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Andreina Ricci Simona Piccolella Antonio Fiorentino Federico Pepi Brigida D'Abrosca Pietro Monaco 《Rapid communications in mass spectrometry : RCM》2010,24(11):1543-1556
Mass spectrometric fragmentation data of neo‐clerodane diterpenes are almost inexistent but they can prove helpful for the qualitative and quantitative analysis of these compounds as well as for the identification of unknown compounds belonging to this class of plant secondary metabolites. [M–H]– ions of nine neo‐clerodane diterpenes (1–9), recently isolated from Teucrium chamaedrys, were generated by electrospray ionization and were fragmented in the collision cell of a Triple Quadrupole (TQ) and of a Quadrupole Ion Trap (QIT) mass spectrometer. The deprotonated neo‐clerodane glucosides, chamaedryoside A and B (1, 2), readily lost the sugar residue to give, as their main fragmentation channel, the neo‐clerodane ions, I and II, which were structurally characterized by TQ and QIT MS. The collision‐activated dissociation (CAD) mass spectra of I and II and of deprotonated neo‐clerodanes 3–9 allowed us to reach some general conclusions on the fragmentation pathways of this class of compounds. For example, teuflin and its OH derivatives, teucrin A, teuflidin and 6‐β‐hydroxyteucridin, showed a characteristic fragmentation pattern involving the loss of 94 Da and 124 Da from the lactone moiety, whereas a loss of 44 Da was observed for teucrin E, and of 58 Da for teucrin F and G. In addition, several compound‐specific fragmentations were observed and can be proposed for the identification of individual compounds. The systematic approach allowed us to hypothesize the mechanisms of the most important collision‐activated dissociation/isomerization channels. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
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A novel numerical scheme for slug capturing in pipes using a 1‐dimensional transient hyperbolic 5‐equation 2‐fluid model is presented. Previous work has shown that 1‐dimensional 2‐fluid models are able to capture slug flow automatically. In this work, a similar approach is further developed using a new numerical scheme, applied to a hyperbolic 5‐equation 2‐fluid model. Starting from a finite volume discretisation of a 5‐equation 2‐fluid hyperbolic model and adding appropriate closure relations, a second‐order code is implemented and applied to air‐water flows in horizontal pipes, simulating the 2‐phase to 1‐phase flow process. The code is evaluated in some common standard test cases. A slug capturing application is also discussed. We show, in an air/water horizontal pipe, slug initiation, growth, and development. Moreover, a grid refinement analysis is performed showing that the method is grid independent and we show the code capability to take into account eventual surface tension effects, through the instantaneous pressure relaxation process. Finally, a prediction of flow regime transitions is shown and compared with a well‐known theoretical flow pattern map in addition to a preliminary comparison of computed slug characteristics against well‐known empirical correlations. 相似文献
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Dr. Pietro Delcanale Dr. David Porciani Dr. Silvia Pujals Dr. Alexander Jurkevich Andrian Chetrusca Dr. Kwaku D. Tawiah Prof. Dr. Donald H. Burke Prof. Dr. Lorenzo Albertazzi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(42):18705-18714
Tumor cell-surface markers are usually overexpressed or mutated protein receptors for which spatiotemporal regulation differs between and within cancers. Single-molecule fluorescence imaging can profile individual markers in different cellular contexts with molecular precision. However, standard single-molecule imaging methods based on overexpressed genetically encoded tags or cumbersome probes can significantly alter the native state of receptors. We introduce a live-cell points accumulation for imaging in nanoscale topography (PAINT) method that exploits aptamers as minimally invasive affinity probes. Localization and tracking of individual receptors are based on stochastic and transient binding between aptamers and their targets. We demonstrated single-molecule imaging of a model tumor marker (EGFR) on a panel of living cancer cells. Affinity to EGFR was finely tuned by rational engineering of aptamer sequences to define receptor motion and/or native receptor density. 相似文献