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Pinus nigra var. laricio bark and its hot-water extracts (HWE) obtained at an analytical and pilot plant scale have been characterized in terms of phenolic extractives, condensed tannins (CTs), carbohydrates and inorganic compounds. Analytical extractions with aqueous acetone were also performed for comparison with HWE. The bark contains 35.5 g kg−1 CT, and two-thirds of it could be extracted. Analytical HWE at 75°C led to a total yield of 56.4 g kg−1. The extracts are mainly composed of phenolic compounds (50.7%) and pectins (19.7%). CTs amount to 17.9% of the extracts and are procyanidins with a mean degree of polymerization (DP) of about 9. Non-tannin phenolic oligomers also occurred in the extracts, which could be identified by pyrolysis gas chromatography mass spectrometry (Py-GC/MS) as lignin fragments. Matrix-assisted laser desorption/ionization-time-of-flight-mass spectrometry (MALDI-TOF MS) revealed that the CT is a flavanol derivative in methylated form. Further characterization and tailoring of the HWE properties is needed in the context of their specific application.

The hot water (HW) extraction of Norway spruce (Picea abies [Karst.]) delivers condensed tannins and considerable amounts of other compounds. Yield and composition of the HW extracts were investigated as a function of natural weathering for up to 15 months. Total phenol monomers and oligomers were detected by Folin-Ciocaltau assay after fractionation by solid phase extraction (SPE). Procyanidins (PC) were determined by HPLC-UV after acid thiolysis and carbohydrates by HPLC combined with acid hydrolysis. Topochemistry of the bark before and after extraction was investigated by UV-microspectrometry (UMSP) and non-extractable PC analyzed by direct thiolysis on the bark. The influence of the parameters on the yield and composition of the extracts were evaluated, such as the extraction temperature, time and the addition of sodium sulfate and urea. Prolonged weathering resulted in a considerable decrease of the total extraction yield, partly because of leaching of phenolic monomers, mono- and oligosaccharides. The yield of phenolic oligomers also decreased at a moderate rate, while the yield of polysaccharides (pectins) was almost stable. Non-extractable and non-leachable compounds deposited in the cell lumens represent the majority of the phenolic extractives in spruce bark. Sequential extractions performed at increasing temperature proved to be a suitable method for the recovery of tannin-rich extracts.

Condensed tannins extracted from European softwood bark are recognized as alternatives to synthetic phenolics. The extraction is generally performed in hot water, leading to simultaneous extraction of other bark constituents such as carbohydrates, phenolic monomers and salts. Characterization of the extract's composition and identification of the extracted tannins' molecular structure are needed to better identify potential applications. Bark from Silver fir (Abies alba [Mill.]), European larch (Larix decidua [Mill.]), Norway spruce (Picea abies [Karst.]), Douglas fir (Pseudotsuga menziesii [Mirb.]) and Scots pine (Pinus sylvestris [L.]) were extracted in water at 60°C. The amounts of phenolic monomers, condensed tannins, carbohydrates, and inorganic compounds in the extract were determined. The molecular structures of condensed tannins and carbohydrates were also investigated (HPLC-UV combined with thiolysis, MALDI-TOF mass spectrometry, anion exchange chromatography). Distinct extract compositions and tannin structures were found in each of the analysed species. Procyanidins were the most ubiquitous tannins. The presence of phenolic glucosides in the tannin oligomers was suggested. Polysaccharides such as arabinans, arabinogalactans and glucans represented an important fraction of all extracts. Compared to traditionally used species (Mimosa and Quebracho) higher viscosities as well as faster chemical reactivities are expected in the analysed species. The most promising species for a bark tannin extraction was found to be larch, while the least encouraging results were detected in pine. A better knowledge of the interaction between the various extracted compounds is deemed an important matter for investigation in the context of industrial applications of such extracts.

Condensed tannins extracted from the bark of softwoods have been proven to be suitable compounds in the formulation of environmentally friendly adhesives and resins. Their chemical structure has been shown to significantly influence their properties and possible applications. Condensed tannins extracted from the bark of Norway spruce (Picea abies [Karst.]) and Silver fir (Abies alba [Mill.]) still lack a detail characterization of their chemical structure. In an effort to address this deficiency, barks from these species were collected and extracted in water at 60°C. The dried extracts were analyzed by MALDI-TOF mass spectrometry to identify the building blocks and to determine the degree of polymerization of the tannin oligomers. The condensed tannins extracted from spruce bark at the used conditions were mainly composed of procyanidins with a polymerization degree up to 13. Silver fir extracts revealed a predominance of prodelphinidins with a polymerization degree up to 9. The presence of less common building blocks such as stilbene glucosides and flavan-3-ols gallates was also hinted. Different curing times and viscosities in resin formulations are expected between the two studied species, as well as in comparison to the most known and available tannins from tropical species.

The hot water (HW) extraction of Norway spruce (Picea abies [Karst.]) delivers condensed tannins and considerable amounts of other compounds. Yield and composition of the HW extracts were investigated as a function of natural weathering for up to 15 months. Total phenol monomers and oligomers were detected by Folin-Ciocaltau assay after fractionation by solid phase extraction (SPE). Procyanidins (PC) were determined by HPLC-UV after acid thiolysis and carbohydrates by HPLC combined with acid hydrolysis. Topochemistry of the bark before and after extraction was investigated by UV-microspectrometry (UMSP) and non-extractable PC analyzed by direct thiolysis on the bark. The influence of the parameters on the yield and composition of the extracts were evaluated, such as the extraction temperature, time and the addition of sodium sulfate and urea. Prolonged weathering resulted in a considerable decrease of the total extraction yield, partly because of leaching of phenolic monomers, mono- and oligosaccharides. The yield of phenolic oligomers also decreased at a moderate rate, while the yield of polysaccharides (pectins) was almost stable. Non-extractable and non-leachable compounds deposited in the cell lumens represent the majority of the phenolic extractives in spruce bark. Sequential extractions performed at increasing temperature proved to be a suitable method for the recovery of tannin-rich extracts.