Sirkka Liisa Maunu

Structural characterization of water soluble β-glucan of oat bran

β-glucan was isolated from oat bran in a highly purified form. The bran was characterized for its contents of dietary fiber, β-glucan, fat and protein. The isolated β-glucan was free of protein and contained only glucose in GC sugar analysis. Two types of β-glucan were obtained with different solubilities. Their molar masses were 1.6 million for the less soluble and 1.1 million for the more readily soluble type. No structural differences were found. The two-dimensional correlation NMR spectrum of the isolated β-glucan showed that the glucose units are joined with 1,3- and 1,4-linkages only. The oligosaccharides produced by the action of a specific enzyme, lichenase, were analyzed by HPLC and capillary zone electrophoresis. The major products are 32-β-d-glucosyl cellobiose (trisaccharide) and 33-β-d-glucosyl cellotriose (tetrasaccharide), which account for 95% of the whole. Also, 34-β-d-glucosyl cellotetraose (pentasaccharide) and other oligosaccharides with degree of polymerization (DP) higher than 5 were detected as minor components.

Cellulose crystallinity and ordering of hemicelluloses in pine and birch pulps as revealed by solid-state NMR spectroscopic methods

Solid-state 13C NMR spectroscopy was used to determine the degree of cellulose crystallinity (CrI) in kraft, flow-through kraft and polysulphide–anthraquinone (PS–AQ) pulps of pine and birch containing various amounts of hemicelluloses. The applicability of acid hydrolysis and the purely spectroscopic proton spin-relaxation based spectral edition (PSRE) method to remove the interfering hemicellulose signals prior to the determination of CrI were also compared. For softwood pulps, the spectroscopic removal of hemicelluloses by PSRE was found to be more efficient than the removal of hemicelluloses by acid hydrolysis. In addition to that, the PSRE method also provides information on the associations between cellulose and hemicelluloses. On the basis of the incomplete removal of xylan from the cellulose subspectra by PSRE, the deposition of xylan on cellulose fibrils and therefore an ordered ultrastructure of xylan in birch pulps was suggested. The ordered structure of xylan in birch pulps was also supported by the observed change of xylan conformation after regeneration. Similarly, glucomannan in pine pulps may have an ordered structure. According to the 13C CPMAS measurements conducted after acid hydrolysis, the degree of cellulose crystallinity was found to be slightly lower in birch pulps than in the pine pulps. Any significant differences in cellulose crystallinity were not found between the pulps obtained by the various pulping methods. Only in pine PS–AQ pulp, the degree of cellulose crystallinity may be slightly lower than in the kraft pulps containing less hemicelluloses.

Sorption and diffusion of methanol and water in PVDF-g-PSSA and Nafion® 117 polymer electrolyte membranes

Sorption and diffusion properties of poly(vinylidene fluoride)-graft-poly(styrene sulfonic acid) (PVDF-g-PSSA) and Nafion® 117 polymer electrolyte membranes were studied in water/methanol mixtures. The two types of membranes were found to have different sorption properties. The Nafion 117 membrane was found to have a maximum in-solvent uptake around 0.4 to 0.6 mole fraction of methanol, while the PVDF-g-PSSA membranes took up less solvent with increasing methanol concentration. The proton NMR spectra were recorded for membranes immersed in deuterated water/methanol mixtures. The spectra showed that the hydroxyl protons inside the membrane exhibit resonance lines different from the resonance lines of hydroxyl protons in the external solvent. The spectral features of the lines of these internal hydroxyl groups in the membranes were different in the Nafion membrane compared with the PVDF-g-PSSA membranes. Diffusion measurements with the pulsed field gradient NMR (PFG-NMR) method showed that the diffusion coefficient of the internal hydroxyl groups in the solvent immersed Nafion membrane mirrors the changes in the diffusion coefficients of hydroxyl and methyl protons in the external solvent. For the PVDF-g-PSSA membranes, a decrease in the diffusion coefficient of the internal hydroxyl protons was seen with increasing methanol concentration. These results indicate that the morphology and chemical structure of the membranes have an effect on their solvent sorption and diffusion characteristics.

Water sorption and diffusion coefficients of protons and Water in PVDF-g-PSSA polymer electrolyte membranes

Water sorption properties, proton NMR spectra, and diffusion of water and protons in poly(vinylidene fluoride)-graft-polystyrene sulfonic acid (PVDF-g-PSSA) polymer electrolyte membranes were studied. Sorption curves for the membranes with different degrees of grafting in protonated and Na+ form were measured by equilibrating the membranes over saturated salt solutions. The membrane water content was found to be sensitive to changes in relative humidity (RH). The water/sulfonic acid ratio λ for the protonated samples was around 2 at 20% RH and increased to λ ∼ 30 at 100%. Proton NMR, pulsed field gradient proton NMR (PFG-NMR), and impedance measurements were made on membranes with different λ. In the proton NMR spectra only one peak was found, originating from the water in the membrane. The chemical shift of the peak was found to be dependent on the counterion and the water content. The water self-diffusion coefficients DH2O, measured by PFG-NMR, increased with degree of grafting and water content of the membranes. The proton conductivity and the calculated proton mobility decreased more steeply than the DH2O with decreasing water content.

The Effect of Water Plasticization on the Molecular Mobility and Crystallization Tendency of Amorphous Disaccharides

ABSTRACTPurposeTo study how water plasticization affects the molecular mobility and crystallization tendency of freeze-dried trehalose, sucrose, melibiose and cellobiose.MethodsFreeze-dried disaccharides were subjected to different relative humidity atmospheres and their physical stabilities were evaluated. Lyophilizate water sorption tendencies and glass transition temperatures were modeled using Brunauer-Emmett-Teller (BET) and Gordon-Taylor (GT) equations, respectively. Sucrose and cellobiose crystallization tendencies were compared by using the concept of reduced crystallization temperature (RCT), and the molecular mobilities of trehalose and melibiose were compared by measuring their T1H relaxation time constants.ResultsBased on the BET and GT models, water sorption tendency and the resulting plasticizing effect were different in sucrose when compared to the other disaccharides. Trehalose and melibiose exhibited generally slower crystallization rates when compared to sucrose and cellobiose. Amorphous melibiose was shown to be particularly stable within the studied water content range, which may have partly been caused by its relatively slow molecular mobility.ConclusionsSlow amorphous-to-crystalline transition rate is known to be important for lyoprotecting excipients when formulating a robust drug product. The physical stabilities of amorphous trehalose and melibiose even with relatively high water contents might make their use advantageous in this respect compared to sucrose and cellobiose.

A CP/MAS 13C-NMR study of cellulose structure on the surface of refined kraft pulp fibers

The average lateral fibril and fibril aggregate dimensions and the crystallinity of the cellulose in a spruce kraft pulp were investigated by CP/MAS 13C-NMR spectroscopy in combination with spectral fitting. Cellulose isolated by chlorite-delignification and acid hydrolysis from fines fractions enriched in surface material and long fiber fractions enriched in bulk material exhibited no major differences in either lateral dimensions or crystallinity index.

Aggregation of the interpolymer complex of poly(methacrylic acid) and poly(vinyl pyrrolidone) in aqueous solutions

The aggregation of the interpolymer complexes between poly(methacrylic acid) (PMAA) and poly(vinyl pyrrolidone) (PVP) was investigated using the light scattering technique. The fast complexation of the polymers in aqueous solution is followed by aggregation which is very sensitive to pH. The aggregation behaviour was found to change noticeably when the pH increases from 3.2 to 3.9. The time dependence of the particle size as well as the size distribution at different pH was analysed.

The effect of drying method on the properties and nanoscale structure of cellulose whiskers

Cellulose whiskers were prepared from wood- and cotton-based microcrystalline cellulose and dried by two methods: freeze-drying or air-drying. The effect of drying method on the properties and structure of the whiskers were studied. Furthermore, the influence of the source of cellulose on the nanoscale structure was investigated. Drying method was observed to slightly influence the thermal stability of cellulose whiskers, whereas the char residue varied significantly depending on the drying process performed. Small- and wide-angle X-ray scattering and solid state nuclear magnetic resonance spectroscopy were used to examine the crystallinity and nanoscale structure of the dried whiskers. It was observed that the crystal structure and crystallinity of cellulose whiskers remained during all treatments, whereas their nanoscale structure was significantly influenced by drying method, neutralization, and source of cellulose. Relationships between thermal behavior and nanoscale structure were reported and discussed.

A physico-chemical characterisation of new raw materials for microcrystalline cellulose manufacturing

A detailed physico-chemical characterisation of potential new cellulose sources (rice husk, hemp stalk, and coniferous needles), and microcrystalline cellulose (MCC) manufactured from them, was made in this work. The length and the width of the cellulose crystallites were determined by wide-angle X-ray scattering (WAXS), crystallinities were studied by means of WAXS and solid state cross polarisation magic angle spinning 13C nuclear magnetic resonance (NMR) spectroscopy, and the packing and the cross-sectional shape of the microfibrils were determined by small-angle X-ray scattering. When MCC was prepared from rice husks and hemp stalks an acceptable yield was obtained. Crystallinities obtained with solid state NMR spectroscopy and WAXS were highest for MCC prepared from hemp stalks, and lowest for rice husk MCC. The crystallite sizes of MCC samples studied in this work varied more than in those MCC samples which were prepared from conventional plant sources, and crystallite size and cellulose crystallinity were related. When taking into account rather high values of specific surface, hemp stalks and rice husks appear as a promising raw materials for MCC production.

The stability and dissolution properties of solid glucagon/γ-cyclodextrin powder

In the present study, the solid-state stability and the dissolution of glucagon/gamma-cyclodextrin and glucagon/lactose powders were evaluated. Freeze-dried powders were stored at an increased temperature and/or humidity for up to 39 weeks. Pre-weighed samples were withdrawn at pre-determined intervals and analyzed with HPLC-UV (HPLC=high performance liquid chromatography, UV=ultraviolet), HPLC-ESI-MS (ESI-MS=electrospray ionization mass spectrometry), SEC (size-exclusion chromatography), turbidity measurements and solid-state FTIR (Fourier Transform Infrared Spectroscopy). Dissolution of glucagon was evaluated at pH 2.5, 5.0 and 7.0. In addition, before storage, proton rotating-frame relaxation experiments of solid glucagon/gamma-cyclodextrin powder were conducted with CPMAS ((13)C cross-polarization magic-angle spinning) NMR (nuclear magnetic resonance) spectroscopy. In the solid state, glucagon was degraded via oxidation and aggregation and in the presence of lactose via the Maillard reaction. The solid-state stability of glucagon/gamma-cyclodextrin powder was better than that of glucagon/lactose powder. In addition, gamma-cyclodextrin improved the dissolution of glucagon at pH 5.0 and 7.0 and delayed the aggregation of glucagon after its dissolution at pH 2.5, 5.0 and 7.0. There was no marked difference between the proton rotating-frame relaxation times of pure glucagon and gamma-cyclodextrin, and thus, the presence of inclusion complexes in the solid state could not be ascertained by CPMAS NMR. In conclusion, when compared to glucagon/lactose powder, glucagon/gamma-cyclodextrin powder exhibited better solid-state stability and more favorable dissolution properties.