Macromolecular Model of the Pectic Polysaccharides Isolated from the Bark of Norway Spruce (Picea abies)

The bark of Norway spruce (Picea abies) contains up to 13% pectins that can be extracted by pressurized hot water, which constitute a valuable renewable resource in second-generation lignocellulosic biorefineries. This article proposes, for the first time, structural molecular models for the pectins present in spruce bark. Pectin fractions of tailored molar masses were obtained by fractionation of the pressurized hot water extract of the inner bark using preparative size-exclusion chromatography. The monosaccharide composition, average molar mass distribution, and the glycosidic linkage patterns were analyzed for each fraction. The pectin fraction with high molecular weight (M(w) of 59,000 Da) contained a highly branched RG-I domain, which accounted for 80% of the fraction and was mainly substituted with arabinan and arabinogalactan (type I and II) side chains. On the other hand, the fractions with lower molar masses (M(w) = 15,000 and 9000 Da) were enriched with linear homogalacturonan domains, and also branched arabinan populations. The integration of the analytical information from the macromolecular size distributions, domain composition, and branch lengths of each pectin fraction, results in a comprehensive understanding of the macromolecular architecture of the pectins extracted from the bark of Norway spruce. This paves the way for the valorization of spruce bark pectic polymers in targeted applications based on their distinct polymeric structures and properties.