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Peter Max Gehrig Bernd Roschitzki Dorothea Rutishauser Sonja Reiland Ralph Schlapbach 《Rapid communications in mass spectrometry : RCM》2009,23(10):1435-1445
In order to investigate gas‐phase fragmentation reactions of phosphorylated peptide ions, matrix‐assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI) tandem mass (MS/MS) spectra were recorded from synthetic phosphopeptides and from phosphopeptides isolated from natural sources. MALDI‐TOF/TOF (TOF: time‐of‐flight) spectra of synthetic arginine‐containing phosphopeptides revealed a significant increase of y ions resulting from bond cleavages on the C‐terminal side of phosphothreonine or phosphoserine. The same effect was found in ESI‐MS/MS spectra recorded from the singly charged but not from the doubly charged ions of these phosphopeptides. ESI‐MS/MS spectra of doubly charged phosphopeptides containing two arginine residues support the following general fragmentation rule: Increased amide bond cleavage on the C‐terminal side of phosphorylated serines or threonines mainly occurs in peptide ions which do not contain mobile protons. In MALDI‐TOF/TOF spectra of phosphopeptides displaying N‐terminal fragment ions, abundant b–H3PO4 ions resulting from the enhanced dissociation of the pSer/pThr–X bond were detected (X denotes amino acids). Cleavages at phosphoamino acids were found to be particularly predominant in spectra of phosphopeptides containing pSer/pThr–Pro bonds. A quantitative evaluation of a larger set of MALDI‐TOF/TOF spectra recorded from phosphopeptides indicated that phosphoserine residues in arginine‐containing peptides increase the signal intensities of the respective y ions by almost a factor of 3. A less pronounced cleavage‐enhancing effect was observed in some lysine‐containing phosphopeptides without arginine. The proposed peptide fragmentation pathways involve a nucleophilic attack by phosphate oxygen on the carbon center of the peptide backbone amide, which eventually leads to cleavage of the amide bond. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
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The addition–deletion theorems for hyperplane arrangements,which were originally shown by Terao [J. Fac. Sci. Univ. TokyoSect. IA Math. 27 (1980) 293–320.], provide useful waysto construct examples of free arrangements. In this article,we prove addition–deletion theorems for multiarrangements.A key to the generalization is the definition of a new multiplicity,called the Euler multiplicity, of a restricted multiarrangement.We compute the Euler multiplicities in many cases. Then we applythe addition–deletion theorems to various arrangements,including supersolvable arrangements and the Coxeter arrangementof type A3, to construct free and non-free multiarrangements. 相似文献
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Daniel Castaño Díez Max Gunzburger Angela Kunoth 《Numerical Methods for Partial Differential Equations》2008,24(6):1388-1404
We extend the multiscale finite element viscosity method for hyperbolic conservation laws developed in terms of hierarchical finite element bases to a (pre‐orthogonal spline‐)wavelet basis. Depending on an appropriate error criterion, the multiscale framework allows for a controlled adaptive resolution of discontinuities of the solution. The nonlinearity in the weak form is treated by solving a least‐squares data fitting problem. © 2008 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 2008 相似文献
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