Structure elucidation of cyclic pyoverdins and examination of rearrangement reactions in MS/MS experiments by determination of exact product ion masses |
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Authors: | Schäfer Mathias Fuchs Regine Budzikiewicz Herbert Springer Andreas Meyer Jean-Marie Linscheid Michael |
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Institution: | Institut für Organische Chemie, Universit?t zu K?ln, Greinsstr. 4, 50939 K?ln, Germany. mathias.schaefer@uni-koeln.de |
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Abstract: | Structure elucidation of naturally occurring linear and cyclic peptidic compounds can be complicated by rearrangement reactions induced upon collision activation (CA) when parts of the molecule migrate, suggesting incorrect substitution patterns. Such complex rearrangements are examined and discussed for two iron complexing compounds produced by the bacterial genus Pseudomonas (so-called pyoverdins). Various MS2- and MS3-product ion experiments were performed using a quadrupole-ion trap (QIT) at low resolution and a FT-ICR at high resolution allowing accurate mass determinations. The results of the multidimensional study confirm the proposed processes. On the basis of the series of tandem-MS experiments the structure of a new pyoverdin from a P. fluorescens strain PVD(D47)] is deduced. |
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Keywords: | rearrangement reactions cyclic peptides pyoverdins FT‐ICR‐MS exact mass measurements |
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