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 (Mw 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 (Mw = 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.

Isolation and characterization of cellulose nanocrystals from spruce bark in a biorefinery perspective.

The present study reports for the first time the isolation of cellulose fibers and cellulose nanocrystals (CNCs) from the bark of Norway spruce. The upgrading of bark cellulose to value-added products, such as CNCs, is part of the "bark biorefinery" concept. The removal of non-cellulosic constituents was monitored throughout the isolation process by detailed chemical composition analyses. The morphological investigation of the CNCs was performed using AFM and showed the presence of nanocrystals with an average length of 175.3 nm and a diameter of 2.8 nm, giving an aspect ratio of around 63. X-ray diffraction (XRD) analyses showed that the crystallinity index increased with successive treatments to reach a final value greater than 80% for CNCs. The thermal degradation of the isolated bark CNCs started at 190 °C. Spruce bark appeared to be a new promising industrial source of cellulose fibers and CNCs.

Hot-water extracts from the inner bark of Norway spruce with immunomodulating activities.

The inner bark of Norway spruce (Picea abies) was sequentially extracted with hot water at 100°C, 140°C and 160°C. The hot-water extracts (IB 100°C, IB 140°C and IB 160°C) contained pectic polysaccharides and showed immunostimulating activities. Structural analyses of their carbohydrate content, including glycosidic linkage analyses, revealed the presence of pectins with a large rhamnogalacturonan RG-I domain ramified with highly-branched arabinans. IB 100°C also contained a large amount of terminal glucosyl residues, indicating the presence of highly substituted polymers. IB 160°C was mainly composed of starch. The hot-water extracts were tested for two biological activities, namely complement fixation and macrophage stimulation. IB 100°C exhibited the highest complement fixation activity, with a 1.7-times higher ICH50 than the control pectin, while IB 140°C and IB 160°C gave similar ICH50 values as the control. Macrophages were stimulated by IB 100°C and IB 140°C in a dose-dependent manner, but not by IB 160°C. IB 100°C presented the highest activity toward macrophages, comparable to the control pectin.