Analysis of commercial proanthocyanidins. Part 3: the chemical composition of wattle (Acacia mearnsii) bark extract.

Wattle (Acacia mearnsii) bark extract is an important renewable industrial source of natural polymers for leather tanning and adhesive manufacturing. The wattle bark proanthocyanidin oligomers have 5-deoxy extender units that render the interflavanyl bonds resistant to acid catalysed hydrolysis and their composition cannot be determined via conventional thiolysis. We combined established phyto- and synthetic chemistry perspectives with an electrospray mass spectrometry investigation to establish that the flavan-3-ol based oligomers consist of a starter unit which is either catechin or gallocatechin, angularly bonded to fisetinidol or predominantly robinetinidol extender units.

Analysis of commercial proanthocyanidins. Part 2: An electrospray mass spectrometry investigation into the chemical composition of sulfited quebracho (Schinopsis lorentzii and Schinopsis balansae) heartwood extract.

Proanthocyanidins (PACs) are natural plant-derived polymers used in leather tanning, wood adhesives, water purification, and mud additives for oil drilling. Quebracho (Schinopsis lorentzii and Schinopsis balansae) heartwood and mimosa (Acacia mearnsii) bark extracts are the major industrial sources of PACs. These commercial extracts are often sulfited via treatment with sodium hydrogen sulfite to reduce their viscosity and increase their solubility in water. An ESI-MS investigation into the molecular composition of sulfited (cold-water-soluble) quebracho heartwood extract indicates that sulfitation of the PACs occurs via S(N)2 attack of a sulfite ion at both C-2 and C-4 of the constituent flavan-3-ol monomer extender units. Attack at C-2 leads to the opening of the pyran ring. This releases an additional electron-donating phenolic hydroxy group on the A-ring and renders the extract more nucleophilic and suitable for the manufacturing of adhesives. Attack at C-4 leads to interflavanyl bond fission and decrease of the PAC oligomer chain length. The introduction of sulfonic acid moieties at C-2 or C-4 increases the polarity and water solubility of the hot water soluble (unsulfited) extract and transforms it into a cold-water-soluble extract.