Combinatorics of proanthocyanidins in wine†
Condensed tannin are polymers comprised of procyanidin and prodelphinidin units and found in wine, chocolate, apples and many other foods. Current analytical methods to characterize these tannins provide aggregate functional results, such as quantified protein binding, important for its relation to astringency. A more detailed understanding of the constituents has become accessible via mass spectrometry (MS) with high resolution and tandem MS techniques. Analysis of wine tannin by these methods provides thousands of signals, far too many to assess using standard techniques. We propose targeted mass filtering using a table of predicted proanthocyanidin oligomers. Condensed tannin in wine is comprised of 4 constitutionally distinct subunits (catechin, catechin gallate, gallocatechin, and gallocatechin gallate), each of which has 4 stereoisomers. Accounting for all 16 subunits, there are over 5 million possible oligomers from monomer to decamer. Since mass spectroscopy is generally blind to stereoisomeric variations, the number of possible observable MS signals can be reduced to a list of 1000. By applying specialized combinatoric functions, a table for the now manageable compilation of possible proanthocyanidin oligomers has been created containing the compound subunit compositions, molecular formulae, and molecular ion signals for the interpretation of condensed tannin mass spectra. Mathematical formulae for the enumeration of possible compounds in any chemical system composed of polymers with discrete subunits resulted from this endeavor and are presented in general form with specific application to this system. As these condensed tannins react with anthocyanins, forming pigmented tannin, the table created here can also be the foundation of a database for the very complex red wine pigments. The system described here could also be applied to the analysis of proanthocyanidins in chocolate and other foods.