Åsa Östlund

Dissolution and Gelation of Cellulose in TBAF/DMSO Solutions: The Roles of Fluoride Ions and Water

Solutions of cellulose in a mixture of tetrabutylammonium fluoride and dimethyl sulfoxide (TBAF/DMSO) containing small and varying amounts of water were studied by nuclear magnetic resonance (NMR). By measuring the composition dependences of (19)F NMR and (1)H NMR chemical shifts and line widths, details on the dissolution and gelation mechanisms for cellulose in TBAF/DMSO were elucidated. Our results suggest that the strongly electronegative fluoride ions act as hydrogen bond acceptors to cellulose hydroxyl groups, thus dissolving the polymer by breaking the cellulose-cellulose hydrogen bonds and by rendering the chains an effective negative charge. It was found that the fluoride ions also interact strongly with water. Small amounts of water remove the fluoride ions from the cellulose chains and allow reformation of the cellulose-cellulose hydrogen bonds, which leads to formation of highly viscous solutions or gels even at low cellulose concentrations.

Adsorption of Arabinoxylan on Cellulosic Surfaces: Influence of Degree of Substitution and Substitution Pattern on Adsorption Characteristics

This study presents results that show that the fine structure of arabinoxylan affects its interaction with cellulosic surfaces, an important understanding when designing and evaluating properties of xylan-cellulose-based materials. Arabinoxylan samples, with well-defined structures, were prepared from a wheat flour arabinoxylan with targeted enzymatic hydrolysis. Turbidity measurements and analyses using NMR diffusometry showed that the solubility and the hydrodynamic properties of arabinoxylan are determined not only by the degree of substitution but also by the substitution pattern. On the basis of results obtained from adsorption experiments on microcrystalline cellulose particles and on cellulosic model surfaces investigated with quartz crystal microbalance with dissipation monitoring, it was also found that arabinoxylan adsorbs irreversibly on cellulosic surfaces and that the adsorption characteristics, as well as the properties of the adsorbed layer, are controlled by the fine structure of the xylan molecule.

Insights into the interplay between molecular structure and diffusional motion in 1-alkyl-3-methylimidazolium ionic liquids: a combined PFG NMR and X-ray scattering study

We report on how the local structure and the diffusional motion change upon increasing the alkyl chain length in 1-alkyl-3-methylimidazolium cation ionic liquids. This study has been performed by combining pulse field gradient (PFG) nuclear magnetic resonance (NMR) spectroscopy and small angle X-ray scattering (SAXS) experiments. The cationic side chain length varies from ethyl (n = 2) to hexadodecyl (n = 16), while the anion is always bis(trifluoromethanesulfonyl)imide (TFSI). We find that the self-diffusivity of the individual ionic species is correlated to the local structure in the corresponding ionic liquid, namely the nano-segregation into polar and non-polar domains. In agreement with previous results, we observe that for relatively short alkyl chains the cations diffuse faster than the anions; however we also note that this difference becomes less evident for longer alkyl chains and a cross-over is identified at n ≈ 8 with the anions diffusing faster than the cations. Our results indicate that this controversial behavior can be rationalized in terms of different types of cation-cation and anion-anion orderings, as revealed by a detailed analysis of the correlation lengths and their dispersion curves obtained from SAXS data. We also discuss the validity of the Stokes-Einstein relation for these ionic liquids and the evolution of the extrapolated cationic radius that was found to depend non-strictly linearly on n, in agreement with the cation-cation correlation lengths.

Modification of crystallinity and pore size distribution in coagulated cellulose films

In this study the effects of altering the coagulation medium during regeneration of cellulose dissolved in the ionic liquid 1-ethyl-3-methylimidazolium acetate, were investigated using solid-state NMR spectroscopy and NMR cryoporometry. In addition, the influence of drying procedure on the structure of regenerated cellulose was studied. Complete conversion of the starting material into regenerated cellulose was seen regardless of the choice of coagulation medium. Coagulation in water predominantly formed cellulose II, whereas coagulation in alcohols mainly generated non-crystalline structures. Subsequent drying of the regenerated cellulose films, induced hornification effects in the form of irreversible aggregation. This was indicated by solid-state NMR as an increase in signal intensity originating from crystalline structures accompanied by a decrease of signal intensity originating from cellulose surfaces. This phenomenon was observed for all used coagulants in this study, but to various degrees with regard to the polarity of the coagulant. From NMR cryoporometry, it was concluded that drying induced hornification generates an increase of nano-sized pores. A bimodal pore size distribution with pore radius maxima of a few nanometers was observed, and this pattern increased as a function of drying. Additionally, cyclic drying and rewetting generated a narrow monomodal pore size pattern. This study implies that the porosity and crystallinity of regenerated cellulose can be manipulated by the choice of drying condition.

Comparison of PEI-PEG and PLL-PEG copolymer coatings on the prevention of protein fouling

The effect of surface charge on the protein resistance of adsorbed layers of poly(ethylene imine)-[g]-poly(ethylene glycol), PEI-PEG, and poly(L-lysine)-[g]-poly(ethylene glycol), PLL-PEG, was studied. Mixed and monofunctional self-assembled monolayers, SAMs, on gold were obtained by adsorption of 16-mercapto-1-hexadecanoic acid and 16-mercapto-1-hexadecanol. The surface charge was systematically varied by changing the ratio of the two alkanethiols. The graft copolymers PEI-PEG and PLL-PEG were adsorbed at the SAMs and tested for resistance towards human serum albumin and fibrinogen. The adsorbed amount of copolymers increased with increasing negative surface charge. However, the best protein resistance was found at an intermediate surface charge. The PLL-PEG covered surfaces showed better protein resistance than the PEI-PEG covered surfaces. Thus, this work demonstrates that an adsorbed layer of PEG-grafted PEI and, in particular, PEG-grafted PLL is efficient in preventing protein adsorption when there is charge neutralization between the copolymer and the underlying surface.

Chemical shift imaging NMR to track gel formation

In this work we have combined (1)H and (19)F NMR chemical shift images to investigate the dynamic processes of gel formation of a cellulose solution. Chemical shift imaging (CSI) NMR is shown to be a valuable technique for studying phase changes in soft materials. The technique provides spatial position of each chemical component, and by repeatedly recording sample images the dynamic rearrangements in the material can be followed in detail. CSI NMR follows the same principles as magnetic resonance imaging, but can be performed on most of the nowadays commercial NMR probes. Position resolution of the chemical shift gives the opportunity to derive diffusion rate data of individual components during the gel formation process. The results suggest that the method can be used for detailed studies of dynamic processes in multi-component systems and to extract diffusion coefficients for the components investigated.

Determination of self-diffusion coefficient and hydrodynamic radius of xylan by NMR diffusometry (NMRd)

No abstract available

Preparation of Viscose Fibres Stripped of Reactive Dyes and Wrinkle-Free Crosslinked Cotton Textile Finish

The chemical recycling of cellulosic fibres may represent a next-generation fibre–fibre recycling system for cotton textiles, though remaining challenges include how to accommodate fibre blends, dyes, wrinkle-free finishes, and other impurities from finishing. These challenges may disrupt the regeneration process steps and reduce the fibre quality. This study examines the impact on regenerated viscose fibre properties of a novel alkaline/acid bleaching sequence to strip reactive dyes and dimethyloldihydroxyethyleneureas (DMDHEU) wrinkle-free finish from cotton textiles. Potentially, such a bleaching sequence could advantageously be integrated into the viscose process, reducing the costs and environmental impact of the product. The study investigates the spinning performance and mechanical properties (e.g., tenacity and elongation) of the regenerated viscose fibres. The alkaline/acid bleaching sequence was found to strip the reactive dye and DMDHEU wrinkle-free finish from the cotton fabric, so the resulting pulp could successfully be spun into viscose fibres, though the mechanical properties of these fibres were worse than those of commercial viscose fibres. This study finds that reactive dyes and DMDHEU wrinkle-free finish affect the viscose dope quality and the regeneration performance. The results might lead to progress in overcoming quality challenges in cellulosic chemical recycling.

The CO2 capturing ability of cellulose dissolved in NaOH(aq) at low temperature

Herein, we explore the intrinsic ability of cellulose dissolved in NaOH(aq) to reversibly capture CO2. The stability of cellulose solutions differed significantly when adding CO2 prior to or after the dissolution of cellulose. ATR-IR spectroscopy on cellulose regenerated from the solutions, using ethanol, revealed the formation of a new carbonate species likely to be cellulose carbonate. To elucidate the interaction of cellulose with CO2 at the molecular level, a 13C NMR spectrum was recorded on methyl α-D-glucopyranoside (MeO-Glcp), a model compound, dissolved in NaOH(aq), which showed a difference in chemical shift when CO2 was added prior to or after the dissolution of MeO-Glcp, without a change in pH. The uptake of CO2 was found to be more than twice as high when CO2 was added to a solution after the dissolution of MeO-Glcp. Altogether, a mechanism for the observed CO2 capture is proposed, involving the formation of an intermediate cellulose carbonate upon the reaction of a cellulose alkoxide with CO2. The intermediate was observed as a captured carbonate structure only in regenerated samples, while its corresponding NMR peak in solution was absent. The reason for this is plausibly a rather fast hydrolysis of the carbonate intermediate by water, leading to the formation of CO32−, and thus increased capture of CO2. The potential of using carbohydrates as CO2 capturing agents in NaOH(aq) is shown to be simple and resource-effective in terms of the capture and regeneration of CO2.

Molecular Insights into Covalently Stained Carious Dentine Using Solid-State NMR and ToF-SIMS

Dyes currently used to stain carious dentine have a limited capacity to discriminate normal dentine from carious dentine, which may result in overexcavation. Consequently, finding a selective dye is still a challenge. However, there is evidence that hydrazine-based dyes, via covalent bonds to functional groups, bind specifically to carious dentine. The aim of this study was to investigate the possible formation of covalent bonds between carious dentine and 15N2-hydrazine and the hydrazine-based dye, 15N2-labelled Lucifer Yellow, respectively. Powdered dentine from extracted carious and normal teeth was exposed to the dyes, and the staining reactions were analysed using time-of-flight secondary ion mass spectrometry (ToF-SIMS), solid-state 13C-labelled nuclear magnetic resonance (NMR) and 15N-NMR spectroscopy. The results showed that 15N2-hydrazine and 15N2-labelled Lucifer Yellow both bind to carious dentine but not to normal dentine. It can thus be concluded that hydrazine-based dyes can be used to stain carious dentine and leave normal dentine unstained.