Substitution pattern elucidation of hydroxypropyl Pinus pinaster (Ait.) bark polyflavonoid derivatives by ESI(−)‐MS/MS

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 (C 15 , 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 C 15 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.