlike conventional internal standard (IS) methods, M.ISC omits the need for time-consuming species identification by utilizing multiple IS species simultaneously to minimize signal biases. The effectiveness of M.ISC was validated through the analysis of six standard reference samples, with the results of LOD and LOQ also being calculated by the error propagation approach. The traditional chemical analytical methods (TCAM), external standard calibration (EC) and single IS methods were also evaluated as comparative purpose. Nonetheless, M.ISC emerges as a straightforward matrix-correction strategy, offering a simple and efficient alternative to traditional calibration methods for iodine detection by ICP-MS.</p>\u0000 </div>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"60 1","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142931998","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":"Sodiation of Enhanced Green Fluorescent Protein (EGFP) in Basic Solution Studied by Electrospray Mass Spectrometry","authors":"Kenzo Hiraoka, Satoshi Ninomiya, Stephanie Rankin-Turner, Noa Suzuki, Satoko Akashi","doi":"10.1002/jms.5111","DOIUrl":"10.1002/jms.5111","url":null,"abstract":"<div>\u0000 \u0000 <p>In our previous work, the sodiation of melittin, cytochrome <i>c</i>, and ubiquitin in a 1 mM NaOH water/methanol solution was studied by electrospray mass spectrometry. It was suggested that the α-helix is more resistant to sodiation than the β-sheet. In this study, sodiation of enhanced green fluorescent protein (EGFP) composed of a β-barrel was studied in 1% CH<sub>3</sub>COOH (AcOH) or 1 mM NaOH water/methanol solution by electrospray mass spectrometry. Although EGFP was denatured in an acidic solution, it maintains a near-native structure in a basic solution. For the 1% AcOH solution, the protonated EGFP, [EGFP + nH − mH + mNa]<sup>n+</sup>, with <i>n</i> = 14 − 36 and <i>m</i> = 0 was detected. For 1 mM NaOH, the number <i>n</i> for [EGFP + nH − mH + mNa]<sup>n+</sup> was found to increase with the sodiation number <i>m</i> and vice versa for [EGFP + nH − mH + mNa]<sup>n−</sup>. Namely, Na<sup>+</sup> adducts counteract the negative charges of deprotonated acidic residues. The protonated EGFP detected as major ions for basic 1 mM NaOH was ascribed to the more surface-active H<sub>3</sub>O<sup>+</sup>(aq) than OH<sup>−</sup>(aq).</p>\u0000 </div>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"60 1","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142932002","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":"Cryogenic TOF-SIMS Around Sublimation Temperature of Quench-Condensed Noble Gas (Ne, Ar, and Kr) Films","authors":"Taku T. Suzuki","doi":"10.1002/jms.5107","DOIUrl":"10.1002/jms.5107","url":null,"abstract":"<div>\u0000 \u0000 <p>A possible TOF-SIMS analysis of surface phase transitions has recently been proposed for limited cases such as polymers and ionic liquids. In the present study, we have extended this analysis to quench-condensed noble gas films. The newly developed cryogenic TOF-SIMS allowed both measurements of TOF-SIMS below 4 K, and low-energy ion scattering spectroscopy that is used to prepare a clean surface. It was found that the TOF-SIMS intensity variation by increasing the temperature at a constant ramp rate (temperature-programmed TOF-SIMS) shows steep changes due to sublimation. Thus, the possibility of analyzing the surface phase transition at the local region defined by the incident ion beam of (cryogenic) TOF-SIMS was demonstrated in the present study.</p>\u0000 </div>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"60 1","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142877071","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}
Xianwen Lou, Michel van Houtem, René P. M. Lafleur, Sandra M. C. Schoenmakers, Joost L. J. van Dongen, Anja R. A. Palmans
{"title":"Bothersome Back Exchange in MALDI Plume and Its Impact on Hydrogen/Deuterium Exchange Mass Spectrometry Analysis","authors":"Xianwen Lou, Michel van Houtem, René P. M. Lafleur, Sandra M. C. Schoenmakers, Joost L. J. van Dongen, Anja R. A. Palmans","doi":"10.1002/jms.5108","DOIUrl":"10.1002/jms.5108","url":null,"abstract":"<p>One critical issue in hydrogen/deuterium exchange mass spectrometry (HDX MS) analysis is the deleterious back exchange. Herein, we report that when matrix-assisted laser desorption/ionization (MALDI) is used, the MALDI process itself can also cause significant back exchange. The back exchange occurred inside the reactive MALDI plume was investigated by depositing a fully deuterated sample prepared in D<sub>2</sub>O on top of a preloaded dried layer of matrix. A benzene-1,3,5-tricarboxamide (BTA) compound that can form supramolecular polymer in water and five peptides of angiotensin II (AT), pentaglycine (5G), pentaalanine (5A), cyclohexaglycine (C6G), and cyclohexaalanine (C6A) were selected as the testing compounds. Just like the situation in solution, the back exchange for the side chains and end groups is fast in the MALDI plume, while for the backbone amides, it is slow and dependent on the primary structure of the peptide. For the peptides tested, 5%–15% of D-labels in the backbone amides can be lost during the MALDI process. This degree of back exchange, although not an unbearable problem for most HDX MS applications as 85%–95% of the informative labels would still survive, could seriously limit the use of MALDI in the HDX MS analysis of supramolecular assemblies. For these assemblies, the EX1-like mechanism with two distinct distributions is common, and the back exchange could gravely distort or even merge the distinct isotopic distributions, which are the characteristic symbols of EX1.</p>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"60 1","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11664201/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142877023","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":"Ghost Peaks of Aromatic Metabolites Induced by Corona Discharge Artifacts in LC-ESI-MS/MS","authors":"Yayoi Hongo, Daisuke Fukuyama, Lee Chuin Chen, Kanako Sekimoto, Hiroshi Watanabe","doi":"10.1002/jms.5102","DOIUrl":"10.1002/jms.5102","url":null,"abstract":"<p>LC-ESI-MS/MS is a preferred method for detecting and identifying metabolites, including those that are unpredictable from the genome, especially in basal metazoans like <i>Cnidaria</i>, which diverged earlier than bilaterians and whose metabolism is poorly understood. However, the unexpected appearance of a “ghost peak” for dopamine, which exhibited the same <i>m/z</i> value and MS/MS product ion spectrum during an analysis of <i>Nematostella vectensis</i>, a model cnidarian, complicated its accurate identification. Understanding the mechanism by which “ghost peaks” appear is crucial to accurately identify the monoamine repertoire in early animals so as to avoid misassignments. Verification experiments showed that <i>in-source</i> oxidation of tyramine, which produced an intense signal, was responsible for this “ghost peak.” This artifact commonly occurs among aromatic compounds with high signal intensities and appears at the same <i>m/z</i> as their respective in vivo oxidized metabolites. In metabolomics, spectra contain diverse signals from complex biological mixtures, making it difficult to recognize artifact peaks. To prevent misassignments, despite +16 Da differences, adequate chromatographic separation of metabolites from their respective in vivo oxidation precursors is necessary. Whereas both electrolysis and gas-phase corona discharge can cause <i>in-source</i> oxidation in ESI, corona discharge proved to be the dominant factor. Additionally, the presence of multiple oxygen atom sources was suggested by the voltage-dependent mass shift of +16 Da to +18 Da of the “ghost peak” when using <sup>18</sup>O-labeled water as a solvent. Accurate metabolite identification using LC-ESI-MS/MS requires accounting for <i>in-source</i> products that can mimic in vivo products.</p>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"60 1","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11664113/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142877089","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}
Deeksha Khandelwal, Pankaj Kumar, P. V. Kumar, Atul K. Singh, Mahadev Rawat, Anit Dawar, R. Sharma, S. Ojha, S. Gargari, P. K. Mukherjee, S. Chopra, A. C. Pandey
{"title":"Performance Optimization of a Large Geometry High Resolution-Secondary Ion Mass Spectrometer (HR-SIMS) for High Precision Measurements of Oxygen Isotopic Composition (δ18O) and U–Pb Geochronology in Zircon","authors":"Deeksha Khandelwal, Pankaj Kumar, P. V. Kumar, Atul K. Singh, Mahadev Rawat, Anit Dawar, R. Sharma, S. Ojha, S. Gargari, P. K. Mukherjee, S. Chopra, A. C. Pandey","doi":"10.1002/jms.5103","DOIUrl":"10.1002/jms.5103","url":null,"abstract":"<div>\u0000 \u0000 <p>A large geometry high resolution secondary ion mass spectrometer (HR-SIMS) has been established as a part of the National Geochronology Facility (NGF) at Inter-University Accelerator Centre (IUAC), New Delhi. The performance of the instrument related to high spatial resolution, high mass resolving power (MRP), sensitivity of the instrument to measure low abundant isotopes, and sensitivity of the instrument for <sup>206</sup>Pb signal under different conditions are optimized and presented in this paper. We report the precision of the order of ~ 0.2‰ for oxygen isotopes measurement in 91500 reference material zircon and measured δ<sup>18</sup>O value of 10.08‰ ± 0.18‰ (2SD), which is in agreement with the recommended values. For U–Pb age measurement in zircon, Plešovice and FCT reference materials are measured as unknown and their <sup>206</sup>Pb/<sup>238</sup>U ages agree with the reported values within the uncertainties. A long-term evaluation of <sup>206</sup>Pb/<sup>238</sup>UO and <sup>206</sup>Pb/<sup>238</sup>U isotopic measurement ratio is also presented.</p>\u0000 </div>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"60 1","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142877109","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":"Mass Spectrometry Imaging for Spatial Toxicology Research","authors":"Tian (Autumn) Qiu","doi":"10.1002/jms.5104","DOIUrl":"https://doi.org/10.1002/jms.5104","url":null,"abstract":"<p>The spatial information of xenobiotics distribution, metabolism, and toxicity mechanisms in situ has drawn increasing attention in both pharmaceutical and environmental toxicology research to aid drug development and environmental risk assessments. Mass spectrometry imaging (MSI) provides a label-free, multiplexed, and high-throughput tool to characterize xenobiotics, their metabolites, and endogenous molecules in situ with spatial resolution, providing knowledge on spatially resolved absorption, distribution, metabolism, excretion, and toxicity on the molecular level. In this perspective, we briefly summarize applications of MSI in toxicology on xenobiotic distribution and metabolism, quantification, toxicity mechanisms, and biomarker discovery. We identified several challenges regarding how we can fully harness the power of MSI in both fundamental toxicology research and regulatory practices. First, how can we increase the coverage, sensitivity, and specificity in detecting xenobiotics and their metabolites in complex biological matrices? Second, how can we link the spatial molecular information of xenobiotics to toxicity consequences to understand toxicity mechanisms, predict exposure outcomes, and aid biomarker discovery? Finally, how can we standardize the MSI experiment and data analysis workflow to provide robust conclusions for regulation and drug development? With these questions in mind, we provide our perspectives on the future directions of MSI as a promising tool in spatial toxicology research.</p>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"59 12","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jms.5104","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142764011","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}
Caroline P. Carvalho, Thiago C. Canevari, Marcos N. Eberlin
{"title":"Molecular Ion: An Extended, Fully Collective, and More Contemporary Definition","authors":"Caroline P. Carvalho, Thiago C. Canevari, Marcos N. Eberlin","doi":"10.1002/jms.5106","DOIUrl":"https://doi.org/10.1002/jms.5106","url":null,"abstract":"","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"59 12","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142764012","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}