Chromatography based profiling of feruloylated arabinans and galactans.

Profiling of pectic arabinans and galactans by analysis of the released oligosaccharides after backbone cleavage provides information on the complexity of the polymer structure. In plants of the family Amaranthaceae, arabinan and galactan substitution with ferulates extends the polysaccharide complexity, changing its chemical properties. Knowledge of the ferulate environment is crucial to understand structure-function-relationships of feruloylated pectins. Here, we present an approach to separate enzymatically generated feruloylated and non-feruloylated arabino- and galactooligosaccharides, followed by deesterification and semiquantitative analysis by HPAEC-PAD using previously reported relative response factors. Application of this approach to sugar beet pectins and insoluble and soluble dietary fiber preparations of amaranth and quinoa suggests that ferulates are preferably incorporated into more complex structures, as nicely demonstrated for feruloylated galactans. Also, ferulate substitution appears to negatively affect enzymatic cleavage by using endo-enzymes. As a consequence, we were able to tentatively identify new feruloylated tri- and tetrasaccharides of galactans isolated from sugar beet pectins.

Chemically Different but Often Mistaken Phenolic Polymers of Food Plants: Proanthocyanidins and Lignin in Seeds.

Flavonoid based proanthocyanidins and cinnamyl alcohol based lignins are chemically complex phenolic oligomers/polymers that are found in food plants. Although structurally very different, these two biopolymers are often not distinguished, for example, in the (quantitative) compositional analysis of cell walls and dietary fiber. Here, we analytically distinguish lignin and proanthocyanidins in dietary fiber samples by using degradative and nondegradative techniques and provide information about their occurrence, abundance, and structural characteristics in seeds of chokeberries, cranberries, raspberries, red currants, and grapes. These data revealed that the seeds of botanically diverse fruits largely differ in terms of their phenolic fiber polymers. The mostly hardened tissue of the seeds is not necessarily based on lignified cell walls. For example, red currant and chokeberry seeds almost exclusively contain proanthocyanidins, and raspberry seeds were clearly lignified (G-H-lignin) but did not contain proanthocyanidins. Our data also allows for estimating the bias of proanthocyanidins on different approaches of lignin analysis.

Characterization of covalent, feruloylated polysaccharide gels by pulsed field gradient-stimulated echo (PFG-STE)-NMR.

Translational mobility of guest molecules such as water and glucose in gels that are based on feruloylated polysaccharides appears to be critical to understand their nutritional and functional properties. Here, the applicability of PFG-STE-NMR on feruloylated gels was proven, and relationships to rheological data were studied. Arabinoxylans and pectins were extracted from by-products using varying conditions. Laccase induced coupling of these chemically characterized polymers resulted for most of the feruloylated polysaccharides in homogeneous gels. Rheological studies confirmed that polysaccharide composition affects viscoelastic properties of the resulting gels. Generally, diffusion of water and glucose is hindered in gels. In the feruloylated polysaccharide gels, both polysaccharide concentration and extraction conditions affect the diffusion behavior of these molecules. A simple correlation between rheological data and mobility of guest molecules has not generally been found: although long time acid extracted pectins form highly elastic gels, water diffusion in these gels is less hindered.