Supercritical fluid extraction of Eucalyptus globulus bark: a promising approach for triterpenoid production

Eucalyptus bark contains significant amounts of triterpenoids with demonstrated bioactivity, namely triterpenic acids and their acetyl derivatives (ursolic, betulinic, oleanolic, betulonic, 3-acetylursolic, and 3-acetyloleanolic acids). In this work, the supercritical fluid extraction (SFE) of Eucalyptus globulus deciduous bark was carried out with pure and modified carbon dioxide to recover this fraction, and the results were compared with those obtained by Soxhlet extraction with dichloromethane. The effects of pressure (100-200 bar), co-solvent (ethanol) content (0, 5 and 8% wt), and multistep operation were studied in order to evaluate the applicability of SFE for their selective and efficient production. The individual extraction curves of the main families of compounds were measured, and the extracts analyzed by GC-MS. Results pointed out the influence of pressure and the important role played by the co-solvent. Ethanol can be used with advantage, since its effect is more important than increasing pressure by several tens of bar. At 160 bar and 40 degrees C, the introduction of 8% (wt) of ethanol greatly improves the yield of triterpenoids more than threefold

Non-cellulosic heteropolysaccharides from sugarcane bagasse - Sequential extraction with pressurized hot water and alkaline peroxide at different temperatures

The xylan-rich hemicellulose components of sugarcane bagasse were sequentially extracted with pressurized hot-water extraction (PHWE) and alkaline peroxide. The hemicelluloses were found to contain mainly arabinoxylans with varying substitutions confirmed by different chemical and spectroscopic methods. The arabinoxylans obtained from PHWE were found to be more branched compared to those obtained after alkaline extraction. Sequential extraction could be useful for the isolation of hemicelluloses with different degree of branching, molar mass, and functional groups from sugarcane bagasse, which can be of high potential use for various industrial applications

Bio-Based Hydrogels With Ion Exchange Properties Applied to Remove Cu(II), Cr(VI), and As(V) Ions From Water

Hydrogels with ion exchange properties were synthesized from compounds derived from wood biopolymer hemicellulose and from commercial vinyl monomers to be tested as active materials for the removal of Cu(II), Cr(VI), and As(V) ions. The hemicellulose O-acetyl galactoglucomannan (GGM) was used as the precursor material, and through a transesterification reaction, GGM was converted into a macromonomer GGM-glycidyl methacrylate (GGM-GMA). Subsequently, the GGM-GMA macromonomer, containing more than one methacrylate group, was used as a crosslinking agent in the synthesis of hydrogels through free-radical polymerization reactions in combination with a 2-acrylamido-2-methyl-1-propanesulfonic acid monomer to produce a cation exchange hydrogel. Also, (3-acrylamidopropyl)trimethylammonium chloride monomer was applied together with the GGM-GMA to form hydrogels that can be used as anion exchange hydrogel. The hydrogels were characterized by Fourier transform-infrared (FT-IR), H-1-NMR spectroscopy, and thermogravimetric analysis (TGA), as well as derivative thermogravimetry (DTG). The microstructure of the hydrogels was characterized by scanning electron microscopy (SEM) analysis with X-ray microanalysis energy-dispersive spectroscopy (EDS). The results obtained regarding the absorption capacity of the Cu(II), Cr(VI), and As(V) ions were studied as a function of the pH value and the initial concentration of the metal ions in the solutions. Absorption was carried out in consecutive batches, and it was found that the poly(GGM-GMA/AMPSH) hydrogel reached an absorption capacity of 90 mg g(-1) for Cu(II). The poly(GGM-GMA/APTACl) hydrogel reached values of 69 and 60 mg g(-1) for Cr(VI) and As(V) oxyanions, respectively. Tests with polymer blends (mixtures of anionic and cationic hydrogels) were also carried out to remove Cu(II), Cr(VI), and As(V) ions from multi-ionic solutions, obtaining satisfactory results

Synthesis of SET-LRP-induced galactoglucomannan-diblock copolymers

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 -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 Cu-0/Me-6-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

Cationic hemicellulose-based hydrogels for arsenic and chromium removal from aqueous solutions

In this work the synthesis of hemicellulose-based hydrogels and their application for the removal of arsenic and chromium ions is described. In a first step O-acetyl galactoglucomannan (GGM) was subjected to a transesterification applying glycidyl methacrylate (GMA) for the synthesis of novel GGM macromonomers. Two distinguished and purified GGM fractions with molar mass of 7.1 and 28 kDa were used as starting materials. The resulting GGM macromonomers (GGM-MA) contained well-defined amounts of methacrylate groups as determined by H-1 NMR spectroscopy. Selected GGM-MA derivatives were consecutively applied as a crosslinker in the synthesis of tailored hydrogels using [2-(methacryloyloxy)ethyl]trimethylammonium chloride (MeDMA) as monomer. The swelling rate of the hydrogels was determined and the coherence between the swelling rate and the hydrogel composition was examined. The morphology of the GGM-based hydrogels was analysed by SEM and the hydrogels revealed a high surface area and were assessed in respect to their ability to remove arsenate and chromate ions from aqueous solutions. The presented bio-based hydrogels are of high interest especially for the mining industries as a sustainable material for the treatment of their highly contaminated wastewaters