Pre-flocculation of filler has been tested as a concept for improving the retention of filler and the strength properties of the sheet. The impact of the size of the filler floes on the mechanical retentionin a fibre network was investigated using a modified laboratory hand sheet former. The mechanical retention was found to increase linearly with both particle size and grammage of the fibre web. These results were confirmed in a full scale production trial on the FEX pilot paper machine at Innventia. Here different filler floe sizes were created through different chemical pre-flocculation strategies. The particle size in the flow to the headbox was measured with FBRM, and a linear relation between particle size and filler retention was found. Corresponding linear relation was seen in a pilot trial when adding filler and retention aid conventionally. This implies that mechanical retention constitute an important part of the filler retention not only upon pre-flocculation but also with conventional addition of filler and retention aid. Thus, the particle size before the headbox can be a good indicator of the retention level. For the conventional application of a two component retention aid system, the increased filler retention correlated to impaired formation and decreased sheet strength. On the contrary, pre-flocculation led to an increase in both sheet strength and filler retention, demonstrating the advantage of pre-flocculating filler.
With the aim of investigating kraft lignin as a raw material for carbon fibre production, different lignins have been stabilised in air at conditions varied according to a full factorial experimental design. The lignins under examination were purified kraft lignin powders originating from birch, spruce/pine and Eucalyptus globules, as well as lignin fibres originating from birch with 5 poly(ethylene oxide) (PEO) added as a plasticiser. The influence of temperature, time and heating rate on yield and glass-transition temperature (Tg) was investigated. The highest yield was achieved after stabilisation at 280°C during 2h with a heating rate of 0.2°C min -1. The Tg of all lignin powders was increased when stabilisation occurred under harsher conditions. X-ray photoelectron spectroscopy analysis (XPS) of both the outer surface and the cleaved cross-section of individual lignin/PEO fibres showed a clear gradient in the degree of chemical modification, with the major change occurring on the surface resulting in the appearance of a skin-core structure after stabilisation. The behaviour of the lignin fibres during stabilisation is similar to that of pitch-based fibres, indicating good possibilities for lignin as raw material for carbon fibre production.
The plant cell wall exhibits a hierarchical structure, in which the organization of the constituents on different levels strongly affects the mechanical properties and the performance of the material. In this work, the interactions between cellulose and xylan in a model system consisting of a bacterial cellulose/glucuronoxylan (extracted from aspen, Populus tremula) have been studied and compared to that of a delignified aspen fiber material. The properties of the materials were analyzed using Dynamical Mechanical Analysis (DMA) with moisture scans together with dynamic Infra Red -spectroscopy at dry and humid conditions. The results showed that strong interactions existed between the cellulose and the xylan in the aspen holocellulose. The same kinds of interactions were seen in a water-extracted bacterial cellulose/xylan composite, while unextracted material showed the presence of xylan not interacting with the cellulose. Based on these findings for the model system, it was suggested that there is in hardwood one fraction of xylan that is strongly associated with the cellulose, taking a similar role as glucomannan in softwood.
Wood and wood materials are highly sensitive to moisture in the environment. To a large extent this relates to the hygroscopicity of wood hemicelluloses. In order to increase our understanding of the effects of moisture sorption of the major wood hemicelluloses, glucomannan and xylan, model experiments using films of amorphous konjak glucomannan and rye arabinoxylan were conducted. Moisture-induced expansion and stiffness softening were characterized using dynamic mechanical testing. Both hemicelluloses showed a threshold around 5Â % of moisture content above which swelling increased whereas the modulus decreased by more than 70Â %. FTIR spectra, using H2O and D2O, indicated that even at high RH about 15Â % of the hydroxyl groups were not accessible to hydrogen exchange by D2O. For xylan both hydroxyl groups were found to exchange in the same manner while for the glucomannan the O(6)H group seemed to be the most accessible.
We report a Rh-catalyzed, enantioselective silylation of arene C–H bonds directed by a (hydrido)silyl group. (Hydrido)silyl ethers that are formed in situ by hydrosilylation of benzophenone or its derivatives undergo asymmetric C–H silylation in high yield with excellent enantioselectivity in the presence of [Rh(cod)Cl]2 and a chiral bisphosphine ligand. The stereoselectivity of this process also allows enantioenriched diarylmethanols to react with site selectivity at one aryl group over the other. Enantioenriched benzoxasiloles from the silylation process undergo a range of transformations to form C–C, C–O, C–I, or C–Br bonds.
A rather extensive degradation of cellulose and hemicelluloses was found in waterlogged oak wood samples from the ancient warship Vasa by size exclusion chromatography with the solvent system lithium chloride/N,N-dimethylacetamide (LiCl/DMAc). The degradation has mainly occurred after salvage of the wreck, probably as a consequence of keeping iron contaminated wood in contact with air. The most likely explanation is Fenton type of reactions degrading the wood polymers and oxidising reduced sulphur forms to sulphuric acid. An increased degradation rate of the Vasa wood can be anticipated in the future if the sulphuric acid cannot be neutralised and the oxidative reactions cannot be quenched.
The interaction of water with cellulose stages many unresolved questions. Here 2H MAS NMR and IR spectra recorded under carefully selected conditions in 1H-2H exchanged, and re-exchanged, cellulose samples are presented. It is shown here, by a quantitative and robust approach, that only two of the three available hydroxyl groups on the surface of cellulose fibrils are exchanging their hydrogen with the surrounding water molecules. This finding is additionally verified and explained by MD simulations which demonstrate that the 1HO(2) and 1HO(6) hydroxyl groups of the constituting glucose units act as hydrogen-bond donors to water, while the 1HO(3) groups behave exclusively as hydrogen-bond acceptors from water and donate hydrogen to their intra-chain neighbors O(5). We conclude that such a behavior makes the latter hydroxyl group unreactive to hydrogen exchange with water.
The marine secondary metabolite stryphnusin (1) was isolated from the boreal sponge Stryphnus fortis, collected off the Norwegian coast. Given its resemblance to other natural acetylcholinesterase antagonists, it was evaluated against electric eel acetylcholinesterase and displayed inhibitory activity. A library of twelve synthetic phenethylamine analogs, 2a-7a and 2b-7b, containing tertiary and quaternary amines respectively were synthesized to investigate the individual structural contributions to the activity. Compound 7b was the strongest competitive inhibitor of both acetylcholinesterase and butyrylcholinesterase with IC50 values of 57 and 20 μM, respectively. This inhibitory activity is one order of magnitude higher than the positive control physostigmine, and is comparable with several other marine acetylcholinesterase inhibitors. The physiological effect of compound 7b on muscle function and neuromuscular transmission was studied and revealed a selective mode of action at the investigated concentration. This data is of importance as the interference of therapeutic acetylcholinesterase inhibitors with neuromuscular transmission can be problematic and lead to unwanted side effects. The current findings also provide additional insights into the structure-activity relationship of both natural and synthetic acetylcholinesterase inhibitors.
In this study we report polycondensation and co-polymerization of cis-9,10-epoxy-18-hydroxyoctadecanoic acid (1) isolated from birch outer bark using immobilized Candida antarctica lipase B (Novozyme 435) as catalyst to give epoxy activated straight chain polyesters and cyclic macromonomers.
Barettin, 8,9-dihydrobarettin, bromoconicamin and a novel brominated marine indole were isolated from the boreal sponge Geodia barretti collected off the Norwegian coast. The compounds were evaluated as inhibitors of electric eel acetylcholinesterase. Barettin and 8,9-dihydrobarettin displayed significant inhibition of the enzyme, with inhibition constants (Ki) of 29 and 19 μM respectively towards acetylcholinesterase via a reversible noncompetitive mechanism. These activities are comparable to those of several other natural acetylcholinesterase inhibitors of marine origin. Bromoconicamin was less potent against acetylcholinesterase, and the novel compound was inactive. Based on the inhibitory activity, a library of 22 simplified synthetic analogs was designed and prepared to probe the role of the brominated indole, common to all the isolated compounds. From the structure-activity investigation it was shown that the brominated indole motif is not sufficient to generate a high acetylcholinesterase inhibitory activity, even when combined with natural cationic ligands for the acetylcholinesterase active site. The four natural compounds were also analysed for their butyrylcholinesterase inhibitory activity in addition and shown to display comparable activities. The study illustrates how both barettin and 8,9-dihydrobarettin display additional bioactivities which may help to explain their biological role in the producing organism. The findings also provide new insights into the structure-activity relationship of both natural and synthetic acetylcholinesterase inhibitors.
We report the significant role of synthetic routes and the importance of solvents in the synthesis of org.-inorg. lead iodide materials. Through one route, the intercalation of DMF in the crystal structure was obsd. leading to a one--dimensional (1D) [NH3(CH2)4NH3]Pb2I6 structure of the product. This product was compared with the two-dimensional (2D) [NH3(CH2)4NH3]PbI4 recovered from aq. solvent based synthesis with the same precursors. UV-visible absorption spectroscopy showed a red-shift of 0.1 eV for the band gap of the 1D network in relation to the 2D system. This shift primarily originates from a shift in the valence band edge as detd. from photoelectron- and X-ray spectroscopy results. These findings also suggest the iodide 5p orbital as the principal component in the d. of states in the valence band edge. Single crystal data show a change in the local coordination around iodide, while in both materials, lead atoms are surrounded by iodide atoms in octahedral units. The cond. of the one-dimensional material ([NH3(CH2)4NH3]Pb2I6) was 50% of the two-dimensional material ([NH3(CH2)4NH3]PbI4). The fabricated solar cells reflect these changes in the chem. and electronic structure of both materials, although the total light conversion efficiencies of solar cells based on both products were similar.
Dynamic Fourier Transform Infra-Red (FT-IR) spectroscopy was used to examine the effect of a low sulphonation treatment on the ultrastructure of the primary cell wall of spruce wood. Sheets made from enriched primary cell wall material coming from a low sulphonated thermomechanical pulp were used for studying the viscoelastic response of the polymers using dynamic FT-IR spectroscopy. The overall ultrastructure of the primary cell wall remained largely unaltered, due to the exceptionally low degree of sulphonation used. However, an increased softening of the material as well as a weakening of the lignin;pectin, lignin;protein and pectin;protein interactions were observed. The suggestion is that, together with a structural modification of the lignin, it is the increased viscoelasticity of the material, resulting from the breaking down of the interactions among the polymers, that is the cause for the lower energy demand, when refining correspondingly low sulphonated chips.
The mechanical and physical properties of wood fibres depend to a large extent on the orientation of the polymers, mainly the cellulose microfibrils, within the supramolecular structure of the cell wall. Under moist conditions, the arrangement within the polymer matrix may play a dominant role for mechanical properties in general and, especially, in the transverse direction. In this context, it is of special interest to determine the orientation of glucomannan and xylan, being the essential components of softwood hemicelluloses, and of lignin in wood fibres. Fourier transform infrared (FTIR) microscopy was used to examine the orientation of the main wood polymers in transversal and longitudinal direction of spruce fibres. We investigated fibres made from a thermomechanical pulp, in which the outer fibre wall layers were removed by mechanical action, and chemically delignified fibres. The polarised FTIR measurements indicated that glucomannan and xylan appear to have a parallel orientation with regard to the orientation of cellulose and, in all probability, an almost parallel orientation with regard to the fibre axis. Lignin was found to be less oriented in the fibre wall, although its arrangement is not fully isotropic. In the longitudinal direction of the fibres, there were no significant changes in the molecular orientation of the studied polymers.