European Journal of Mass Spectrometry最新文献

{"title":"A pattern-recognition-based clustering method for non-invasive diagnosis and classification of various gastric conditions.","authors":"Abhijit Maity,&nbsp;Sayoni Bhattacharya,&nbsp;Anil C Mahato,&nbsp;Sujit Chaudhuri,&nbsp;Manik Pradhan","doi":"10.1177/14690667231174350","DOIUrl":"https://doi.org/10.1177/14690667231174350","url":null,"abstract":"<p><p>Conventional endoscopic biopsy tests are not suitable for early detection of the acute onset and progression of peptic ulcer as well as various gastric complications. This also limits its suitability for widespread population-based screening and consequently, many people with complex gastric phenotypes remain undiagnosed. Here, we demonstrate a new non-invasive methodology for accurate diagnosis and classification of various gastric disorders exploiting a pattern-recognition-based cluster analysis of a breathomics dataset generated from a simple residual gas analyzer-mass spectrometry. The clustering approach recognizes unique breathograms and \"breathprints\" signatures that clearly reflect the specific gastric condition of an individual person. The method can selectively distinguish the breath of peptic ulcer and other gastric dysfunctions like dyspepsia, gastritis, and gastroesophageal reflux disease patients from the exhaled breath of healthy individuals with high diagnostic sensitivity and specificity. Moreover, the clustering method exhibited a reasonable power to selectively classify the early-stage and high-risk gastric conditions with/without ulceration, thus opening a new non-invasive analytical avenue for early detection, follow-up, and fast population-based robust screening strategy of gastric complications in the real-world clinical domain.</p>","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":"29 3","pages":"192-199"},"PeriodicalIF":1.3,"publicationDate":"2023-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9689204","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Flash pyrolysis vacuum ultraviolet photoionization mass spectrometry of cycloheptane: A study of the initial decomposition mechanism.","authors":"Kuanliang Shao,&nbsp;Ge Sun,&nbsp;Mariah Gomez,&nbsp;Xinghua Liu,&nbsp;Jingsong Zhang","doi":"10.1177/14690667221142699","DOIUrl":"https://doi.org/10.1177/14690667221142699","url":null,"abstract":"<p><p>Thermal decomposition of cycloheptane was studied using flash pyrolysis coupled with vacuum ultraviolet (118.2 nm) single photon ionization time-of-flight mass spectrometry at temperatures ranging from 295 K to 1380 K. C-C bond breaking of cycloheptane leading to the 1,7-heptyl diradical was considered as the initiation step. The 1,7-heptyl diradical could readily isomerize to 1-heptene and decompose into several fragments, with dissociation to •C₄H₉ and •C₃H₅ as the predominant product channel. The 1,7-heptyl diradical could undergo direct dissociation, as evidenced by the production of the C₅H₁₀ species. Quantum chemistry calculations at UCCSD(T)/cc-pVDZ//UB3LYP/cc-pVDZ level of theory on the initial reaction pathways of cycloheptane were also carried out to support the experimental observations. Other possible initiation channels, as well as some secondary reaction products, were also identified.</p>","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":"29 2","pages":"88-96"},"PeriodicalIF":1.3,"publicationDate":"2023-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9600274","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Proximity effects in the electron ionisation mass spectra of substituted cinnamamides.","authors":"Adam R Michalik,&nbsp;Nathan W Fenwick,&nbsp;Richard Telford,&nbsp;Archie W Johnson,&nbsp;William Hc Martin,&nbsp;Richard D Bowen","doi":"10.1177/14690667231153777","DOIUrl":"https://doi.org/10.1177/14690667231153777","url":null,"abstract":"<p><p>The electron ionisation mass spectra of an extensive set of 53 ionised monosubstituted and disubstituted cinnamamides [XC₆H₄CH=CHCONH₂, X = H, F, Cl, Br, I, CH₃, CH₃O, CF₃, NO₂, CH₃CH₂, (CH₃)₂CH and (CH₃)₃C; and XYC₆H₃CH=CHCONH₂, X = Y = Cl; and X, Y = F, Cl or Br] are reported and discussed. Particular attention is paid to the significance of loss of the substituent, X, from the 2-position, via a rearrangement that is sometimes known as a proximity effect, which has been reported for a range of radical-cations, but is shown in this work to be especially important for ionised cinnamamides. When X is in the 2-position of the aromatic ring, [M - X]⁺ is formed to a far greater extent than [M - H]⁺; in contrast, when X is in the 3-position or 4-position, [M - H]⁺ is generally much more important than [M - X]⁺. Parallel trends are found in the spectra of XYC₆H₃CH=CHCONH₂: the signal for [M - X]⁺ dominates that for [M - Y]⁺ when X is in the 2-position and Y in the 4-position or 5-position, irrespective of the nature of X and Y. Further insight is obtained by studying the competition between expulsion of X^· and alternative fragmentations that may be described as simple cleavages. Loss of ^·NH₂ results in the formation of a substituted cinnamoyl cation, [XC₆H₄CH=CHCO]⁺ or [XYC₆H₃CH=CHCO]⁺; this process competes far less effectively with the proximity effect when X is in the 2-position than when it is in the 3-position or 4-position. Additional information has been obtained by investigating the competition between formation of [M - H]⁺ by the proximity effect and loss of CH₃^· by cleavage of a 4-alkyl group to give a benzylic cation, [R¹R²CC₆H₄CH=CHCONH₂]⁺ (R¹, R² = H, CH₃).</p>","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":"29 2","pages":"75-87"},"PeriodicalIF":1.3,"publicationDate":"2023-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10068410/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9246388","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Prof. Dr Michael Przybylski (* 25.3.1948; † 27.2.2023).","authors":"Jürgen Grotemeyer","doi":"10.1177/14690667231165876","DOIUrl":"https://doi.org/10.1177/14690667231165876","url":null,"abstract":"","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":"29 2","pages":"67"},"PeriodicalIF":1.3,"publicationDate":"2023-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9587638","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The analytical solution for the optimum voltage on regularizing electrodes of the open dynamically harmonized cell.","authors":"Anton Lioznov, Evgeny Nikolaev","doi":"10.1177/14690667231164552","DOIUrl":"10.1177/14690667231164552","url":null,"abstract":"<p><p>The Fourier transform ion cyclotron resonance method holds the lead in mass accuracy and resolving power among all other mass spectrometry methods. The dynamically harmonized cell is largely responsible for the supremacy. This cell has an ideal hyperbolic trapping potential after averaging over fast cyclotron motion. Recently we have introduced an open modification of the cell (especially useful with ultrahigh magnetic fields) and have found the analytical solution for the averaged potential inside it. The voltage on specific \"regularizing\" electrodes determines how close a potential is to the hyperbolic one. In this article, we find the optimal voltage on these \"regularizing\" electrodes analytically. This will assist with both further analysis and tuning of the trap after manufacturing.</p>","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":"29 2","pages":"97-101"},"PeriodicalIF":1.3,"publicationDate":"2023-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9601816","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Insight into <i>in silico</i> prediction and chemical degradation study of osimertinib mesylate by LC-HRMS and NMR: Investigation of a typical case of alkaline pH-mediated oxidative degradation product.","authors":"Vivek Dhiman,&nbsp;Balasaheb B Chavan,&nbsp;Niharika Ramarapu,&nbsp;Gananadhamu Samanthula","doi":"10.1177/14690667231162345","DOIUrl":"https://doi.org/10.1177/14690667231162345","url":null,"abstract":"Osimertinib mesylate is a third-generation epidermal growth factor receptor tyrosine kinase inhibitor used to treat nonsmall-cell lung cancer. The objective was to understand in silico prediction and chemical-based stress testing of the osimertinib mesylate. A total of eight degradation products (DPs) were formed under chemical stress testing. An in silico tool viz., Zeneth predicted a higher percentage of DPs. The separation of all the DPs was achieved using reversed phase high-performance liquid chromatography, employing X-Bridge C18 column with ammonium acetate (pH adjusted to 7.50 with ammonia) and acetonitrile as mobile phase. The overall results showed it underwent significant degradation in acidic, alkaline, and oxidative conditions. In rest of the conditions, osimertinib mesylate was found to be stable or slight degradation was observed in photolytic condition. The structure of DPs was elucidated with a comparison of data generated from high-resolution mass spectrometry (HRMS) of osimertinib mesylate and its degradation products. To confirm the unambiguous regioisomers, one-dimensional (1D) and two-dimentional (2D) nuclear magnetic resonance studies were performed. Furthermore, the N-oxide position was assigned for the first time using the Meisenheimer rearrangement reaction in atmospheric pressure chemical ionization mode. Interestingly, an unusual reaction of DP2 formation was observed at alkaline conditions. In silico tools such as DEREK and Sarah predicted osimertinib mesylate and most of the DPs found to be structural alert for mutagenicity.","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":"29 2","pages":"123-131"},"PeriodicalIF":1.3,"publicationDate":"2023-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9238890","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Quantitation of small molecules from liquid chromatography-mass spectrometric accurate mass datasets using CycloBranch.","authors":"Jiří Novák,&nbsp;Kevin A Schug,&nbsp;Vladimír Havlíček","doi":"10.1177/14690667231164766","DOIUrl":"https://doi.org/10.1177/14690667231164766","url":null,"abstract":"<p><p>Gaussian and exponentially modified Gaussian functions were incorporated into integrating algorithms used by an open-source, cross-platform tool called CycloBranch. The quantitation is demonstrated on bacterial pyoverdines separated by fine isotope features. Using our algorithm, we can separate the m/z values 694.25802 and 694.26731 (a 0.009 Da difference), where the former belongs to the most intense peak of pyoverdine D (PvdD), and the latter to the second most intense peak of pyoverdine E (PvdE) in the respective isotopic clusters of [M + Fe-H]²⁺ ions. The areas under chromatographic curves of standards were analyzed for the limit of detection (LOD), limit of quantitation (LOQ), and regression coefficient calculations. The quantitative module returned a LOD and LOQ of 1.4 and 4.3 ng/mL, respectively, for both PvdD and PvdE in human urine. If present and detected in mass spectra, the intensities of user-defined [M + H]⁺, [M + Na]⁺, [M + K]⁺, [M + Fe-H]²⁺, or other ion types, can be accumulated and used for quantitation. The quantitation result is returned by CycloBranch in seconds or minutes, contrary to an hours-long manual approach, prone to user-born errors originating from necessary copying among various software environments. Native Bruker, Waters, Thermo, txt, mgf, mzML, and mzXML data formats are supported in CycloBranch, which is freely available at https://ms.biomed.cas.cz/cyclobranch.</p>","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":"29 2","pages":"102-110"},"PeriodicalIF":1.3,"publicationDate":"2023-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9294015","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mass spectrometric detection of ion pairs containing rigid copper clusters and weakly coordinating counter ions using liquid injection field desorption/ionisation.","authors":"Julia Taubert,&nbsp;Matthias Vogt,&nbsp;Robert Langer","doi":"10.1177/14690667221139419","DOIUrl":"https://doi.org/10.1177/14690667221139419","url":null,"abstract":"<p><p>A comparative mass spectrometric investigation using electrospray ionisation (ESI) and liquid injection field desorption/ionisation (LIFDI) techniques is reported for the highly luminescent and cationic copper cluster [(PCP)<math><msub><mrow></mrow><mn>3</mn></msub></math>Cu<math><msub><mrow></mrow><mn>4</mn></msub></math>]<math><msup><mrow></mrow><mo>+</mo></msup></math> (<b>1[Formula: see text]</b>, PCP = [1,3-(Ph<math><msub><mrow></mrow><mn>2</mn></msub></math>P)<math><msub><mrow></mrow><mn>2</mn></msub></math>C<math><msub><mrow></mrow><mn>6</mn></msub></math>H<math><msub><mrow></mrow><mn>3</mn></msub></math>]<math><msup><mrow></mrow><mo>-</mo></msup></math>). Depending on the available counter ion X<math><msup><mrow></mrow><mo>-</mo></msup></math>, ion pairs consisting of the original or a modified cluster cation and the weakly coordinating counter ion can be detected by LIFDI-high-resolution-mass spectrometry in addition to the cluster cation. Notably, only large counter ions with an extremely low tendency for metal coordination give rise to the observation of ion pairs, whereas smaller ions such as BF<math><msubsup><mrow></mrow><mn>4</mn><mo>-</mo></msubsup></math> do not show peaks corresponding to ion pairs in their mass spectra. In principle, two pathways were identified for the formation of positively charged ion pairs: (i) association of a generated Cu<math><msup><mrow></mrow><mo>+</mo></msup></math> ion to the neutral ion pair [(PCP)<math><msub><mrow></mrow><mn>3</mn></msub></math>Cu<math><msub><mrow></mrow><mn>4</mn></msub></math>]X (<b>1+X</b>, X<math><msup><mrow></mrow><mo>-</mo></msup></math> = BAr<math><msubsup><mrow></mrow><mn>20</mn><mi>F</mi></msubsup></math>, BAr<math><msubsup><mrow></mrow><mn>24</mn><mi>F</mi></msubsup></math>) and (ii) abstraction of an electron from the neutral ion pair [(PCP)<math><msub><mrow></mrow><mn>3</mn></msub></math>Cu<math><msub><mrow></mrow><mn>4</mn></msub></math>]X (<b>1+X</b>), leading to the oxidised ion pair <b>[1+X][Formula: see text]</b> (X<math><msup><mrow></mrow><mo>-</mo></msup></math> = Al(OR<math><msup><mrow></mrow><mi>F</mi></msup></math>)<math><msub><mrow></mrow><mn>4</mn></msub></math>).</p>","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":"29 2","pages":"68-74"},"PeriodicalIF":1.3,"publicationDate":"2023-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9339495","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploratory data fusion of untargeted multimodal LC-HRMS with annotation by LCMS-TOF-ion mobility: White wine case study.","authors":"Mpho Mafata,&nbsp;Maria Stander,&nbsp;Keabetswe Masike,&nbsp;Astrid Buica","doi":"10.1177/14690667231164096","DOIUrl":"https://doi.org/10.1177/14690667231164096","url":null,"abstract":"<p><p>Applied sciences have increased focus on omics studies which merge data science with analytical tools. These studies often result in large amounts of data produced and the objective is to generate meaningful interpretations from them. This can sometimes mean combining and integrating different datasets through data fusion techniques. The most strategic course of action when dealing with products of unknown profile is to use exploratory approaches. For omics, this means using untargeted analytical methods and exploratory data analysis techniques. The current study aimed to perform data fusion on untargeted multimodal (negative and positive mode) liquid chromatography-high-resolution mass spectrometry data using multiple factor analysis. The data fusion results were interpreted using agglomerative hierarchical clustering on biplot projections. The study reduced the thousands of spectral signals processed to less than a hundred features (a primary parameter combination of retention time and mass-to-charge ratios, RT_m/z). The correlations between cluster members (samples and features from) were calculated and the top 10% highly correlated features were identified for each cluster. These features were then tentatively identified using secondary parameters (drift time, ion mobility constant and collision cross-section values) from the ion mobility spectra. These ion mobility (secondary) parameters can be used for future studies in wine chemical analysis and added to the growing list of annotated chemical signals in applied sciences.</p>","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":"29 2","pages":"111-122"},"PeriodicalIF":1.3,"publicationDate":"2023-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10068406/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9601254","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rapid detection of serum free light chains by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.","authors":"Zelal Zuhal Kaya,&nbsp;Muhittin Serdar,&nbsp;Fehime Aksungar,&nbsp;Meltem Kilercik,&nbsp;Mustafa Serteser,&nbsp;Ahmet Tarik Baykal","doi":"10.1177/14690667231153616","DOIUrl":"https://doi.org/10.1177/14690667231153616","url":null,"abstract":"<p><p><b>Introduction:</b> Serum free light chain (FLC) measurements are increasingly prominent for patients with plasma cell disorders (PCDs) in screening, prognostic stratification, and monitoring therapy responses. <b>Objectives:</b> We aimed to develop a sensitive, reliable, and accurate method for diagnosing PCDs that can notably decrease the time and cost of current methods. <b>Methods:</b> Here, we present a novel approach for FLC measurement using immunoenrichment on micro-affinity chromatography in combination with matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry (MS) detection. In this study, serum free kappa (κ) and free lambda (λ) light chain (LC) levels in the serum of 105 patients were compared between the nephelometric serum FLC quantification and MALDI-TOF MS detection. <b>Results:</b> Cohen's kappa coefficient between the MALDI-TOF MS-based method and the FLC assay revealed an almost perfect agreement in the case of normal (negative) results (κ = 0.92; 95% confidence interval (CI): 0.837 to 0.968) and a good agreement in the case of increased (positive) results (κ = 0.76; 95% CI: 0.608 to 0.870). In Spearman's correlation analysis, the best correlation was found between serum free κ/λ ratios (r = 0.628, 0.496 to 0.732; <i>p</i> <0.0001). Our method showed sensitivity (92.5%) and specificity (76.3%) for discrimination between the κ/λ FLC ratio compared to the serum FLC assay. <b>Conclusion:</b> The proposed method can significantly contribute to diagnosing and monitoring PCDs as it can significantly be time-saving, cost-effective in FLC measurement.</p>","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":"29 2","pages":"132-140"},"PeriodicalIF":1.3,"publicationDate":"2023-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9238069","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}