Kinetics of acid hydrolysis of water-soluble spruce O-acetyl galactoglucomannans.

Water-soluble O-acetyl galactoglucomannan (GGM) is a softwood-derived polysaccharide, which can be extracted on an industrial scale from wood or mechanical pulping waters and now is available in kilogram scale for research and development of value-added products. To develop applications of GGM, information is needed on its stability in acidic conditions. The kinetics of acid hydrolysis of GGM was studied at temperatures up to 90 degrees C in the pH range of 1-3. Molar mass and molar mass distribution were determined using size exclusion chromatography with multiangle laser light scattering and refractive index detection. The molar mass of GGM decreased considerably with treatment time at temperatures above 70 degrees C and pH below 2. The molar mass distribution broadened with hydrolysis time. A first-order kinetic model was found to match the acid hydrolysis. The reaction rate constants at various pH values and temperatures were calculated on the basis of the first-order kinetic model. Furthermore, the activation energy, E, was obtained from the Arrhenius plot. The activation energy E was 150 kJ mol (-1) for acid hydrolysis of spruce GGM. The apparent rate constant during acid hydrolysis increased by a factor of 10 with a decrease in pH by 1 unit, regardless of temperature. In addition, gas chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry were applied to study the released GGM monomers and oligomers.

Norway spruce galactoglucomannans exhibiting immunomodulating and radical-scavenging activities.

Wood-derived naturally acetylated galactoglucomannans (AcGGM) can be recovered even in ton-scale at mechanical pulp mills using spruce as raw material. These cell wall polysaccharides have a great potential as hydrocolloids and bioactive polymers in food and pharmaceutical applications, or as starting material for production of functional polymers. The immunostimulatory activity of both AcGGM and its deacetylated form (GGM) was now in vitro tested. The biological response of both AcGGM and GGM in the lymphocyte transformation test was dose-dependent. The direct mitogenic as well as comitogenic activities of the AcGGM were comparable to those of the immunogenic corn cob xylan used as control, and GGM showed significantly higher biological responses also at lower doses. In contrast to GGM, AcGGM possessed also DPPH radical-scavenging activity. The results suggested that the spruce AcGGM and GGM are potentially important as additives with immuno-potentiating and antioxidant properties in food products and pharmaceutical formulations.

Pyrolysis of softwood carbohydrates in a fluidized bed reactor.

In the present work pyrolysis of pure pine wood and softwood carbohydrates, namely cellulose and galactoglucomannan (the major hemicellulose in coniferous wood), was conducted in a batch mode operated fluidized bed reactor. Temperature ramping (5 degrees C/min) was applied to the heating until a reactor temperature of 460 degrees C was reached. Thereafter the temperature was kept until the release of non-condensable gases stopped. The different raw materials gave significantly different bio-oils. Levoglucosan was the dominant product in the cellulose pyrolysis oil. Acetic acid was found in the highest concentrations in both the galactoglucomannan and in the pine wood pyrolysis oils. Acetic acid is most likely formed by removal of O-acetyl groups from mannose units present in GGM structure.

Antimicrobial and cytotoxic knotwood extracts and related pure compounds and their effects on food-associated microorganisms.

Knotwood or bark extracts prepared from 30 species of hard and soft wood trees as well as selected pure compounds (lignans, stilbenes and flavonoids) were assayed for their antimicrobial activity against a battery of both gram positive and negative bacteria, yeasts, and filamentous fungi (Bacillus cereus, Staphylococcus aureus, Listeria monocytogenes, Lactobacillus plantarum, Escherichia coli, Salmonella infantis, Pseudomonas fluorescens, Candida albicans, Saccharomyces cerevisiae, Aspergillus fumigatus and Penicillium brevicompactum). By far the most consistent antibacterial and antifungal properties were associated with extracts of Pinus species. These extracts showed also cytotoxicity against a mouse hepatoma cell line. Both antimicrobial and cytotoxic properties correlated with the stilbene content of the extracts. Purified stilbenes showed the most consistent antimicrobial and cytotoxic activities, while purified lignans had marginal effects, only. The results suggest that stilbenes account both for the antimicrobial and cytotoxic properties of Pinus knotwood extracts.

Quantification of a broad spectrum of lignans in cereals, oilseeds, and nuts.

Twenty-four plant lignans were analyzed by high-performance liquid chromatography-tandem mass spectrometry in bran extracts of 16 cereal species, in four nut species, and in two oilseed species (sesame seeds and linseeds). Eighteen of these were lignans previously unidentified in these species, and of these, 16 were identified in the analyzed samples. Four different extraction methods were applied as follows: alkaline extraction, mild acid extraction, a combination of alkaline and mild acid extraction, or accelerated solvent extraction. The extraction method was of great importance for the lignan yield. 7-Hydroxymatairesinol, which has not previously been detected in cereals because of destructive extraction methods, was the dominant lignan in wheat, triticale, oat, barley, millet, corn bran, and amaranth whole grain. Syringaresinol was the other dominant cereal lignan. Wheat and rye bran had the highest lignan content of all cereals; however, linseeds and sesame seeds were by far the most lignan-rich of the studied species.

A novel antioxidant phenyl disaccharide from Populus tremula knotwood.

The complete characterization of two compounds obtained from the acetone extract of Populus tremula knotwood has been was achieved using LC-DAD-MS, MS/MS, IR and NMR. The new compounds were unequivocally identified as a mixture of the ester isomers of the (E) and (Z) p-coumarate of 1-O-rutinose. The isomers showed the capacity to inhibit lipid peroxidation induced by tert-butylhydroperoxide and to trap peroxyl radicals, as determined by a chemiluminescence method. These new phenyl disaccharides also showed a significant ORAC (oxygen radical absorbance capacity) value, i.e. 11.7 microM TE (Trolox Equivalents).

Galactoglucomannan-rich hemicellulose extract from Norway spruce (Picea abies) exerts beneficial effects on chronic prostatic inflammation and lower urinary tract symptoms in vivo.

Galactoglucomannan (GGM) is the main hemicellulose class in wood of coniferous trees and could be potentially utilized as a possible health-promoting substance for food and pharmaceutical industry. Our aim was to evaluate effects of orally administered GGM-rich extract from Norway spruce in a rat model of chronic prostatitis associated with lower urinary tract symptoms (LUTS). Prostatic inflammation and LUTS was induced in male rats using testosterone and 17ß-estradiol exposure for 18 weeks. Rats were treated with 2% GGM dissolved in drinking water during weeks 13-18. Pelvic pain response, LUT function and histopathological evaluation of the prostate were assessed. The results show that hormonal exposure induced LUTS seen as decreased urine flow rate, increased bladder pressure, voiding times, bladder capacity and residual urine volumes. GGM had positive effects on urodynamical parameters by decreasing the basal bladder pressure, increasing the urine flow rate and volume, reducing the residual volume and increasing micturition intervals. GGM reduced the extent of the hormone exposure-induced prostatic inflammation. Increase of pelvic pain induced by hormone exposure was only slightly affected by GGM treatment. The results suggest that orally administered GGM may have potential usage for improving lower urinary tract function associated with chronic prostatic inflammation.

Surface characterization by XPS, contact angle measurements and ToF-SIMS of cellulose fibers partially esterified with fatty acids.

The topochemistry of the controlled heterogeneous esterification of cellulose fibers with fatty acid chlorides of different chain length, both in swelling and non-swelling media, was assessed by X-ray Photoelectron Spectroscopy (XPS), Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) and contact angle measurements. On the one hand, the results provided by the combined use of these three powerful techniques showed unambiguously the occurrence of the reaction at the fibers' surface and, on the other hand, the XPS results showed that the surface coverage with the fatty acid moieties increased with their chain length, but was only modestly affected by the degree of substitution (DS), suggesting that when the esterification yield was increased (higher DS values), an in-depth reaction also occurred, particularly when DMF was used as a cellulose swelling medium, involving the OH groups buried below the fibers' surface.

Anionic groups on cellulosic fiber surfaces investigated by XPS, FTIR-ATR, and different sorption methods.

Anionic groups (AGs) on different cellulosic fiber surfaces were investigated by methylene blue (MB) and polyelectrolyte (PE) sorption, X-ray photoelectron spectroscopy (XPS), and total attenuated reflectance infrared spectrometry (FTIR-ATR). The MB sorption isotherms fitted well the Langmuir equation that gave consistent estimations of sorption capacities. FTIR-ATR showed that MB molecules had extensive accessibility to the fiber wall pores. Estimation of surface AGs by PE sorption gave much higher values than a new method combining MB sorption and XPS measurements (MB-XPS). The surface AGs in different cellulosic fibers accounted for 1-3% of the total AG content as revealed by MB-XPS. It was suggested that PE molecules can penetrate the fiber wall and form loops or unattached segments at external fiber surfaces that disrupt the PE sorption stoichiometry. The competition of MB and PE for the anionic sites in papermaking was assessed and it was shown that MB ions have a much stronger affinity to AGs than PE molecules.