Petri Kilpeläinen

Effects of pressurized hot water extraction on the nanoscale structure of birch sawdust

Pressurized hot water extraction with a flow-through system was used to extract hemicelluloses and lignin from birch sawdust. The structure of the extraction residue was studied on various levels. Molecular mass distributions were determined with gel permeation chromatography and the crystal structure of cellulose was characterized using wide-angle X-ray scattering (WAXS). Information on the short-range order of cellulose microfibrils and on the nanoscale pore structure was obtained with small-angle X-ray scattering (SAXS), and the micrometre scale cellular morphology was imaged with X-ray microtomography. The pressurized hot water treatment was observed to increase the lateral width of cellulose crystallites, determined with WAXS, whereas a possible small decrease in the crystallinity of cellulose compared to native wood was detected. The molecular mass of cellulose remained at a relatively high level. According to the SAXS results, a tighter lateral association of cellulose microfibrils was observed in the extracted samples, which possibly led to opening of pores between bundles of microfibrils, as indicated by an increased specific surface area. A reduction in the thickness of the fibre cell walls was evidenced by X-ray microtomography.

Continuous propionic acid production with Propionibacterium acidipropionici immobilized in a novel xylan hydrogel matrix.

The cell immobilization potential of a novel xylan based disulfide-crosslinked hydrogel matrix reinforced with cellulose nanocrystals was studied with continuous cultivation of Propionibacterium acidipropionici using various dilution rates. The cells were immobilized to hydrogel beads suspended freely in the fermentation broth or else packed into a column connected to a stirred tank reactor. The maximum propionic acid productivity for the combined stirred tank and column was 0.88gL(-1)h(-1) and the maximum productivity for the column was determined to be 1.39gL(-1)h(-1). The maximum propionic acid titer for the combined system was 13.9gL(-1) with a dilution rate of 0.06h(-1). Dry cell density of 99.7gL(-1) was obtained within the column packed with hydrogel beads and productivity of 1.02gL(-1)h(-1) was maintained in the column even with the high circulation rate of 3.37h(-1).

Novel thiol- amine- and amino acid functional xylan derivatives synthesized by thiol–ene reaction

In the present work, novel thioether xylans were synthesized via a simple procedure using water as solvent. First, allyl groups were introduced on the backbone of xylan by etherification of allyl chloride in aqueous alkaline conditions at 40°C, providing degree of substitution (DS) values up to 0.49. On the second step, the allyl groups were reacted with thioacetic acid, cysteamine hydrochloride or cysteine providing novel thiol-, amine- or amino acid functionalized xylans. The presented modular approach offers broad possibilities for developing new polysaccharide based materials. The thioacetic acid - ene reaction is reported for the first time for polysaccharide modification, yielding a protected thiol that can be stored at atmospheric conditions and can be deprotected by simple hydrolysis just prior to use, providing a versatile water soluble polythiol. The free thiol-groups were utilized for hydrogel formation through thiol-thiol oxidative coupling, allowing good control over the hydrogel shape, such as 3D hydrogel scaffolds and cross-linked foams. Further, the thiol-containing xylan was used to modify filter paper surface by a simple dipping method, which provides a novel and convenient way for introducing thiol-functionality on paper surface.

Effect of xylan structure on reactivity in graft copolymerization and subsequent binding to cellulose.

The grafting reactivities with glycidyl methacrylate (GMA) of five xylans from hardwood and cereal sources were compared. The structural property that best predicted the reactivities of xylans with GMA was the fraction of 4-O-methylglucuronic acid (MeGlcA) substitution. A comparatively high level of arabinose substitution was also positively correlated to reactivity with GMA. The impact of MeGlcA and arabinose branching groups is likely attributed to the solubilizing effect of these substituents. Consistent with this prediction, low water solubility and high lignin content were found to hinder reactivity. Even though oligomeric substrates have the advantage of water solubility, modified xylo-oligosaccharides were difficult to purify. Accordingly, delignified and high-molecular weight xylans that are soluble or dispersible in water are best suited for this type of backbone derivatization. Adsorption studies with a quartz crystal microbalance with dissipation indicated that grafting lowered the total adsorption of arabinoxylan but did not significantly affect the fraction of xylans adsorbed irreversibly on cellulose.