Improved methods for evaluating the molar mass distributions of cellulose in kraft pulp

Multi‐angle laser light scattering (MALLS) was used to characterize birch kraft pulps with respect to their absolute molecular mass distributions (MMDs). The pulps were dissolved in lithium chloride/N,N‐dimethylacetamide and separated by size exclusion chromatography (SEC). The weight‐average and number‐average molecular masses of the cellulose fractions of the pulps obtained from the absolute MALLS measurements were compared with the molar masses obtained by direct‐standard‐calibration relative pullulan standards. Discrepancies between the two detection methods were found, and two ways of correlating the relative pullulan molar masses to the absolute molar masses were examined. In the first method, the correlation was made over a large range of molecular masses. The second method correlated the molecular masses of the standards to the molecular masses of samples by the calculation of fictitious, cellulose‐equivalent molar masses of the standards. With the preferred second method, a more correct MMD of kraft pulp samples could, therefore, be obtained from an SEC system calibrated with narrow standards. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1170–1179, 2003     

Near Wall Studies of Pulp Suspension Flow Using LDA

A detailed study of the flow behaviour in the near wall region of pulp suspensions up to 4.7% have been performed using Laser Doppler Anemometry (LDA) in pipe flow. Axial mean velocity profiles show a distinct plug flow and an increase of the plug region as the flow rate decreases and fibre concentration increases. An attempt is made to relate the LDA data‐rate to fibre concentration, which indicates a dilution region at 1‐2 mm from the wall that is larger than the annulus region. The dilution region increases with increasing flow rate, decreasing concentration and when using longer pulp fibres.     

The fate of fuel-nitrogen during gasification of biomass in a pressurised fluidised bed gasifier

The distribution of fuel-nitrogen in gases, tar and char from gasification of biomass in a pressurised fluidised bed gasifier was investigated. Four species of biomass: birch, Salix, Miscanthus and Reed canary grass were gasified at 0.4 MPa and 900 °C. Oxygen-enriched nitrogen was used as fluidising agent. As a reference, gasification of Daw Mill coal was also carried out under the same experimental conditions. The experimental results illustrate that both the nature of the original fuels and the chemical structure of the nitrogen in the fuel have influence on the distribution of fuel-nitrogen in gases (NH₃, HCN, NO), tar and char under the employed experimental conditions. The present work also shows that the types of nitrogen heterocyclic compounds (NHCs) in the tar from different kinds of biomass are the same and the major compound is pyridine. However, the distribution of the various NHCs in the tar from the four species of biomass varies: the higher the content of fuel-nitrogen, the higher the concentration of two-ring NHCs in the tar. An effective method for extracting NHCs from the acidic absorption of the product gas was introduced in the present work. The method makes use of solid phase extraction (SPE) by a silica-based C₁₈ tube to extract the NHCs which subsequently were analysed by gas chromatography (GC) with flame ionisation detection (FID). The recovery and reproducibility of the SPE technique for NHCs is discussed.     

Syntheses of female sex pheromone precursors of pine sawfly species and of some structurally related methyl-branched long-chain 2-alkanols

3,7-Dimethyl-2-undecanol, 3,7,9-trimethyl-2-tridecanol, and 3,7, 11-trimethyl-2-tridecanol were synthesized as racemic mixtures in moderate yields. The alcohols are known precursors of the female sex pheromones of the pine sawfly species Diprion nipponica, Macrodiprion nemoralis, and Microdiprion pallipes, respectively. Stereoisomeric mixtures of 3,8,12-trimethyl-2-tridecanol, erythro-(2R,3R,11R/S)-3,11-dimethyl-2-tetradecanol, 3,5-dimethyl-2-tetradecanol, and 5,7-dimethyl-2-tetradecanol, structurally related to sex pheromone alcohol precursors of pine sawfly species, were also synthesized in moderate yields. The key reaction in the syntheses was the ring opening of mg src="/content/fecphxu7mwckq6tr/xxlarge947.gif" alt="gamma" align="MIDDLE" BORDER="0">-butyrolactones by using different alkyl lithiums as nucleophiles.     

Swelling and mechanical properties of cellulose hydrogels. I. Preparation,characterization, and swelling behavior

Cellulose hydrogels have been synthesized by reacting solutions of cellulose xanthate with different amounts of epichlorohydrin (0–24% w/w on cellulose) after which the cellulose was regenerated. The weight fraction of crystalline cellulose, determined by density measurements, decreases with the extent of chemical crosslinking and was estimated to vary between 30 and 42% for dry gels. The degree of equilibrium swelling in water of the prepared hydrogels varied between 3.05 and 6.33 g water/g dry gel (g/g). The degree of swelling decreases with increasing chemical crosslinking. As a result of the irreversible changes occurring during drying, the degree of swelling in water can be reduced down to 0.74 g/g. According to density gradient column measurements, the partial specific volume of water is 0.865 cm³/g at water contents below 0.13 g/g. It is suggested that water having this partial specific volume is the specific hydration water. At higher water contents, the partial specific volume of gel water equals the specific volume of bulk water. It is implicit in the interpretation of the density data in terms of a two state model of gel water that the crystallinity of cellulose is independent of the water content. Depending on the degree of swelling, heat treatment resulted in either an irreversible increase or decrease of the degree of swelling.     

Synthetic polymeric absorbent for dye based on chemically crosslinked acrylamide/mesaconic acid hydrogels

Adsorption properties of copolymers of acrylamide and mesaconic acid (CAME) in aqueous Basic Blue 12 (Nile blue chloride) solution have been investigated. Chemically crosslinked CAME hydrogels with various compositions were prepared from ternary mixtures of acrylamide (A), mesaconic(ME) acid, and water by free radical polymerization in aqueous solution, using a multifunctional crosslinker such as ethylene glycol dimethacrylate (EGDMA). Dynamic swelling tests in water was applied to the hydrogels. Weight swelling ratio (S) values have been calculated. Sorption of Basic Blue 12 (BB 12) onto CAME hydrogels was studied by batch sorption technique at 25°C. In the experiments of the sorption, L type sorption in the Giles classification system was found. Some binding parameters such as initial binding constant (K_i), equilibrium constant (K), monolayer coverage (n), site‐size (u), and maximum fractional occupancy (Ô) for CAME hydrogels‐BB 12 binding system were calculated by using Klotz, Scatchard, and Langmuir linearization methods. Finally, the amount of sorbed BB 12 per gram of dry hydrogel (q) was calculated to be 2.28 × 10^?6–7.91× 10^?6 mol BB 12 per gram for hydrogels. Sorption % was changed range 16.09–58.86%. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 405–413, 2006     

Associations between apolipoprotein E genotype and circulating F<Subscript>2</Subscript>-isoprostane levels in humans

Apolipoprotein E (apoE), an important determinant of plasma lipoprotein metabolism, has three common alleles (&amp;#949;2, &amp;#949;3, and &amp;#949;4). Population studies have shown that the risk of diseases characterized by oxidative damage, such as coronary heart disease and Alzheimer&amp;#8217;s disease, is significantly higher in &amp;#603;4 carriers. We evaluated the association between apoE genotypes and plasma F₂-isoprostane levels, an index of lipid peroxidation, in humans. Two hundred seventy-four healthy subjects (104 males, 170 females; 46.9±13.0 yr; 200 whites, 74 blacks; 81 nonsmokers, 64 passive smokers, and 129 active smokers) recruited for a randomized clinical antioxidant intervention trial were included in this analysis. ApoE genotype was determined by PCR and restriction enzyme digestion. Free plasma F₂-isoprostane was measured by GC-MS. Genotype groups were compared using multiple regression analysis with adjustment for sex, age, race, smoking status, body mass index, plasma ascorbic acid, and &amp;#946;-carotene. Subjects with &amp;#949;3/&amp;#949;4 and &amp;#949;4/&amp;#949;4 genotype (&amp;#949;4-carriers) and with &amp;#949;2/&amp;#949;3 and &amp;#949;3/&amp;#949;3 (non-&amp;#949;4-carriers) were pooled for analysis. In subjects with high cholesterol levels (total cholesterol above 200 mg/dl), plasma F₂-isoprostane levels were 29% higher in &amp;#949;4 carriers than in non-&amp;#949;4-carriers (P=0.0056). High-cholesterol subjects that are &amp;#949;4 carriers have significantly higher levels of lipid peroxidation as assessed by circulating F₂-isoprostane levels.     

Synthesis and properties of chitosan-modified poly(vinyl butyrate)

Modification of chitosan by grafting of vinyl butyrate was carried out in homogeneous phase using potassium persulfate as redox initator and 1.5% acetic acid as solvent. The percent grafting and grafting efficiency were analysed and the high grafting efficiency up to 94% was observed. The effects of reaction variables such as monomer concentration, initiator concentration, temperature and reaction time were investigated. It was observed that the solubility of chitosan was markedly reduced after grafting with vinyl butyrate. The grafted product is insoluble in common organic solvents as well in dilute organic and inorganic acids. Characterization of the graft copolymers were carried out by using Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC) and Scanning Electron Microscopy (SEM) technics. Characteristic signal of carbonyl group was observed at 1,731 cm^&amp;#8722;1 which belongs to the poly vinyl butyrate segments in the graft copolymer. The melting transition of the chitosan main chain in the copolymer shifted to 124°C from its original value 101°C. In addition to these, we have also studied topology of the graft copolymer and the SEM micrograph showed continuous homogenous matrix which means there is no phase separation.     

Crystal structural refinement of the new compound TmAlB14

Single crystals of the new phase TmAlB₁₄ were grown using the high-temperature solution method. The crystal structure of TmAlB₁₄ was refined from X-ray powder diffraction data using the Rietveld method. The structure is of MgAlB₁₄-type with the space group Imma and unit cell parameters a = 5.8212(3) Å, B = 10.3837(2) Å and C = 8.1762(3) Å. The final, conventional R-valve and profile R-value are 0.031 and 0.064, respectively. The structure is characterized by a partial occupancy of both metal positions and a splitting of the thulium atomic position.