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https://hdl.handle.net/2440/53502
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Type: | Journal article |
Title: | Characteristic negative ion fragmentations of deprotonated peptides containing post-translational modifications: mono-phosphorylated Ser, Thr and Tyr. A joint experimental and theoretical study |
Author: | Andreazza, H. Fitzgerald, M. Bilusich, D. Hoffmann, R. Hoffmann, P. Eichinger, P. Bowie, J. |
Citation: | Rapid Communications in Mass Spectrometry, 2008; 22(20):3305-3312 |
Publisher: | John Wiley & Sons Ltd |
Issue Date: | 2008 |
ISSN: | 0951-4198 1097-0231 |
Statement of Responsibility: | Hayley J. Andreazza, Mark Fitzgerald, Daniel Bilusich, Ralf Hoffmann, Peter Hoffmann, Peter C. H. Eichinger and John H. Bowie |
Abstract: | Peptides and proteins may contain post-translationally modified phosphorylated amino acid residues, in particular phosphorylated serine (pSer), threonine (pThr) and tyrosine (pTyr). Following earlier work by Lehmann et al., the [M-H]- anions of peptides containing pSer and pThr functionality show loss of the elements of H3PO4. This process, illustrated for Ser (and using a model system), is CH3CONH-C(CH2OPO3H2)CONHCH(3) --> [CH3CONHC(==CH2)CONHCH3 (-OPO3H2)] (a) --> [CH3CONHC(==CH2)CONHCH3-H]- + H3PO4, a process endothermic by 83 kJ mol(-1) at the MP2/6-31++G(d,p)//HF/6-31++G(d,p) level of theory. In addition, intermediate (a) may decompose to yield CH3CONHC(==CH2)CONHCH3 + H2PO4 - in a process exothermic by 3 kJ mol(-1). The barrier to the transition state for these two processes is 49 kJ mol(-1). Characteristic cleavages of pSer and pThr are more energetically favourable than the negative ion backbone cleavages of peptides described previously. In contrast, loss of HPO3 from [M-H]- is characteristic of pTyr. The cleavage [NH2CH(CH2-C6H4-OPO3H-)CO2H] --> [NH2C(CH2-C6H4-O-)CO2H (HPO3)] (b) --> NH2CH(CH2-C6H4-O-)CO2H + HPO3 is endothermic by 318 kJ mol(-1) at the HF/6-31+G(d)//AM1 level of theory. In addition, intermediate (b) also yields NH2CH(CH2-C6H4-OH)CO2H + PO3 - (reaction endothermic by 137 kJ mol(-1)). The two negative ion cleavages of pTyr have a barrier to the transition state of 198 kJ mol(-1) (at the HF/6-31+G(d)//AM1 level of theory) comparable with those already reported for negative ion backbone cleavages. |
Keywords: | Protons Tyrosine Threonine Serine Peptides Spectrometry, Mass, Electrospray Ionization Protein Processing, Post-Translational Amino Acid Sequence Phosphorylation Molecular Sequence Data |
Description: | The definitive version may be found at www.wiley.com |
DOI: | 10.1002/rcm.3736 |
Grant ID: | ARC |
Published version: | http://dx.doi.org/10.1002/rcm.3736 |
Appears in Collections: | Aurora harvest 5 Chemistry and Physics publications |
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