European Journal of Mass Spectrometry最新文献

{"title":"Liquid chromatography-electrospray ionization-mass spectrometry/mass spectrometry characterization of depsides and depsidones from the Chilean lichen <i>Parmotrema perlatum</i>.","authors":"Grover Castañeta, Beatriz Sepulveda, Carlos Areche","doi":"10.1177/14690667241240477","DOIUrl":"10.1177/14690667241240477","url":null,"abstract":"<p><p>Lichens are recognized by their unique compounds and diverse applications in food, medicines, and cosmetics. Using ultra-high pressure liquid chromatography, coupled with a high-resolution mass spectrometer, metabolomic profiling of the lichen <i>Parmotrema perlatum,</i> from a methanolic extract, was performed. Based on characteristic fragmentation patterns, twenty-five lichenic substances were tentatively identified including 5 depsides, 12 depsidones, 2 diphenyl ethers, 1 aromatic considered as possible artifact, 1 dibenzofuran, 1 carbohydrate, 1 organic acid, and 2 undefined compounds. To the best of our knowledge, this is a more complete report of their phytochemistry from <i>P perlatum</i>. Our findings of the <i>P perlatum</i> profile may contribute and complement the current data of the <i>Parmotrema</i> genus.</p>","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":" ","pages":"125-132"},"PeriodicalIF":1.3,"publicationDate":"2024-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140206501","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":"Method for determination of elemental impurities in metronidazole benzoate using inductively coupled plasma mass spectrometry.","authors":"Maoxian Tian, Hui Zhang, Huajun Fan, Mingxing Yin, Wenqing Wang, Chunyang Shi","doi":"10.1177/14690667231211696","DOIUrl":"10.1177/14690667231211696","url":null,"abstract":"<p><p>The elemental impurities in pharmaceutical products have aroused widespread concern among respective supervising authorities and official pharmacopoeias since they are harmful and have no therapeutic effects. Metronidazole benzoate is used extensively to treat a variety of infections. However, impurities will inevitably be introduced in the manufacturing process of metronidazole benzoate. Hence, in this study, a sensitive method was developed for trace determination of elemental impurities in metronidazole benzoate active pharmaceutical ingredients by using inductively coupled plasma mass spectrometry in kinetic energy discrimination mode. The method was validated for system suitability, specificity, linearity, sensitivity, accuracy, and precision according to USP chapter <233> Elemental Impurities-Procedure. The method had good linearity with correlation coefficients > 0.99. The limits of detection were in the range of 0.0003-0.1411 μg/g, which was lower than the acceptable limit and indicated the high sensitivity of the method. The method was accurate with the recoveries in the range of 92%-107%. Moreover, the content of seven elemental impurities in the three batches of metronidazole benzoate active pharmaceutical ingredients by this method was originally below their limits and less than 30% of permitted daily exposure, meeting the requirement of International Council for Harmonization Q3D guidelines. Thus, this newly developed and validated method for estimating elemental impurities in metronidazole benzoate active pharmaceutical ingredients was within the permitted limit and suitable for routine use.</p>","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":" ","pages":"60-64"},"PeriodicalIF":1.3,"publicationDate":"2024-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71479675","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":"Dipole and quadrupole resonance excitation in linear quadrupoles.","authors":"N V Konenkov","doi":"10.1177/14690667231204359","DOIUrl":"10.1177/14690667231204359","url":null,"abstract":"<p><p>In the development of commercial quadrupole mass spectrometers, there is an interest in improving the performance characteristics such as transmission, resolution, and mass range. In particular, parametric and dipolar resonance excitation of trapping ions are used for linear quadrupole mass filters. Theoretical methods and numerical simulation of ion trajectories were applied for study of ion-optical properties. The review is devoted to description of different excitation methods to improve QMF performance and consists of three parts. The first part presents the results of a linear ion trap simulation for various operating conditions and excitation methods. The second part considers the effects of dipole excitation (DE) on the performance of the quadrupole mass filter. The last part analyzes the formation of stability islands by different methods of quadrupole excitation. To date conditions of mass separation in quadrupole mass filters with sin wave supply were described for stability islands of the first and third stability regions formed by quadrupole and DE. By complicating the electronics such methods allow to overcome the destructive influence of electric field distortions and obtain a resolving power and ion transmission efficiency comparable with commercial devices. At quadrupole resonance excitation by a two-frequency signal, it is possible to reduce the length of electrodes three times without losses in resolution and transmission, which reduces the cost of rod set production with micrometer accuracy. Dipole resonance excitation allows controlling the shape of the mass peak by changing amplitude and phase of the auxiliary AC signal. The main factors affecting the resolving power of a linear ion trap are described theoretically. The numerical modeling results are confirmed by experiment.</p>","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":" ","pages":"3-37"},"PeriodicalIF":1.3,"publicationDate":"2024-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41195743","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":"Intramolecular interactions and the neutral loss of ammonia from collisionally activated, protonated ω-aminoalkyl-3-hydroxyfurazans.","authors":"J Stuart Grossert, Donatella Boschi, Marco L Lolli, Robert L White","doi":"10.1177/14690667231214672","DOIUrl":"10.1177/14690667231214672","url":null,"abstract":"<p><p>Gas phase fragmentation reactions of monoprotonated 4-(3-aminopropyl)- and 4-(4-aminobutyl)-3-hydroxyfurazan were investigated to examine potential interactions between functional groups. The two heterocyclic alkyl amines were ionized by electrospray ionization (ESI, positive mode) and fragmented using tandem mass spectrometry (MS/MS). The fragmentation pathways were characterized using pseudo MS³ experiments, precursor-ion scans, and density functional computations. For both heterocyclic ions, loss of ammonia was the only fragmentation process observed at low collision energies. Computational analysis indicated that the most feasible mechanism was intramolecular nucleophilic displacement of ammonia from the protonated ω-aminoalkyl side chain by N5 of the furazan ring. The alkylated nitrogen in the resulting bicyclic product ion facilitated N-O bond cleavage; subsequent neutral losses of nitric oxide (NO) and carbon monoxide (CO) occurred by homolytic bond cleavages. Next in the multistep sequence, neutral loss of ethylene from a radical cation was observed. A less favorable, competing fragmentation pathway of protonated 4-(3-aminopropyl)-3-hydroxyfurazan was consistent with cleavage of the 3-hydroxyfurazan ring and losses of NO and CO. Overall, the similar fragmentation behavior found for protonated 4-(3-aminopropyl)- and 4-(4-aminobutyl)-3-hydroxyfurazan differed from that previously characterized for furazan analogs with shorter alkyl chains. These observations demonstrate that a small change in the structure of multifunctional, heterocyclic alkyl amines may significantly influence interactions between distinct functional groups and the nature of the fragmentation process.</p>","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":" ","pages":"38-46"},"PeriodicalIF":1.1,"publicationDate":"2024-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10809737/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136396974","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":"Evaluation of SP3 for antibody-free quantification of tau in CSF mimic and brain by mass spectrometry.","authors":"Chloé Jacquemin, Nicolas Villain, Rita Azevedo, Susana Boluda, Etienne A Thévenot, François Fenaille, Foudil Lamari, François Becher","doi":"10.1177/14690667231218912","DOIUrl":"10.1177/14690667231218912","url":null,"abstract":"<p><p>Tubulin-associated unit (tau) has an important role in the pathogenesis and the diagnosis of Alzheimer's disease (AD) and other tauopathies. In view of the diversity of tau proteoforms, antibody-free methods represent a good approach for unbiased quantification. We adapted and evaluated the single-pot, solid-phase-enhanced sample-preparation (SP3) protocol for antibody-free extraction of the tau protein in cerebro-spinal fluid (CSF) mimic and in human brain. A total of 13 non-modified peptides were quantified by high-resolution mass spectrometry (HRMS) after digestion of tau by trypsin. We significantly improved the basic SP3 protocol by carefully optimizing the organic solvents and incubation time for tau binding, as well as the digestion step for the release directly from the SP3 beads of the 13 tau peptides. These optimizations proved to be primarily beneficial for the most hydrophilic tau peptides, increasing the sequence coverage of recombinant tau. Mean recovery in CSF mimic of the 13 non-modified peptides was of 53%, with LODs ranging from 0.75 to 10 ng/mL. Next, we tested the optimized SP3 protocol on pathological tau extracted from the soluble fraction from an AD brain sample (middle frontal gyrus). We could successfully identify and quantify biologically relevant tau peptides including representative peptides of two isoforms and two phospho-peptides (pTau217 and pTau181).</p>","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":" ","pages":"65-75"},"PeriodicalIF":1.3,"publicationDate":"2024-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139520369","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":"Coordination and fragmentation chemistry of CyMe₄-BTPhen complexes with lanthanides and actinides: A combined investigation by ESI-MS and DFT calculations.","authors":"Qiqi Zhang, Yang Liu, Shuping Tan, Yan Chen, Xinyue Liang, Weiqun Shi, Yonggang Zhao","doi":"10.1177/14690667231206035","DOIUrl":"10.1177/14690667231206035","url":null,"abstract":"<p><p>To further understand the complexation and fragmentation during the extraction process, the formation of 2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-12,4-benzotriazin-3-yl)-1,10-phenanthroline (CyMe₄-BTPhen) complexes with lanthanides (Ln = La, Ce, Nd, Sm, Eu, Yb) and actinides (UO₂²⁺, Th⁴⁺) was observed by electrospray ionization mass spectrometry (ESI-MS) technique and density functional theory (DFT) calculations. Mass spectrometry titrations showed the variation relationship of different complexes in acetonitrile. For lanthanides, the major complexes were 1:2 species ([Ln(L)₂]³⁺ and [Ln(L)₂(NO₃)]²⁺) with a ratio of 1:2, which were observed at the initial addition of Ln³⁺, whereas the species ([Ln(L)(NO₃)₂]⁺) with a ratio of 1:1 was detected when the [Ln]/[L] concentration ratio reached 1.0. For UO₂²⁺ and Th⁴⁺ complexes, 1:1 or 1:2 species ([UO₂L(NO₃)]⁺, Th(L)₂(NO₃)³⁺ and Th(L)₂(NO₃)₂²⁺) were formed. The fragmentation chemistry of both the ligand and the complex cations was characterized in detail by collision-induced dissociation. The fragmentation process of CyMe₄-BTPhen was unfolded sequentially on both sides of the ligand by cleavage of C-C and C-N bonds. DFT calculations provided a detailed analysis of the structures and thermodynamics of those complexes, which indicated that the stable complexes formed in acetonitrile solution were consistent with the ESI-MS results.</p>","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":" ","pages":"47-59"},"PeriodicalIF":1.3,"publicationDate":"2024-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41117565","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":"Simultaneous quantification of tiotropium bromide impurities G + H in capsule formulation by LC-MS/MS.","authors":"Serdar Erkol, Müge Güleli, Cem Çalışkan, Sevgi Kocaoba","doi":"10.1177/14690667231217879","DOIUrl":"10.1177/14690667231217879","url":null,"abstract":"<p><p>Tiotropium Bromide is a long-acting bronchodilator that is used in the treatment of chronic obstructive pulmonary disease (COPD) and asthma bronchodilator or bronchiolitis, which are substances that expand the bronchi and reduce resistance in the respiratory tract and increase airflow to the lungs. For Tiotropium Bromide found in inhaler capsules to treat COPD, determining the relevant impurities G and H, which are not UV active, is crucial. For this purpose, a new and sensitive liquid chromatography triple-quadrupole mass spectrometry (LC-MS/MS) detection with electrospray ionization by using multiple reaction monitoring in the positive mode method was developed and validated. The identity of the compounds was supported by using LC-Q/TOF. All chromatographic studies were performed with a Zorbax Eclipse XDB-C8 (150 mm x 4.6 mm, 5.0 µm) column with a total injection time of 13 min at a flow rate of 0.4 ml/min as a gradient. The limit of detection (LOD) and limit of quantitation (LOQ) in the current study range were determined as 1.0 ppb and 2.5 ppb, respectively. The results of the validation parameters following the ICH Q2(R1) guideline were determined within the acceptance criteria.</p>","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":" ","pages":"76-83"},"PeriodicalIF":1.3,"publicationDate":"2024-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138458772","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":"Corrigendum to The analytical solution for the optimum voltage on regularizing electrodes of the open dynamically harmonized cell.","authors":"","doi":"10.1177/14690667241227669","DOIUrl":"10.1177/14690667241227669","url":null,"abstract":"","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":" ","pages":"NP1"},"PeriodicalIF":1.3,"publicationDate":"2024-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139520365","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":"Toward a MALDI in-source decay (ISD) method for top-down analysis of protein footprinting.","authors":"Ruidong Jiang, Don L Rempel, Michael L Gross","doi":"10.1177/14690667231202695","DOIUrl":"10.1177/14690667231202695","url":null,"abstract":"<p><p>Irreversible protein footprinting is a mass spectrometry-based approach in which solvent-accessible sites of a protein are modified to assess high-order protein structure. Structural insights can be gained by determining the position and extents of modification. The usual approach to obtain the \"footprint\" is to analyze the protein through bottom-up LC-MS/MS. In this approach, the proteins are digested to yield a mixture of peptides that are then separated by LC before locating the modification sites by MS/MS. This process consumes substantial amounts of time and is difficult to accelerate for applications that require quick and high-throughput analysis. Here, we describe employing matrix-assisted laser desorption/ionization (MALDI) in-source decay (ISD) to analyze a footprinted small test protein (ubiquitin) via a top-down approach. Matrix-assisted laser desorption/ionization is easily adapted for high-throughput analysis, and top-down strategies can avoid lengthy proteolysis and LC separation. We optimized the method with model peptides and then demonstrated its feasibility on ubiquitin submitted to two types of footprinting. We found that MALDI ISD can produce a comprehensive set of fragment ions for small proteins, affording footprinting information in a fast manner and giving results that agree with the established methods, and serve as a rough measure of protein solvent accessibility. To assist in the implementation of the MALDI approach, we developed a method of processing top-down ISD data.</p>","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":" ","pages":"292-302"},"PeriodicalIF":1.1,"publicationDate":"2023-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11092977/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41164327","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":"Identification of human hexahydrocannabinol metabolites in urine.","authors":"Willi Schirmer, Volker Auwärter, Julia Kaudewitz, Stefan Schürch, Wolfgang Weinmann","doi":"10.1177/14690667231200139","DOIUrl":"10.1177/14690667231200139","url":null,"abstract":"<p><p>Hexahydrocannabinol (HHC) is a cannabinoid that has been known since 1940 but has only recently found its way into recreational use as a psychoactive drug. HHC has been used as a legal alternative to tetrahydrocannabinol (THC) in many countries, but first countries already placed it under their narcotic substances law. Our aim was to evaluate a reliable analytical method for the proof of HHC consumption by LC-MS/MS and GC-MS. We identified the two epimers of HHC and metabolites after HHC consumption by two volunteers (inhalation by use of a vaporizer and oral intake). LC-HR-MS/MS, LC-MS/MS and GC-MS with literature data (EI-MS spectra of derivatives) and reference compounds - as far as commercially available - were used for metabolite identification. Phase-II-metabolites (glucuronides) of HHC and OH-HHC were found in urine samples with LC-HR-MS/MS and LC-MS/MS. The main metabolite was tentatively identified with GC-MS as 4'OH-HHC (stereochemistry on C9 and C4' unknown). Another major side-chain hydroxylated metabolite found by LC-MS/MS could not be unambiguously identified. Both epimers of 11-OH-HHC were found in considerable amounts in urine. (8<i>R</i>, 9<i>R</i>)-8-OH-HHC was identified as a minor metabolite with GC-MS and LC-MS/MS. While (9<i>S</i>)-HHC was found in urine after oral intake and inhalation of HHC, the more psychoactive epimer (9<i>R</i>)-HHC was only found in urine after inhalation. Several other minor metabolites were detected but not structurally identified. We found that after oral or inhalative consumption the urinary main metabolites of a diastereomeric mixture of HHC are different from the respective, major Δ⁹-THC metabolites (11-OH-Δ⁹-THC and 11-nor-9-carboxy-Δ⁹-THC). Although a sensitive LC-MS/MS and GC-SIM-MS method were set-up for the reference compounds (9<i>R</i>)-11-nor-9-carboxy-HHC and (9<i>S</i>)-11-nor-9-carboxy-HHC, these oxidation products were not detected in urine with these techniques. To further increase sensitivity, a GC-MS/MS method was developed, and the 11-nor-9-carboxy metabolites of HHC were confirmed to be present as minor metabolites.</p>","PeriodicalId":12007,"journal":{"name":"European Journal of Mass Spectrometry","volume":" ","pages":"326-337"},"PeriodicalIF":1.3,"publicationDate":"2023-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"10296648","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}