RESUMO
BACKGROUND: Acetylated galactoglucomannan (AcGGM) is a complex hemicellulose found in softwoods such as Norway spruce (Picea abies). AcGGM has a large potential as a biorefinery feedstock and source of oligosaccharides for high-value industrial applications. Steam explosion is an effective method for extraction of carbohydrates from plant biomass. Increasing the reaction pH reduces the combined severity ( R 0 ' ) of treatment, affecting yields and properties of extracted oligosaccharides. In this study, steam explosion was used to extract oligosaccharides from Norway spruce wood chips soaked with sodium citrate and potassium phosphate buffers with pH of 4.0-7.0. Yields, monosaccharide composition of released oligosaccharides and biomass residue, their acetate content and composition of their lignin fraction were examined to determine the impact of steam explosion buffering on the extraction of softwood hemicellulose. RESULTS: Reducing the severity of steam explosion resulted in lower yields, although the extracted oligosaccharides had a higher degree of polymerization. Higher buffering pH also resulted in a higher fraction of xylan in the extracted oligos. Oligosaccharides extracted in buffers of pH > 5.0 were deacetylated. Buffering leads to a removal of acetylations from both the extracted oligosaccharides and the hemicellulose in the residual biomass. Treatment of the residual biomass with a GH5 family mannanase from Aspergillus nidulans was not able to improve the AcGGM yields. No hydroxymethylfurfural formation, a decomposition product from hexoses, was observed in samples soaked with buffers at pH higher than 4.0. CONCLUSIONS: Buffering the steam explosion reactions proved to be an effective way to reduce the combined severity ( R 0 ' ) and produce a wide range of products from the same feedstock at the same physical conditions. The results highlight the impact of chemical autohydrolysis of hemicellulose by acetic acid released from the biomass in hydrothermal pretreatments. Lower combined severity results in products with a lower degree of acetylation of both the extracted oligosaccharides and residual biomass. Decrease in severity appears not to be the result of reduced acetate release, but rather a result of inhibited autohydrolysis by the released acetate. Based on the results presented, the optimal soaking pH for fine-tuning properties of extracted AcGGM is below 5.0.
RESUMO
There is a growing interest in a more wholesome utilization of biomass as the need for greener chemistry and non-mineral oil-based products increases. Lignin is the largest renewable resource for aromatic chemicals, which is found in all types of lignocellulosic biomass. Steam-explosion of lignocellulosic biomass is a useful pretreatment technique to make the polymeric material more available for processing. However, this heat-based pretreatment is known to result in the formation of pseudo-lignin, a lignin-like polymer made from carbohydrate degradation products. In this work, we have analyzed steam-exploded birch with a varying severity factor (3.1-5.0) by pyrolysis-gas chromatography-mass spectrometry, 2D-NMR, and Fourier transform infrared spectroscopy. The main results reveal a consumption of acetic acid at higher temperatures, with the increase of furan components in the pyrolyzate. The IR and NMR spectral data support these results, and there is a reason to believe that the conditions for humin formation are accomplished under steam explosion. Pseudo-lignin seems to be a humin-like compound.
RESUMO
Several microorganisms produce small quantities of polyunsaturated hydrocarbons and such natural products are of interest. Starting from the ethyl ester of eicosapentaenoic acid, the total synthesis of the natural product (all-Z)-hentriaconta-3,6,9,12,15,19,22,25,28-nonaene has been achieved in eight steps and 15% overall yield. The synthesis is based on a stereoselective Wittig reaction and confirms the all-Z-configuration of the nine double bonds in this highly unsaturated natural product.
