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. 2018 Feb;17(1):1-16.
doi: 10.1007/s11101-017-9507-3. Epub 2017 May 9.

Procyanidins: a comprehensive review encompassing structure elucidation via mass spectrometry

Emily A Rue  1 , Michael D Rush  1 , Richard B van Breemen  1
Affiliations

Procyanidins: a comprehensive review encompassing structure elucidation via mass spectrometry

Emily A Rue et al. Phytochem Rev. 2018 Feb.

Abstract

Procyanidins are polyphenols abundant in dietary fruits, vegetables, nuts, legumes, and grains with a variety of chemopreventive biological effects. Rapid structure determination of these compounds is needed, notably for the more complex polymeric procyanidins. We review the recent developments in the structure elucidation of procyanidins with a focus on mass spectrometric approaches, especially liquid chromatography-tandem mass spectrometry (LC-MS/MS) and matrix-assisted laser desorption ionization (MALDI) MS/MS.

Keywords: Procyanidins; oligomeric; polymeric; structure elucidation.

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Figures

Figure 1
Figure 1
Chemical structures of monomeric and polymeric procyanidins (Xie and Dixon 2005; Tsao 2010)
Figure 2
Figure 2
Electrospray serves as an atmospheric pressure interface between the HPLC and the mass spectrometer while simultaneously facilitating the formation of gas-phase ions of non-volatile and thermally labile solutes in the mobile phase such as procyanidins
Figure 3
Figure 3
Fragmentation pathway of B-type procyanidin dimer showing the products formed by quinone methide (QM), heterocyclic ring fussion (HRF), and retro-Diels Alder (RDA) reactions (Hellström et al. 2007)
Figure 4
Figure 4
Fragmentation pathway of A-type procyanidin dimer showing the products formed by quinone methide (QM), heterocyclic ring fussion (HRF), and retro-Diels Alder (RDA) reactions (Sui et al. 2016)
Figure 5
Figure 5
Matrix-assisted laser desorption ionization utilizing a laser for desorption of a sample in a matrix material facilitating the protonation/deprotonation of samples such as procyanidins
Figure 6
Figure 6
MALDI-ToF/ToF product ion mass spectrum of deprotonated procyanidin C1. This procyanidin B-type trimer was provided by Jan Glinski of Planta Analytica (New Milford, CT), and the tandem mass spectrum was obtained by Paul Kowalski using a Bruker Daltonics UltrafleXtreme (Billerica, MA) MALDI-ToF/ToF mass spectrometer.
Figure 7
Figure 7
Tetramer proanthocyanidin displaying mixed type configuration (based on Mateos-Martín et al. 2012)
Figure 8
Figure 8
MALDI-ToF/ToF product ion mass spectrum of deprotonated procyanidin A1. This A-type procyanidin dimer was provided by Jan Glinski (Planta Analytica), and the tandem mass spectrum was obtained by Paul Kowalski (Bruker Daltonics).
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