Journal of the American Society for Mass Spectrometry最新文献

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Characterization of Ions Activated by Collision-Induced Dissociation with Collision Energy Up to 30 eV Using 4-Trifluoromethyl-2,3,5,6-tetrafluorobenzylpyridinium "Thermometer Ion". 用4-三氟甲基-2,3,5,6-四氟苯基吡啶“温度计离子”表征碰撞诱导解离激活离子的碰撞能量高达30 eV。
IF 3.1 2区 化学
Journal of the American Society for Mass Spectrometry Pub Date : 2025-04-02 Epub Date: 2025-03-04 DOI: 10.1021/jasms.4c00461
Daiki Asakawa
{"title":"Characterization of Ions Activated by Collision-Induced Dissociation with Collision Energy Up to 30 eV Using 4-Trifluoromethyl-2,3,5,6-tetrafluorobenzylpyridinium \"Thermometer Ion\".","authors":"Daiki Asakawa","doi":"10.1021/jasms.4c00461","DOIUrl":"10.1021/jasms.4c00461","url":null,"abstract":"<p><p>To facilitate the assessment of the internal energy distribution of ions activated by collision-induced dissociation with collision energy in the laboratory frame exceeding 20 eV, the screening of fluorine-containing benzylpyridiniums was performed by evaluating their dissociation energies through quantum chemistry calculations at the CCSD(T)/6-311++G(d,p)//M06-2X-D3/6-311++G(d,p) level of theory. The dissociation energy increased with the presence of a trifluoromethyl group at the 4-position and fluorine atoms at positions 2, 3, 5, and 6 of benzylpyridinium. However, the fluorine atom at the 4-position in benzylpyridinium slightly reduced the dissociation energy, suggesting its electron-donating nature. 4-Trifluoromethyl-2,3,5,6-tetrafluorobenzylpyridinium (CF<sub>3</sub>,F<sub>4</sub>-BnPy<sup>+</sup>) has the highest dissociation energy among the reported benzylpyridiniums and is a suitable thermometer ion for characterizing the internal energy distributions of ions activated by collision-induced dissociation (CID) during tandem mass spectrometry. Using CF<sub>3</sub>,F<sub>4</sub>-BnPy<sup>+</sup> allowed the evaluation of the internal energy distribution of CID-activated ions up to a collision energy of 30 eV in the laboratory frame. The survival yield method using fluorine-substituted benzylpyridiniums and 4-methylbenzylpyridiniums facilitates the optimization of tandem mass spectrometry parameters for the analysis of small molecules, such as metabolites.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":" ","pages":"787-793"},"PeriodicalIF":3.1,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555458","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}
引用次数: 0
The Static Limit in MeV Secondary Ion Mass Spectrometry. MeV次离子质谱法的静态极限。
IF 3.1 2区 化学
Journal of the American Society for Mass Spectrometry Pub Date : 2025-04-02 Epub Date: 2025-03-07 DOI: 10.1021/jasms.5c00024
Mirjana Sepahyar Lorentzen, Boštjan Jenčič, Primož Vavpetič, Primož Pelicon
{"title":"The Static Limit in MeV Secondary Ion Mass Spectrometry.","authors":"Mirjana Sepahyar Lorentzen, Boštjan Jenčič, Primož Vavpetič, Primož Pelicon","doi":"10.1021/jasms.5c00024","DOIUrl":"10.1021/jasms.5c00024","url":null,"abstract":"<p><p>Static limit in secondary ion mass spectrometry (SIMS) is defined as a threshold beam fluence, where secondary ions are desorbed only from the virgin surface. For the common SIMS technique, the static SIMS limit is set to approximately 10<sup>12</sup> ions/cm<sup>2</sup>. Within the present paper, we investigated the applicability of the static limit for a mass spectrometry imaging technique known as MeV-SIMS, where the target surface is bombarded by primary ions within the MeV energy range domain. Here, desorption of secondary ions relies mainly on electronic excitations instead of collision cascades, as is the case for the lower energy primary ion beams. We have measured the disappearance cross sections of several organic targets for three different chlorine primary ion beam energies. Results show how the disappearance cross section depends on the primary ion beam energy. Generally, the static SIMS regime applies for a range of primary ion beam fluences similar to that for the common SIMS technique; however, the dependence of the disappearance cross section within the lower MeV energy domain (up to 10 MeV) exhibits somewhat unexpected characteristics. Further, we thoroughly investigated the dynamics of the secondary ion mass spectra after prolonged primary ion bombardment. Secondary ion yields of various peaks were monitored during analysis, and the corresponding data can be used to identify specific peaks and also to determine fragmentation patterns of analyzed organic molecules.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":" ","pages":"900-905"},"PeriodicalIF":3.1,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11969649/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143575612","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}
引用次数: 0
Pressure-Tunable Photoionization Tandem Ion Mobility Spectrometry for Investigating Proton Transfer Reactions of Binary Systems. 压力可调光离串联离子迁移谱法研究二元体系的质子转移反应。
IF 3.1 2区 化学
Journal of the American Society for Mass Spectrometry Pub Date : 2025-04-02 Epub Date: 2025-03-07 DOI: 10.1021/jasms.5c00051
Yiqian Xu, Qimu Yang, Yi Yu, Xuesong Zhang, Manman Pan, Dandan Jiang, Yuying Dong, Peng Gao, Lei Hua, Chuang Chen, Haiyang Li
{"title":"Pressure-Tunable Photoionization Tandem Ion Mobility Spectrometry for Investigating Proton Transfer Reactions of Binary Systems.","authors":"Yiqian Xu, Qimu Yang, Yi Yu, Xuesong Zhang, Manman Pan, Dandan Jiang, Yuying Dong, Peng Gao, Lei Hua, Chuang Chen, Haiyang Li","doi":"10.1021/jasms.5c00051","DOIUrl":"10.1021/jasms.5c00051","url":null,"abstract":"<p><p>Investigating and manipulating the ion-molecule reactions within the ionization source of ion mobility spectrometry (IMS) or mass spectrometry can contribute to developing advanced ionization sources and novel analytical techniques. In this study, a pressure-tunable photoionization tandem ion mobility spectrometer (PI-tandem-IMS) was developed to investigate the ionization suppression caused by unusual proton transfer reactions in dual-analyte systems in which high proton affinity (PA) ions are deprotonated by low PA molecules. The proton transfer reaction mechanisms in the toluene-acetone and toluene-ethanol systems were studied. The experimental results showed the linear correlation between the ln(<i>S</i><sub>X2H</sub><sup>+</sup>·<i>K</i><sub>0(T</sub><sup>+</sup><sub>)</sub>/<i>S</i><sub>T</sub><sup>+</sup>·<i>K</i><sub>0(X2H</sub><sup>+</sup><sub>)</sub> + 1) and the square of the reactant concentration <i>c</i><sub>X</sub><sup>2</sup>, as well as the cubic power of the pressure <i>p</i><sup>3</sup>. Based on this, the generation of the proton-bound dimers in the toluene-acetone and toluene-ethanol systems was assigned as a termolecular process. The reaction rate coefficients <i>k</i> of the toluene-acetone and toluene-ethanol systems were calculated at different temperatures, and the Arrhenius plot showed that rate coefficients were both negatively correlated with temperature, implying that elevated temperatures suppress the proton transfer reaction. At 313.15 K, the calculated <i>k</i> values for the toluene-acetone and the toluene-ethanol systems were 2.2 × 10<sup>-26</sup> cm<sup>6</sup>/s and 5.2 × 10<sup>-28</sup> cm<sup>6</sup>/s, respectively, suggesting a higher inhibitory effect of acetone on toluene ionization than that of ethanol. Besides, the suppressive effect of reducing the pressure or increasing the reaction region electric field strength on proton transfer reactions was shown, which demonstrated the PI-tandem IMS was a good tool for understanding ion-molecule reactions in the ionization source.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":" ","pages":"914-922"},"PeriodicalIF":3.1,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143571914","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}
引用次数: 0
Revealing Formylation Sites in Intact Amphibian Disulfide Peptides: A Top-Down Study Using ExD. 揭示完整两栖动物二硫肽甲酰化位点:一项自上而下的研究。
IF 3.1 2区 化学
Journal of the American Society for Mass Spectrometry Pub Date : 2025-04-02 Epub Date: 2025-03-03 DOI: 10.1021/jasms.4c00456
Tatiana Yu Samgina, Dmitrii M Mazur, Yury V Vasil'ev, Michael C Hare, Albert T Lebedev
{"title":"Revealing Formylation Sites in Intact Amphibian Disulfide Peptides: A Top-Down Study Using ExD.","authors":"Tatiana Yu Samgina, Dmitrii M Mazur, Yury V Vasil'ev, Michael C Hare, Albert T Lebedev","doi":"10.1021/jasms.4c00456","DOIUrl":"10.1021/jasms.4c00456","url":null,"abstract":"<p><p>Mass spectrometry contributed significantly to the creation of proteomics as a science and is now the principal analytical tool of proteomics. Although the bottom-up approach remains the most popular, more and more studies apply the top-down method for sequencing. Novel tandem mass spectrometry methods resolved numerous sequencing problems and allowed for the analysis of intact peptides and even proteins. Natural frog peptides are convenient models to develop mass spectrometry methods for <i>de novo</i> sequencing of intact biomolecules. Here we demonstrate the ability of ExD tandem mass spectrometry to sequence intact peptides from skin secretions of <i>Pelophylax ridibundus</i> from the Rostov (Russia) population. Studying that secretion, we detected an array of mono- and diformylated skin peptides at various sites of the backbone. The main goal of the study dealt with the determination of the formylation sites of these up to 46-mer long peptides. ExD reliably solved the problem without any additional mass spectrometry experiments or preliminary chemical derivatization. We propose a mechanism for the observed formylation and a biochemical and experimental rationale.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":" ","pages":"771-777"},"PeriodicalIF":3.1,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539882","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}
引用次数: 0
Identification and Mitigation of Pyrolysis Products in Laser-Cut Paper for Paper Spray Mass Spectrometry. 激光切割纸中热解产物的识别与缓解
IF 3.1 2区 化学
Journal of the American Society for Mass Spectrometry Pub Date : 2025-04-02 Epub Date: 2025-03-05 DOI: 10.1021/jasms.4c00499
Magnus Rydberg, Alexis Ochoa, Katherine Dayana Barrera Campos, Christine Skaggs, Ashur Rael, Nicholas Manicke
{"title":"Identification and Mitigation of Pyrolysis Products in Laser-Cut Paper for Paper Spray Mass Spectrometry.","authors":"Magnus Rydberg, Alexis Ochoa, Katherine Dayana Barrera Campos, Christine Skaggs, Ashur Rael, Nicholas Manicke","doi":"10.1021/jasms.4c00499","DOIUrl":"10.1021/jasms.4c00499","url":null,"abstract":"<p><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":" ","pages":"829-838"},"PeriodicalIF":3.1,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143565632","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}
引用次数: 0
A Highly Efficient and Automated Magnetic Bead Extraction Method Overcomes the Matrix Effect in LC-MS/MS Analysis of Human Serum Steroid Hormones. 高效自动化磁珠提取方法克服了LC-MS/MS分析中基质效应的影响。
IF 3.1 2区 化学
Journal of the American Society for Mass Spectrometry Pub Date : 2025-04-02 Epub Date: 2025-03-05 DOI: 10.1021/jasms.4c00338
Xiaoyi Yi, Xiaojing Huang, Yufeng Xiong, Yingsong Wu
{"title":"A Highly Efficient and Automated Magnetic Bead Extraction Method Overcomes the Matrix Effect in LC-MS/MS Analysis of Human Serum Steroid Hormones.","authors":"Xiaoyi Yi, Xiaojing Huang, Yufeng Xiong, Yingsong Wu","doi":"10.1021/jasms.4c00338","DOIUrl":"10.1021/jasms.4c00338","url":null,"abstract":"<p><p>Profiling of steroid hormones is incredibly valuable in clinical settings for diagnosing endocrine disorders. However, the presence of matrix effects and labor-intensive manual work in LC-MS/MS analysis has hindered its routine application. In the present study, a highly efficient and automated magnetic bead extraction method was developed to address matrix effects and quantitatively profile 15 steroid hormones in human serum. Octadecyl (C18) and <i>N</i>-vinylpyrrolidone divinylbenzene (HLB) modified magnetic beads were compared for enriching steroids from human serum. Following enrichment, the beads were separated using a magnetic field; the matrix was cleaned, and the steroid hormones were eluted from the beads for LC-MS/MS analysis. This entire process of enrichment, cleanup, and elution was conducted automatically, making it simple, fast, and cost-effective. The results indicated that steroid hormones could be selectively enriched from human serum in just 1 min using C18 magnetic beads. The absolute matrix effect, evaluated as the relative response between human serum matrix and methanol solution, ranged from 89.2% to 113.1% for low levels, from 82.3% to 112.0% for medium levels, and from 91.7% to 111.0% for high levels. The intrabatch coefficients of variation (CVs) and interbatch CVs were between 3.1% and 13.4% and between 3.0% and 13.7%, respectively. Recoveries were between 87.6% and 114.3% for low levels, 94.0% and 105.0% for medium levels, and 91.9% and 111.7% for high levels. The clinical application was demonstrated by profiling steroid hormones in 160 pregnant women at various gestational weeks. The results suggested that the automated magnetic bead extraction method for LC-MS/MS could effectively address matrix effects in profiling steroid hormones. To our knowledge, this is the first automated magnetic bead extraction method for LC-MS/MS profiling of steroid hormones in clinical practice.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":" ","pages":"699-712"},"PeriodicalIF":3.1,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555502","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}
引用次数: 0
Mechanism of Copper Stress on Algae Determined Using Mass Spectrometry Molecular Network: Molecular Characteristics and Metabolite Identification. 利用质谱分子网络确定铜胁迫对藻类的作用机制:分子特征和代谢物鉴定。
IF 3.1 2区 化学
Journal of the American Society for Mass Spectrometry Pub Date : 2025-04-02 Epub Date: 2025-03-07 DOI: 10.1021/jasms.4c00426
Yunkun Qian, Shuqi Wu, Yanan Liu, Yanan Chen, Jun Guo, Dong An
{"title":"Mechanism of Copper Stress on Algae Determined Using Mass Spectrometry Molecular Network: Molecular Characteristics and Metabolite Identification.","authors":"Yunkun Qian, Shuqi Wu, Yanan Liu, Yanan Chen, Jun Guo, Dong An","doi":"10.1021/jasms.4c00426","DOIUrl":"10.1021/jasms.4c00426","url":null,"abstract":"<p><p>Algae typically respond to environmental changes by regulating the production and release of metabolites that affect water quality and cause various environmental issues. In this study, we investigated the role of algal organic matter (AOM) in copper [Cu(II)] using high-resolution mass spectrometry and a molecular-network-based nontargeted screening. The abundance and activity of algae were inhibited after the addition of Cu(II). Lipids, proteins, lignins, condensed aromatic structures, CHO-only classes, and nitrogenous organic matter are the primary components of AOM. The addition of extracellular organic matter (EOM) and intracellular organic matter (IOM) promoted the generation of carbohydrates that bonded to Cu(II), thus weakening Cu(II) toxicity. Furthermore, 1006 and 589 unique formulas were observed in the Cu(II)-EOM and Cu(II)-IOM groups, respectively, illustrating that EOM and IOM can induce algae to produce different metabolites to resist Cu(II) stress. Six novel phosphatidylethanolamines (PEs) and three novel phosphatidylglycerols (PGs) were identified in the EOM of the Cu(II)-EOM group. Therefore, AOM addition enhanced the synthesis of novel low-unsaturation and palmitoylated PEs, thereby regulating the immune response of algal cells under Cu(II) stress. Overall, these results demonstrated that Cu(II) can perturb lipid utilization and storage, whereas algae can alleviate Cu(II) toxicity by synthesizing and secreting different lipids.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":" ","pages":"732-741"},"PeriodicalIF":3.1,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143571913","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}
引用次数: 0
Characterizing Protein Solvent Accessible Surface Area in Solution by Dual Polarity Native Mass Spectrometry 双极性天然质谱法表征蛋白质溶液中溶剂可达表面积
IF 3.1 2区 化学
Journal of the American Society for Mass Spectrometry Pub Date : 2025-04-01 DOI: 10.1021/jasms.4c0046510.1021/jasms.4c00465
Lei Yang, Yi Zhao, Xinyan Fu, Wenjing Zhang and Wei Xu*, 
{"title":"Characterizing Protein Solvent Accessible Surface Area in Solution by Dual Polarity Native Mass Spectrometry","authors":"Lei Yang,&nbsp;Yi Zhao,&nbsp;Xinyan Fu,&nbsp;Wenjing Zhang and Wei Xu*,&nbsp;","doi":"10.1021/jasms.4c0046510.1021/jasms.4c00465","DOIUrl":"https://doi.org/10.1021/jasms.4c00465https://doi.org/10.1021/jasms.4c00465","url":null,"abstract":"<p >Native mass spectrometry (nMS) is rapidly emerging as a pivotal technique for exploring protein conformations and protein–ligand interactions. Pioneering research has demonstrated that the charge state distribution (CSD) of proteins in native mass spectra can be indicative of their solvent accessible surface area (SASA). Moreover, beyond SASA, it is postulated that the abundance of acidic and basic amino acids on the protein surface may also impact the CSD. Specifically, basic amino acids tend to acquire positive charges during electrospray ionization (ESI), whereas acidic amino acids are prone to adopting negative charges. Consequently, this study investigates the CSDs of globular proteins in both positive and negative ion modes to provide a comprehensive characterization of protein SASA. Experiments were conducted under both native ESI and native nano-ESI conditions. By harnessing the average charges observed across dual polarity nMS data, we achieved significantly enhanced log linear correlations between protein SASA and its CSDs. The coefficient of determination (<i>R</i><sup>2</sup>) improved from 0.9866 to 0.9888 under ESI conditions and from 0.9677 to 0.9902 under nano-ESI conditions when compared to models utilizing only positive ion mode data. These findings suggest that the SASA of globular proteins can be effectively characterized through the CSDs derived from dual polarity nMS analysis.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"36 5","pages":"991–998 991–998"},"PeriodicalIF":3.1,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910976","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}
引用次数: 0
Multistage Linear Frequency Scanning Mass Analysis Processed by Fractional Fourier Transform 分数阶傅里叶变换处理的多级线性频率扫描质量分析
IF 3.1 2区 化学
Journal of the American Society for Mass Spectrometry Pub Date : 2025-04-01 DOI: 10.1021/jasms.5c0001210.1021/jasms.5c00012
Haoqiang Yan, Liangshun Hu, Shi Zhang, Dayu Li* and Wei Xu*, 
{"title":"Multistage Linear Frequency Scanning Mass Analysis Processed by Fractional Fourier Transform","authors":"Haoqiang Yan,&nbsp;Liangshun Hu,&nbsp;Shi Zhang,&nbsp;Dayu Li* and Wei Xu*,&nbsp;","doi":"10.1021/jasms.5c0001210.1021/jasms.5c00012","DOIUrl":"https://doi.org/10.1021/jasms.5c00012https://doi.org/10.1021/jasms.5c00012","url":null,"abstract":"<p >The common method of mass analysis in a linear ion trap mass spectrometer is to eject ions with different mass-to-charge ratios (<i>m</i>/<i>z</i>) at different times by resonance excitation. Ions are ejected onto an electron multiplier (EM), generating pulsed signals called the ejection signal. Typically, the ejection signal consisting of multiple pulses is smoothed into a wider Gaussian-like pulse due to the limited bandwidth of the electronic system. For different scan rates and different samples, this bandwidth-limited electronic system and signal smoothing process will differentially increase the peak width and thus decrease the mass resolution. In this study, experiments at different scan rates were performed on a “Brick” miniature linear ion trap mass spectrometer. We propose a multistage linear frequency scanning mode that achieves improved mass resolution and extended mass range, in which fractional Fourier transform is applied to process the ejection signals. The proposed signal processing method improves the mass resolution and mitigates the impact of ghost peaks attributed to scattered ion ejection. A peak width of 0.84 Da at a <i>m</i>/<i>z</i> value of 242 and a scan rate of 8000 Da/s was achieved in experiments.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"36 5","pages":"1093–1099 1093–1099"},"PeriodicalIF":3.1,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910986","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}
引用次数: 0
Size-Exclusion Chromatography–Electrospray-Ionization Mass Spectrometry To Characterize End Group and Chemical Distribution of Poly(lactide-co-glycolide) Copolymers 尺寸排除色谱-电喷雾-电离质谱法表征聚丙交酯-共聚物的端基和化学分布
IF 3.1 2区 化学
Journal of the American Society for Mass Spectrometry Pub Date : 2025-03-31 DOI: 10.1021/jasms.4c0044710.1021/jasms.4c00447
Masashi Serizawa*, Pieter van Delft, Peter J. Schoenmakers, Ron A. H. Peters and Andrea F. G. Gargano*, 
{"title":"Size-Exclusion Chromatography–Electrospray-Ionization Mass Spectrometry To Characterize End Group and Chemical Distribution of Poly(lactide-co-glycolide) Copolymers","authors":"Masashi Serizawa*,&nbsp;Pieter van Delft,&nbsp;Peter J. Schoenmakers,&nbsp;Ron A. H. Peters and Andrea F. G. Gargano*,&nbsp;","doi":"10.1021/jasms.4c0044710.1021/jasms.4c00447","DOIUrl":"https://doi.org/10.1021/jasms.4c00447https://doi.org/10.1021/jasms.4c00447","url":null,"abstract":"<p >The characterization of the microstructure of <i>in vivo</i> degradable polyesters is gaining increased interest thanks to their high-performance applications, such as drug delivery systems. The design of such material requires a high level of understanding of the critical material attributes of the polyesters, such as molecular-weight distribution (MWD), chemical-composition distribution (CCD), and end-groups (functionality-type distribution, FTD). Size-exclusion chromatography (SEC) hyphenated with mass spectrometry (MS) is an effective method for analyzing the microstructure of polymers. While the MWD can be determined by size-exclusion chromatography hyphenated with ultraviolet spectrometry and refractive index, the CCD and FTD can be determined by SEC-MS. However, previous applications of SEC-MS have not assessed if polymer fragmentation can occur during the analysis process. In order to correctly interpret CCD and FTD, it is important to establish whether SEC-MS methods can be applied to biodegradable polymers and to recognize if fragmentation processes occur. In this study, we investigate whether SEC-MS methods can be applied to PLGA biodegradable polyesters. The research demonstrates that the choice of alkali metal salt used during ionization can influence the stability of PLGA during SEC-MS analysis. CsI was found to minimize fragmentations during ESI-MS, simplifying the MS spectra and allowing isomeric PLGA structures to be distinguished. The resulting method facilitates FTD and CCD determination. Additionally, when combined with selective degradation, the described method can provide insights into the “blockiness” of the polymer and support the development of sequence-controlled PLGA synthesis.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":"36 5","pages":"980–990 980–990"},"PeriodicalIF":3.1,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jasms.4c00447","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911167","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}
引用次数: 0
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