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Hemicellulose O-acetyl-galactoglucomannan (GGM) is the main noncellulosic water-soluble polysaccharide in the coniferous softwood Norway spruce, consisting of anhydro-galactose, -glucose, and -mannose. Acid hydrolysis of GGM has been studied in a continuous tube reactor to obtain these sugars under industrially relevant conditions. The reaction was performed under atmospheric pressure at 90°C and 95°C, and hydrochloric acid (HCl) served as catalyst. The influence of the reaction parameters, such as acid concentration (pH), temperature, concentration of the substrate, as well as catalyst and reactant flow rates, has been studied on the conversion efficiency and product distribution. Continuous production of monomeric sugars was achieved without formation of low-molecular by-products. The GGM conversion was high with HCl as catalyst, at 95°C, and a pH of 0.3. The main hydrolysis products were mannose, glucose, and galactose monomers. Minor amounts of sugar dimers were detected among the products. The experimental results are described with a laminar flow model for the continuous reactor. [ABSTRACT FROM AUTHOR]

A major enhancement of grease and water vapor barrier properties was accomplished with a 1-10 g/m coating of O-acetyl galactoglucomannan (GGM) ester or with GGM coatings applied as water dispersions on cartonboard. GGMs were esterified with phthalic and benzoic anhydrides, respectively. The novel phthalic esters of GGM (GGM-Ph) were characterized with HPLC, NMR, and matrix-assisted laser desorption/ionization with mass spectrometry (MALDI-TOF-MS). The degree of substitution of GGM-Ph was obtained by H NMR, C NMR, and HPLC. The GGM esters and GGM were coated onto cartonboard, and they demonstrated good moisture and very good grease resistance even with thin 1-3 g/m coatings. The time for penetration of 0.1 % rapeseed oil was 54 h with the 2.4 g/m coating thickness. The lowest water vapor transmission value was 39 g/m/24 h with 9.7 g/m coating. The GGM esters had clearly higher water resistance and slightly higher grease barrier values than native GGM. High-molar-mass-based GGM (50 kg/mol) and GGM-Ph rendered better water vapor and grease barrier properties than low-molar-mass GGM (9 kg/mol) and GGM-Ph. The GGM-based coatings can be safely used on an industrial scale as water was used as a solvent. As obtained from non-food-based side-stream wood-based resources, GGM and GGM esters project a sustainable and modern conception for barrier purposes in food packaging. [ABSTRACT FROM AUTHOR]

ABSTRACT Polysaccharides are biorenewable and biodegradable starting materials for the development of functional materials. The synthesis of a monofunctional macroinitiator for single electron transfer-living radical polymerization was successfully developed from a wood polysaccharide- O-acetyl galactoglucomannan (GGM) using a beforehand synthesized amino-functional α-bromoisobutyryl derivative applying reductive amination. The GGM macroinitiator was employed to initiate a controlled radical polymerization of [2-(methacryloyloxy)ethyl]trimethylammonium chloride (MeDMA), methyl methacrylate (MMA), and N-isopropylacrylamide (NIPAM) using Cu0/Me6-Tren as a catalyst. The either charged or amphiphilic GGM- b-copolymers with different chain lengths of the synthetic block were successfully synthesized without prior hydrophobization of the GGM chain and dimethyl sulfoxide (DMSO) or DMSO/water mixtures were used as solvents. This novel synthetic approach may find untapped potentials particularly for the development of polysaccharide-based amphiphilic additives for cosmetics or paints and for the design of novel temperature or pH responsive polymers with such potential applications as in drug delivery systems or in biocomposites. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 5100-5110 [ABSTRACT FROM AUTHOR]

A class of nonionic polysaccharides-based surfactants were synthesised from O-acetyl galactoglucomannan (GGM), water-soluble hemicelluloses from spruce, using naturally-occurring saturated fatty acids, CH3(CH2)nCOOH (n = 7, 12, and 16). Hemicelluloses can be recovered from waste-streams of papermaking and agricultural processes or isolated by hot water extraction of plant tissues integrated into a biorefinery process. Fatty acids can be recovered as byproducts of the agricultural and food industries. Different synthesis routes were applied to yield amphiphilic derivatives with either a grafted or block structure. Fatty acids activated with 1,1'-carbonyldiimidazole (CDI) were grafted to the backbone of GGM molecules on their hydroxyl groups. Alternatively, synthesised amino-activated fatty acids using ethylenediamine were reacted with the reducing end of GGM. By adjusting the reagent ratios, GGM-based surfactants with different hydrophilic to hydrophobic ratios were prepared. Their surface activity was assessed by measuring the surface tension in water. This study presents an approach to design carbohydrate-based surfactants using naturally-occurring fatty acids that may find potential applications in such areas as food, cosmetic, and paint formulations. [ABSTRACT FROM AUTHOR]

Highlights • Hemicelluloses were obtained via alternative wood biorefining strategies. • Hemicelluloses were compared as biobased emulsion stabilizers. • Sustainable alkyd paint emulsions were characterized. • Natural hemicellulose-rich isolates showed promising functionality. • The crude technical hemicellulose fractions were the most efficient stabilizers. Abstract Wood biorefining currently involves large-scale industrial processes where a notable portion of raw materials, namely hemicelluloses and lignin, are either lost with the process water, degraded, or burnt for energy. Value-added utilization of polymeric hemicelluloses is challenging due to their intermediate molar mass and the presence of other wood components, such as phenolic residues or wood extractives. Oil-in-water (O/W) emulsions represent a diverse and abundant class of applications in which the natural properties of wood hemicelluloses are beneficial. In the current work, we present highly promising new technical alkyd paint emulsion systems stabilized with hardwood glucuronoxylans (GX) and softwood galactoglucomannans (GGM). Samples from three isolation methods and their further fractionation by ethanol precipitation were systematically compared with regard to hemicellulose composition, interfacial activity, and functionality in emulsions. Emulsification of alkyd resins was successful with both GX and GGM obtained by various biorefining strategies. The highest emulsion stability over storage was achieved using crude non-purified GX and GGM fractions, and was correlated with the presence of phenolic compounds and extractives, interfacial activity, and small droplet size. Hardwood GX and softwood GGM are envisioned as natural emulsifiers of alkyd O/W emulsions, which are examples of diverse and abundantly-used technical dispersions. This study can be utilized as a guideline for targeted extraction of hemicelluloses with desired functionality, and as a protocol for developing environmentally-compatible industrial dispersions. [ABSTRACT FROM AUTHOR]

Abstract: Norway spruce O-acetyl-galactoglucomannans (GGM) are water-soluble hemicelluloses that have potential to be produced in large scale as a side product of the mechanical pulping industry or by hot-water extraction of wood. Chemical modification is often needed to tailor such water-soluble polysaccharides into industrially valuable compounds. In this work, treatment of GGM with butyric and benzoic anhydride in pyridine/dimethylformamide rendered GGM derivatives, which were hydrophobic and partially soluble in organic solvents. The degree of substitution can be adjusted by varying the quantity of the reagent and reaction temperature. The dn/dc value for the benzoyl ester of GGM was determined in 0.05M LiBr DMSO in order to obtain accurate molar mass analysis with SEC-MALLS-RI. Novel substances with adjusted hydrophobicity can thus be prepared on one step synthesis from natural hemicelluloses, which then showed a slight increase in the molar mass upon esterification. [Copyright &y& Elsevier]