Characterization, refining and antioxidant activity of saccharides derived from hemicelluloses of wood and rice husks.

Samples of rice husks, Eucalyptus globulus wood and Pinus pinaster wood (containing arabinoxylan, acetylated glucuronoxylan and acetylated glucomannan as major hemicellulose components, respectively) were subjected to autohydrolysis. The resulting liquid phases, containing mainly hemicellulose-derived saccharides, were refined by physicochemical methods to reduce their contents of monosaccharides and non-saccharide compounds. Raw autohydrolysis liquors and refined concentrates coming from aqueous treatments were assayed for antioxidant activity using the following assays: reducing power (FRAP), DPPH and ABTS radical scavenging activity and protection of ß-carotene-linoleic emulsions from oxidation. The reducing power and radical scavenging capacity of the non refined fractions were comparable to the ones determined for the reference compound butylhydroxytoluene. Hemicellulose concentrated from the different feedstocks and refining protocols showed a dose dependent antioxidant activity in the range of concentrations evaluated. The in vitro antioxidant activity of concentrates correlated with their phenolic content.

Recovery and concentration of antioxidants from winery wastes.

Grape and wine byproducts have been extensively studied for the recovery of phenolic compounds with antioxidant activity and a variety of biological actions. The selective recovery and concentration of the phenolic compounds from the liquid phase separated from further diluted winery wastes has been proposed. Adsorption onto non ionic polymeric resins and further desorption with ethanolic solutions was studied. Several commercial food grade resins were screened with the aim of selecting the most suited for the practical recovery of phenolic compounds with radical scavenging activity. Under the optimized desorption conditions (using Sepabeads SP207 or Diaion HP20 as adsorbents and eluting with 96% ethanol at 50 °C) a powdered yellow-light brown product with 50% phenolic content, expressed as gallic acid equivalents, was obtained. The radical scavenging capacity of one gram of product was equivalent to 2-3 g of Trolox.

Purified phenolics from hydrothermal treatments of biomass: ability to protect sunflower bulk oil and model food emulsions from oxidation.

The phenolic fractions released during hydrothermal treatment of selected feedstocks (corn cobs, eucalypt wood chips, almond shells, chestnut burs, and white grape pomace) were selectively recovered by extraction with ethyl acetate and washed with ethanol/water solutions. The crude extracts were purified by a relatively simple adsorption technique using a commercial polymeric, nonionic resin. Utilization of 96% ethanol as eluting agent resulted in 47.0-72.6% phenolic desorption, yielding refined products containing 49-60% w/w phenolics (corresponding to 30-58% enrichment with respect to the crude extracts). The refined extracts produced from grape pomace and from chestnut burs were suitable for protecting bulk oil and oil-in-water and water-in-oil emulsions. A synergistic action with bovine serum albumin in the emulsions was observed.

Fractionation of antioxidants from autohydrolysis of barley husks.

The liquid phase from nonisothermal autohydrolysis of barley husks was extracted with ethyl acetate and redissolved in ethanol to yield a crude extract (denoted BHEAE), which was subjected to further processing to enhance the antioxidant activity. A fractionation method, carried out for characterization purposes, consisted of the extraction of BHEAE with organic solvents of increasing polarity and further fractionation in Sephadex LH-20. Among the tested solvents, ethyl acetate allowed the highest yield, phenolic content, and antioxidant activity. Upon elution with methanol, products with high DPPH radical scavenging capacity (IC50 = 0.22 g/L) were obtained. The major compounds in the isolate were benzoic and cinnamic acids. Adsorption-desorption in commercial polymeric resins was carried out as an alternative strategy for BHEAE refining. This method is more suited for possible scale-up and provided a concentrate with a Trolox equivalent antioxidant capacity of 9 mM, which was obtained at a yield of 18 g/kg of barley husks.

Supercritical CO2 extraction and purification of compounds with antioxidant activity.

Supercritical fluid extraction (SCFE), based on the utilization of a fluid under supercritical conditions, is a technology suitable for extraction and purification of a variety of compounds, particularly those that have low volatility and/or are susceptible to thermal degradation. The interest in SCFE is promoted by legal limitations of conventional solvents for food and pharmaceutical uses. The physicochemical properties of supercritical CO2 (higher diffusivity, lower viscosity, and lower surface tension than conventional solvents) facilitate mass transfer and allow an environmentally friendly operation. This article presents a comprehensive compilation of data on the supercritical CO2 extraction of antioxidant compounds from vegetal materials, with particular attention to those of a phenolic nature. Aspects concerning the supercritical operation for extraction and fractionation of antioxidants compounds are considered, including equilibrium solubility of pure compounds and effects of the operational conditions on the antioxidant activity of isolated fractions. The data are compared to those reported for synthetic antioxidants and natural extracts obtained by conventional solvent extraction from vegetal matrices.

Assessment of the production of antioxidants from winemaking waste solids.

Winemaking waste solids (WS, resulting from red grapes after fermentation and distillation to recover spirits) were subjected to various processing schemes for isolating fractions with antioxidant activity. The liquors entrapped in WS as received were separated by pressing and freeze-dried to yield a fraction with antioxidant activity (measured as DPPH radical scavenging capacity) comparable to those of synthetic antioxidants. A second approach based on the direct processing of raw WS in sulfuric acid medium under fixed operational conditions and further extraction of hydrolysis liquors with ethyl acetate enabled the isolation of a fraction with higher antioxidant ability at an improved yield. The most favorable approach started with a washing stage leading to liquors (which were directly freeze-dried to yield 1.20 g of extract/100 g of oven-dry WS and presented an EC50 of 0.41 g of extract/L) and washed solids, which were dried and subjected to hydrolytic processing (i) with water as a reactive in an autocatalyzed reaction (autohydrolysis) or (ii) with sulfuric acid solutions to give an ethyl acetate-soluble fraction with improved antioxidant properties (EC50 in the range of 0.18-0.40 g/L). Samples from washing liquors and processing of washed solids in aqueous medium were subjected to chromatographic fractionation and analysis to give isolates with remarkable antioxidant activity (with EC50 as low as 0.07 g/L) and to identify their major components.

Carbon material and bioenergetic balances of xylitol production from corncobs by Debaryomyces hansenii.

The effect of oxygenation on xylitol production by the yeast Debaryomyces hansenii has been investigated in this work using the liquors from corncob hydrolysis as the fermentation medium. The concentrations of consumed substrates (glucose, xylose, arabinose, acetate and oxygen) and formed products (xylitol, arabitol, ethanol, biomass and carbon dioxide) have been used, together with those previously obtained varying the hydrolysis technique, the level of adaptation of the microorganism, the sterilization procedure and the initial substrate and biomass concentrations, in carbon material balances to evaluate the percentages of xylose consumed by the yeast for the reduction to xylitol, alcohol fermentation, respiration and cell growth. The highest xylitol concentration (71 g/L) and volumetric productivity (1.5 g/L.h) were obtained semiaerobically using detoxified hydrolyzate produced by autohydrolysis-posthydrolysis, at starting levels of xylose (S(0)) and biomass (X(0)) of about 100 g/L and 12 g(DM)/L, respectively. No less than 80% xylose was addressed to xylitol production under these conditions. The experimental data collected in this work at variable oxygen levels allowed estimating a P/O ratio of 1.16 mol(ATP)/mol(O). The overall ATP requirements for biomass production and maintenance demonstrated to remarkably increase with X(0) and for S(0) >or= 130 g/L and to reach minimum values (1.9-2.1 mol(ATP)/C-mol(DM)) just under semiaerobic conditions favoring xylitol accumulation.