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Journal of mass spectrometry
John Wiley & Sons Ltd
Journal of mass spectrometry

John Wiley & Sons Ltd

1076-5174

Journal of mass spectrometry/Journal Journal of mass spectrometryICCCREIAHCISCIISTP
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    Fragmentation pathways of deprotonated ortho-hydroxybenzyl alcohol

    Kumar, MeenuZheng, ZhaoyuNishshanka, UpulXia, Hanxue...
    16页
    查看更多>>摘要：The ortho, meta, and para isomers of hydroxybenzyl alcohol can be unequivocally distinguished by the collision-induced dissociation mass spectra of their anions. The presence of a prominent peak at m/z 121 for an elimination of a dihydrogen molecule renders the ortho-isomer spectrum markedly different from those of its meta and para congeners. Investigations carried out with deuterium-labeled isotopologues of the ortho isomer verified that the labile hydrogen atom on the hydroxyl group and one of the benzylic hydrogen atoms are specifically removed in the formation of the m/z 121 ion. The ortho-isomer spectrum also showed a prominent peak at m/z 93. Experimental data indicated that the m/z 93 product ion originates either from a two-step H(2)and CO elimination mechanism or from a direct loss of a HCHO molecule from the precursor anion. The intensity ratio of the m/z 93 and 94 peaks in the spectrum recorded from the m/z 124 ion generated from a sample of o-hydroxybenzyl alcohol dissolved in D2O supported the notion that the direct HCHO loss is the more dominant pathway for the generation of the phenolate ion under low activation conditions. In contrast, the two-step mechanism becomes the more dominant pathway under high collisional activation conditions. The spectrum also showed a weak peak at m/z 105 for a water loss. Based on computational data, the m/z 105 ion generated in this way appears to be a composite generated from a common ion-neutral complex intermediate in which a hydroxyl anion is positioned equidistantly between one of the benzylic hydrogens and a nearby hydrogen atom of the benzene ring. Upon activation, the complex dissociates to form either a phenide or a quinone methide anion. The reaction forming a carbon dioxide adduct under ion-mobility conditions was used to support the proposed water-loss mechanism.
      原文链接:
    • NSTL
    • Wiley

    Rapid diagnosis of papillary thyroid carcinoma with machine learning and probe electrospray ionization mass spectrometry

    Wang, YeChen, ZhenheShima, KeisukeZhong, Dingrong...
    9页
    查看更多>>摘要：Frozen section examination could provide pathological diagnosis for surgery of thyroid nodules, which is time-consuming, skill- and experience-dependent. This study developed a rapid classification method for thyroid nodules and machine learning. Total 69 tissues were collected including 43 nodules and 26 nodule-adjacent tissues. Intraoperative frozen section was first performed to give accurate diagnosis, and the rest frozen specimen were pretreated for probe electrospray ionization mass measurement. By multivariate analysis of mass scan data, a series compounds were found downregulated in the extraction solution of papillary thyroid carcinoma (PTC), but some were found upregulated by mass spectrometry imaging. m/z 758.5713 ([PC[34:2] + H](+)), m/z 772.5845 ([PC[32:0] + K](+)), and m/z 786.6037 ([PC[36:2] + H](+)) were firstly identified as potential biomarkers for nodular goiter (NG). Machine learning was employed by means of support vector machine (SVM) and random forest (RF) algorithms. For classification of PTC from NG, SVM and RF algorithms exhibited the same performance and the concordance was 94.2% and 94.4% between prediction and pathological diagnosis with positive and negative mass dataset, respectively. For the classification of PTC from PTC adjacent tissues, SVM was better than RF and the concordance was 93.8% and 83.3% with positive and negative mass dataset, respectively. With the identified compounds as training features, the sensitivity and specificity are 87.5% and 88.9% for the test set. The developed method could also correctly predict the malignancy of one medullary thyroid carcinoma and one adenomatous goiter (benign). The diagnosis time is about 10 min for one specimen, and it is very promising for the intraoperative diagnosis of papillary thyroid carcinoma.
      原文链接:
    • NSTL
    • Wiley

    Fast and eco-friendly method using atmospheric solids analysis probe mass spectrometry to characterize orange varieties

    Pizzo, Jessica SantosSilva, Jiuliane MartinsSilva Santos, Patricia DanieleVisentainer, Jesui Vergilio...
    7页
    查看更多>>摘要：Orange fruit is one of the most popular types of fruit in the world, and its juice is the main product of its processing. This study aimed to evaluate a simple, fast, and eco-friendly methodology, atmospheric solids analysis probe mass spectrometry (ASAP-MS), to assess the chemical profile of four oranges varieties (Valencia, Folha Murcha, Pera, and Iapar). The oranges' varieties were evaluated for the physicochemical composition (extraction yield, pH, total titratable acidity, total soluble solids [TSS], degrees Brix), ratio (TSS/TA), and bioactive compounds (ASAP-MS analysis). The characterization of oranges resulted in great values of oranges yield according to the varieties (44.00-48.10% [w/w], adequate and characteristic acidity [0.73-1.35%], soluble solids content (10.24-13.80 degrees Brix), pH (3.30-3.96), and ratio (7.59-19.90) level for this fruit. This powerful method showed that all analysis procedures were simple, fast, and easy because there is no need to prepare the sample and the analysis time lasted 2 min. Besides, results obtained exhibited a vast array of chemical groups. Principal component analysis (PCA) defined and distinguished the varieties of the orange. Therefore, ASAP-MS and PCA showed that they are very attractive candidates for routine analysis to monitor the varieties of the orange with its pronounced advantages, besides being contributing to the environment because it does not use any quantities of organic solvents. This methodology was applied for the first time to this type of sample.
      原文链接:
    • NSTL
    • Wiley

    Normalization techniques for high-throughput screening by infrared matrix-assisted laser desorption electrospray ionization mass spectrometry

    Knizner, Kevan T.Bagley, Michael C.Pu, FanElsen, Nathaniel L....
    10页
    查看更多>>摘要：Mass spectrometry (MS) is an effective analytical tool for high-throughput screening (HTS) in the drug discovery field. Infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) MS is a high-throughput platform that has achieved analysis times of sub-seconds-per-sample. Due to the high-throughput analysis speed, methods are needed to increase the analyte signal while decreasing the variability in IR-MALDESI-MS analyses to improve data quality and reduce false-positive hits. The Z-factor is used as a statistic of assay quality that can be improved by reducing the variation of target ion abundances or increasing signal. Herein we report optimal solvent compositions for increasing measured analyte abundances with direct analysis by IR-MALDESI-MS. We also evaluate normalization strategies, such as adding a normalization standard that is similar or dissimilar in structure to the model target drug, to reduce the variability of measured analyte abundances with direct analyses by IR-MALDESI-MS in both positive and negative ionization modes.
      原文链接:
    • NSTL
    • Wiley

    Probing the pyrolysis of methyl formate in the dilute gas phase by synchrotron radiation and theory

    Lowe, BethanyCardona, Alejandro L.Salas, JuanaBodi, Andras...
    11页
    查看更多>>摘要：The thermal dissociation of the atmospheric constituent methyl formate was probed by coupling pyrolysis with imaging photoelectron photoion coincidence spectroscopy (iPEPICO) using synchrotron VUV radiation at the Swiss Light Source (SLS). iPEPICO allows threshold photoelectron spectra to be obtained for pyrolysis products, distinguishing isomers and separating ionic and neutral dissociation pathways. In this work, the pyrolysis products of dilute methyl formate, CH3OC(O)H, were elucidated to be CH3OH + CO, 2 CH2O and CH4 + CO2 as in part distinct from the dissociation of the radical cation (CH3OH+center dot + CO and CH2OH+ + HCO). Density functional theory, CCSD(T), and CBS-QB3 calculations were used to describe the experimentally observed reaction mechanisms, and the thermal decomposition kinetics and the competition between the reaction channels are addressed in a statistical model. One result of the theoretical model is that CH2O formation was predicted to come directly from methyl formate at temperatures below 1200 K, while above 1800 K, it is formed primarily from the thermal decomposition of methanol.
      原文链接:
    • NSTL
    • Wiley

    Electrospray ionization-tandem mass spectrometric study of fused nitrogen-containing ring systems

    Krajsovszky, GaborKiss, Borbala DalmadineLudanyi, KrisztinaMandity, Istvan M....
    4页
    查看更多>>摘要：Four fused nitrogen-containing ring systems were investigated by electrospray ionization-tandem mass spectrometry: Pyridazino-indoles, pyridazino-quinolines, a pyrimido-quinoline derivative and pyrimido-cinnolines. Fragmentation patterns of these compounds are discussed and compared. Several characteristic cross-ring fragments were formed mainly on the pyridazine and pyrimidine rings of the ring systems. The connected Cl, NO2, Me, Ph and more extended heterocyclic substituents influenced the fragmentation.
      原文链接:
    • NSTL
    • Wiley