Journal of the American Society for Mass Spectrometry最新文献

{"title":"Structural Characterization of Dimeric Perfluoroalkyl Carboxylic Acid Using Experimental and Theoretical Ion Mobility Spectrometry Analyses","authors":"Aurore L. Schneiders,&nbsp;Johann Far,&nbsp;Lidia Belova,&nbsp;Allison Fry,&nbsp;Adrian Covaci,&nbsp;Erin S. Baker,&nbsp;Edwin De Pauw and Gauthier Eppe*,&nbsp;","doi":"10.1021/jasms.5c0000710.1021/jasms.5c00007","DOIUrl":"https://doi.org/10.1021/jasms.5c00007https://doi.org/10.1021/jasms.5c00007","url":null,"abstract":"<p >Per- and polyfluoroalkyl substances (PFAS) are contaminants of increasing concern, with over seven million compounds currently inventoried in the PubChem PFAS Tree. Recently, ion mobility spectrometry has been combined with liquid chromatography and high-resolution mass spectrometry (LC-IMS-HRMS) to assess PFAS. Interestingly, using negative electrospray ionization, perfluoroalkyl carboxylic acids (PFCAs) form homodimers ([2M-H]⁻), a phenomenon observed with trapped, traveling wave, and drift-tube IMS. In addition to the limited research on their effect on analytical performance, there is little information on the conformations these dimers can adopt. This study aimed to propose most probable conformations for PFCA dimers. Based on qualitative analysis of how collision cross section (CCS) values change with the mass-to-charge ratio (<i>m</i>/<i>z</i>) of PFCA ions, the PFCA dimers were hypothesized to likely adopt a V-shaped structure. To support this assumption, <i>in silico</i> geometry optimizations were performed to generate a set of conformers for each possible dimer. A CCS value was then calculated for each conformer using the trajectory method with Lennard-Jones and ion-quadrupole potentials. Among these conformers, at least one of the ten lowest-energy conformers identified for each dimer exhibited theoretical CCS values within a ±2% error margin compared to the experimental data, qualifying them as plausible structures for the dimers. Our findings revealed that the fluorinated alkyl chains in the dimers are close to each other due to a combination of C–F···O=C and C–F···F–C stabilizing interactions. These findings, together with supplementary investigations involving environmentally relevant cations, may offer valuable insights into the interactions and environmental behavior of PFAS.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"36 4","pages":"850–861 850–861"},"PeriodicalIF":3.1,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746154","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":"Evolution of Mass Spectrometers for High m/z Biological Ion Formation, Transmission, Analysis and Detection: A Personal Perspective","authors":"Iain D. G. Campuzano*,&nbsp; and ,&nbsp;Joseph A. Loo*,&nbsp;","doi":"10.1021/jasms.4c0034810.1021/jasms.4c00348","DOIUrl":"https://doi.org/10.1021/jasms.4c00348https://doi.org/10.1021/jasms.4c00348","url":null,"abstract":"<p >Mass spectrometry (MS) has become an essential tool in virtually all academic, pharmaceutical, and biopharmaceutical analytical laboratories. The specialized and bespoke area of MS research and application of high <i>m</i>/<i>z</i> ion (&gt;<i>m</i>/<i>z</i> 6000 and high mass, &gt;150 kDa) formation, transmission, analysis, and detection is a relatively new area of focus for MS that has seen dramatic acceleration in interest over the last two decades. Herein we delve into this exciting aspect of MS, discussing how MS instrumentation has been refined and evolved for native-MS analysis. We cover the early groundbreaking experiments showing high <i>m</i>/<i>z</i> ion formation, transmission, and preservation of protein structure in the gas phase. Additionally, we discuss specific instrument optimizations and modifications that have advanced high <i>m</i>/<i>z</i> ion generation, transmission, analysis, and detection, contributing to the research area known as gas-phase structural biology. Native-MS sample introduction methods, emerging technologies, and future perspectives are also examined. Finally, we share personal opinions, observations, and experiences that are new to the community or previously unpublished.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"36 4","pages":"632–652 632–652"},"PeriodicalIF":3.1,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746152","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":"Identification and Mitigation of Pyrolysis Products in Laser-Cut Paper for Paper Spray Mass Spectrometry","authors":"Magnus Rydberg,&nbsp;Alexis Ochoa,&nbsp;Katherine Dayana Barrera Campos,&nbsp;Christine Skaggs,&nbsp;Ashur Rael and Nicholas Manicke*,&nbsp;","doi":"10.1021/jasms.4c0049910.1021/jasms.4c00499","DOIUrl":"https://doi.org/10.1021/jasms.4c00499https://doi.org/10.1021/jasms.4c00499","url":null,"abstract":"<p >Paper spray mass spectrometry (PS-MS) often employs laser cutting to prepare paper substrates, potentially inducing localized thermal decomposition of the cellulose backbone. This work investigates how cellulose pyrolysis products and inherent background molecules within the paper affect PS-MS signal quality and evaluates paper pretreatment methods to enhance performance. Comparative analyses of laser-cut and razor-cut paper using mass spectrometry and ultraviolet–visible spectroscopy (UV–vis) showed significant differences. Laser-cut paper exhibited elevated MS blank signals and higher absorbance in the 200–400 nm UV region, indicating increased chemical abundance and complexity. Gas chromatography–mass spectrometry (GC-MS) identified over 20 residual compounds on laser-cut paper absent in razor-cut samples, half of which were identified as known cellulose pyrolysis products. Washing the paper substrates with methanol, water, or dilute nitric acid significantly reduced both pyrolysis products and background molecules, with water showing the most improvement. Analyses of morphine, fentanyl, methamphetamine, voriconazole, and fluconazole showed no reduction in the signal after washing, with fentanyl and methamphetamine exhibiting a significantly increased MS signal, regardless of the cutting method. This work reveals that while pyrolysis products from laser cutting contribute to increased chemical noise, inherent background molecules in the paper also play a significant role. A simple water wash mitigates both issues, potentially improving the overall PS-MS performance for a range of analytes.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"36 4","pages":"829–838 829–838"},"PeriodicalIF":3.1,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746153","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":"HRMS-Viewer: Software for High Resolution Mass Spectrometry Formula Assignment and Data Visualization.","authors":"Junyang Chen, Chen He, Jianxun Wu, Yahe Zhang, Quan Shi","doi":"10.1021/jasms.4c00442","DOIUrl":"10.1021/jasms.4c00442","url":null,"abstract":"<p><p>Accurately assigning formulas to thousands of peaks generated by ultrahigh resolution mass spectrometry in a single analysis poses a significant challenge, especially when dealing with diverse molecular compositions across complex mixtures. This difficulty is further compounded by the lack of an established universal mass calibration and formula assignment method. We have developed HRMS-Viewer, a Python-based software tool designed for processing ultrahigh resolution mass spectrometry data specific to petroleum and natural organic matter (NOM). The software employs an efficient, experience-driven approach for small molecule formula assignment, offering a streamlined yet intuitive workflow. Key features include advanced noise reduction, automatic or manual recalibration, real-time visualization of formula assignment results, and options for manual correction. During the workflow, HRMS-Viewer enables the visualization and manual control of critical steps including noise reduction, recalibration, peak identification, and data review.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":" ","pages":"565-572"},"PeriodicalIF":3.1,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447551","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":"PNGaseF-Generated N-Glycans Adduct onto Peptides in the Gas Phase.","authors":"Valentina Rangel-Angarita, Joann Chongsaritsinsuk, Keira E Mahoney, Lea M Kim, Ryan J Chen, Akua A Appah-Sampong, Isabella P Tran, Alexandra D Steigmeyer, Marie A Hollenhorst, Stacy A Malaker","doi":"10.1021/jasms.4c00431","DOIUrl":"10.1021/jasms.4c00431","url":null,"abstract":"<p><p>Glycoproteomics has recently increased in popularity due to instrumental and methodological advances. That said, O-glycoproteomic analysis is still challenging for various reasons, including signal suppression, search algorithm limitations, and co-occupancy of N- and O-glycopeptides. To decrease sample complexity and simplify analysis, most O-glycoproteomic workflows include PNGaseF digestion, which is an endoglycosidase that removes most N-glycan structures. Here, we report that N-glycans released from PNGaseF digestion were identified during data acquisition and hampered detection of O-glycopeptides. Importantly, we noted instances where free glycans adducted to unmodified peptides in the gas phase and were misidentified by search algorithms as O-glycopeptides. We confirmed the presence of free glycans in other experiments performed in our laboratory, as well as from data generated by other groups. To overcome this limitation, we demonstrated that released N-glycans can be removed using a molecular weight cut off filter prior to (glyco)protease digestion, which improves O-glycoproteomic coverage.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":" ","pages":"542-552"},"PeriodicalIF":3.1,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143405090","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":"Rapid and Non-Targeted Qualitative and Quantitative Detection of miRNA in Complex Biological Samples Using Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry with a 3-Aminoquinoline and 2',4',6'-Trihydroxyacetophenone Ionic Liquid Matrix.","authors":"Shiwen Zhou, Jiancong Liao, Kailin Jiang, Huiwen Wang, Yaqin Liu, Hangming Xiong, Ping Wang, Yuanjiang Pan, Hongru Feng","doi":"10.1021/jasms.4c00369","DOIUrl":"10.1021/jasms.4c00369","url":null,"abstract":"<p><p>A novel ionic liquid MALDI matrix, 3-aminoquinoline/2',4',6'-trihydroxyacetophenone monohydrate (3-AQ/THAP), was developed for the rapid qualitative and quantitative detection of miRNA from biological samples. Compared to the traditional matrix 2,5-dihydroxybenzoic acid (DHB) and previously reported oligonucleotide-specific matrices, such as 3-aminopicolinic acid (3-APA), 3-hydroxypicolinic acid (3-HPA), and 6-aza-2-thiothymine (ATT), the 3-AQ/THAP matrix offers several advantages. It produces fewer alkali metal adduct peaks, exhibits higher sensitivity, and ensures better spot-to-spot repeatability. The 3-AQ/THAP matrix provides broader mass coverage and can effectively detect oligonucleotides ranging from 3-mer to 50-mer while delivering single-base resolution and sequence information. Additionally, it significantly reduces the \"sweet spot\" effect with an RSD of less than 7% over 36 single-spot analyses. For oligonucleotides ranging from 16-mer to 26-mer, the linear range extends from 0.4 μM to 40 μM per spot, with an R² greater than 0.988. Finally, miRNA in human plasma, fetal equine serum, and fetal bovine serum was successfully identified both qualitatively and quantitatively using the 3-AQ/THAP matrix. This matrix demonstrated excellent practicability for the detection of multiple miRNAs in complex biological samples.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":" ","pages":"495-503"},"PeriodicalIF":3.1,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143063009","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":"Faces of Mass Spectrometry/Jose Navarrete-Perea.","authors":"Anne Brenner, J D Brookbank","doi":"10.1021/jasms.5c00020","DOIUrl":"https://doi.org/10.1021/jasms.5c00020","url":null,"abstract":"","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"36 3","pages":"450-452"},"PeriodicalIF":3.1,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555580","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":"In Silico Characterization of Glycan Ions from IM-MS Collision Cross Section.","authors":"Mithony Keng, Kenneth M Merz","doi":"10.1021/jasms.4c00370","DOIUrl":"10.1021/jasms.4c00370","url":null,"abstract":"<p><p>Ion mobility mass spectrometry (IM-MS) can assist in the identification of isobaric chemical analytes by exploiting the difference in their gas phase collision cross-section (CCS) property. In glycomics, reliable glycan characterization remains challenging, even with IM-MS, because of closely related isomeric species and the available binding arrangements of substituted monosaccharides, allowing for the formation of complex structures. Here, we present a computational procedure to obtain gas-phase structural information from the experimental IM-MS CCS data of carbohydrates. The workflow proceeds with high throughput charge modeling of glycan seed structures to determine the precise protonation or deprotonation site. The charge models were then screened by using density functional theory (DFT) to produce candidate charge states for conformation generation. An extensive conformational scoring of the glycan ions was performed quantum mechanically at the DFT D3-B3LYP/6-31G+(d,p) level for the negative mode, [M - H]^-, and at the D3-B3LYP/6-31G(d,p) level for the positive mode, [M + H]⁺. For most of our test set, the computed CCS values from the final geometry optimized structures showed good agreement with experiment. We also demonstrated the capability of characterizing configurational and constitutional isomeric species. Altogether, we believe that the method we used in this work can be used to build a reliable theoretical reference database for glycans that can be used for experimental quality control and for assigning molecular structure to experimental IM-MS CCS information.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":" ","pages":"504-513"},"PeriodicalIF":3.1,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11887428/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143389789","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Analysis of Fentanyl and Fentanyl Analogs Using Atmospheric Pressure Chemical Ionization Gas Chromatography-Mass Spectrometry (APCI-GC-MS).","authors":"Karen A Reyes Monroy, Richard McCrary, Isabelle Parry, Catherine Webber, Teresa D Golden, Guido F Verbeck","doi":"10.1021/jasms.4c00455","DOIUrl":"10.1021/jasms.4c00455","url":null,"abstract":"<p><p>Illicit fentanyl and fentanyl analogs are a growing concern in the United States as opioid related deaths rise. Given that fentanyl analogs are readily obtained by modifying the structure of fentanyl, illicit fentanyl analogs appearing on the black market often contain similar structures, making analogue differentiation and identification difficult. Thus, obtaining both precursor and product ion data during analysis is becoming increasingly valuable in fentanyl analog characterization. In this paper, we provide GC column retention time, precursor, and product ion mass spectrum data for 74 fentanyl analogs that were analyzed using atmospheric pressure chemical ionization-gas chromatography-mass spectrometry (APCI-GC-MS) utilizing a triple quadrupole mass analyzer. During analysis, precursor ions underwent collision induced dissociation (CID) by increasing the collision energy (10, 20, 30, 40, and 50 V) throughout a single run. Data reveal that APCI readily produces product ions of the piperidine and <i>N</i>-alkyl chain but rarely provides data on the acyl group. Furthermore, fentanyl analogs with greater substitution at the <i>N</i>-alkyl chain demonstrate a greater preference for dissociation at the N-αC and αC-βC bond, while greater substitution at the amide group leads to fragmentation at the N-C4 bond.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":" ","pages":"587-600"},"PeriodicalIF":3.1,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11887434/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143078407","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Emission of Alkali Halide Cluster Ions from the Charged Droplets Generated from Electrospray Ionization.","authors":"Seongjae Jang, Minsu Kim, Yoonjin Kim, Junyoung Ahn, Jongcheol Seo","doi":"10.1021/jasms.4c00452","DOIUrl":"10.1021/jasms.4c00452","url":null,"abstract":"<p><p>In this study, the formation and emission of alkali halide cluster ions in charged droplets generated by electrospray ionization (ESI) was investigated using mass spectrometry (MS). We focus on ion emission at the air-solution interface of charged droplets, distinguishing between two mechanisms: the ion evaporation model (IEM), where ions are released directly from the interface, and the charge residue model (CRM), where ions are generated after complete solvent evaporation. Using an iodide/chloride mixture, we analyzed how interfacial affinity influences the composition of the generated alkali halide cluster cations and anions. With the knowledge that iodides have much higher interfacial affinities than chlorides, a relative faction of iodide in the cluster ion enables us to distinguish between IEM and CRM. Small cluster anions and cations exclusively containing iodides are suggested to be from IEM, while the larger cluster ions containing more chlorides are expected to be from CRM. This work clarifies the distinctions between IEM and CRM in alkali halide cluster ion formation and also establishes a robust analytical approach for assessing interfacial affinities of ions using ESI-MS, which may potentially enhance our understanding of interfacial chemistry and its implications in atmospheric and analytical sciences.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":" ","pages":"579-586"},"PeriodicalIF":3.1,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143254451","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}