Substitution pattern elucidation of hydroxypropyl Pinus pinaster (Ait.) bark polyflavonoid derivatives by ESI(−)‐MS/MS |
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| Authors: | Danny E. García Marrero Wolfgang G. Glasser Antonio Pizzi Sebastian Paczkowski Marie‐Pierre G. Laborie |
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| Affiliation: | 1. Freiburger Materialforschungszentrum—FMF, Albert‐Ludwigs University of Freiburg, , D‐79104 Freiburg, Germany;2. Chair of Forest Biomaterials, University of Freiburg, , D‐79085 Freiburg, Germany;3. Department of Sustainable Biomaterials, Virginia Polytechnic Institute and State University, , Blacksburg, VA, 24061 USA;4. Laboratoire d'Etudes et de Recherche sur le Matériau Bois (LERMAB), University of Lorraine, , F‐88000 Epinal, France;5. King Abdulaziz University, , Jeddah, Saudi Arabia |
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| Abstract: | The structure of condensed tannins (CTs) from Pinus pinaster bark extract and their hydroxypropylated derivatives with four degrees of substitution (DS 1, 2, 3 and 4) has been characterized for the first time using negative‐ion mode electrospray ionization tandem mass spectrometry (ESI(?)‐MS/MS). The results showed that P. pinaster bark CTs possess structural homogeneity in terms of monomeric units (C15, catechin). The oligomer sizes were detected to be dimers to heptamers. The derivatives showed typical phenyl‐propyl ether mass fragmentation by substituent elimination (58 amu) and inherent C15 flavonoid fissions. The relative abundance of the product ions revealed a preferential triple, tetra‐/penta‐ and octa‐ hydroxypropylation substitution pattern in the monomer, dimer and trimer derivatives, respectively. A defined order of –OH reactivity towards propylene oxide was established by means of multistage experiments (A‐ring ≥ B‐ring > C‐ring). A high structural heterogeneity of the modified oligomers was detected. Copyright © 2014 John Wiley & Sons, Ltd. |
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| Keywords: | condensed tannins maritime pine bark hydroxypropylation derivatization tandem mass spectrometry degradation of catechin |
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