| 1. |
- Wohlert, Malin, et al.
(författare)
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Cellulose and the role of hydrogen bonds : not in charge of everything
- 2022
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Ingår i: Cellulose. - : Springer Nature. - 0969-0239 .- 1572-882X. ; 29:1, s. 1-23
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Tidskriftsartikel (refereegranskat)abstract
- In the cellulose scientific community, hydrogen bonding is often used as the explanation for a large variety of phenomena and properties related to cellulose and cellulose based materials. Yet, hydrogen bonding is just one of several molecular interactions and furthermore is both relatively weak and sensitive to the environment. In this review we present a comprehensive examination of the scientific literature in the area, with focus on theory and molecular simulation, and conclude that the relative importance of hydrogen bonding has been, and still is, frequently exaggerated.
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| 2. |
- Bergenstråhle, Malin, 1977-, et al.
(författare)
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Dynamics of Cellulose-Water Interfaces : NMR Spin-Lattice Relaxation Times Calculated from Atomistic Computer Simulations
- 2008
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Ingår i: Journal of Physical Chemistry B. - Washington : ACS Publications. - 1520-6106 .- 1520-5207. ; 112:9, s. 2590-2595
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Tidskriftsartikel (refereegranskat)abstract
- Solid-state nuclear magnetic resonance (CP/MAS 13C NMR) spectroscopy has often been used to study cellulose structure, but some features of the cellulose NMR spectrum are not yet fully understood. One such feature is a doublet around 84 ppm, a signal that has been proposed to originate from C4 atoms at cellulose fibril surfaces. The two peaks yield different T1, differing by approximately a factor of 2 at 75 MHz. In this study, we calculate T1 from C4-H4 vector dynamics obtained from molecular dynamics computer simulations of cellulose Iβ-water interfacial systems. Calculated and experimentally obtained T1 values for C4 atoms in surface chains fell within the same order of magnitude, 3-20 s. This means that the applied force field reproduces relevant surface dynamics for the cellulose-water interface sufficiently well. Furthermore, a difference in T1 of about a factor of 2 in the range of Larmor frequencies 25-150 MHz was found for C4 atoms in chains located on top of two different crystallographic planes, namely, (110) and (10). A previously proposed explanation that the C4 peak doublet could derive from surfaces parallel to different crystallographic planes is herewith strengthened by computationally obtained evidence. Another suggested basis for this difference is that the doublet originates from C4 atoms located in surface anhydro-glucose units with hydroxymethyl groups pointing either inward or outward. This was also tested within this study but was found to yield no difference in calculated T1.
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| 3. |
- Bergenstråhle, Malin, 1977-, et al.
(författare)
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Simulation studies of the insolubility of cellulose
- 2010
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Ingår i: Carbohydrate Research. - : Elsevier BV. - 0008-6215 .- 1873-426X. ; 345:14, s. 2060-2066
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Tidskriftsartikel (refereegranskat)abstract
- Molecular dynamics simulations have been used to calculate the potentials of mean force for separating short cellooligomers in aqueous solution as a means of estimating the contributions of hydrophobic stacking and hydrogen bonding to the insolubility of crystalline cellulose. A series of four potential of mean force (pmf) calculations for glucose, cellobiose, cellotriose, and cellotetraose in aqueous solution were performed for situations in which the molecules were initially placed with their hydrophobic faces stacked against one another, and another for the cases where the molecules were initially placed adjacent to one another in a co-planar, hydrogen-bonded arrangement, as they would be in cellulose ID. From these calculations, it was found that hydrophobic association does indeed favor a crystal-like structure over solution, as might be expected. Somewhat more surprisingly, hydrogen bonding also favored the crystal packing, possibly in part because of the high entropic cost for hydrating glucose hydroxyl groups, which significantly restricts the configurational freedom of the hydrogen-bonded waters. The crystal was also favored by the observation that there was no increase in chain configurational entropy upon dissolution, because the free chain adopts only one conformation, as previously observed, but against intuitive expectations, apparently due to the persistence of the intramolecular O3-O5 hydrogen bond.
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| 4. |
- Berglund, Jennie, et al.
(författare)
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Acetylation and Sugar Composition Influence the (In)Solubility of Plant beta-Mannans and Their Interaction with Cellulose Surfaces
- 2020
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Ingår i: ACS Sustainable Chemistry and Engineering. - : AMER CHEMICAL SOC. - 2168-0485. ; 8:27, s. 10027-10040
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Tidskriftsartikel (refereegranskat)abstract
- Plant beta-mannans are complex heteropolysaccharides that represent an abundant resource from lignocellulosic biomass. The influence of the molecular motifs of plant mannans on the backbone flexibility, solubility, and the interaction with cellulose was investigated by computational and experimental approaches. The regioselectivity of the acetyl substitutions at C2 and C3 distinctively influenced backbone flexibility in aqueous media, as revealed by molecular dynamic simulations. The molecular weight and degree of acetylation were tailored for two model seed mannans (galactomannan and glucomannan) and compared to spruce acetylated galactoglucomannan. The thermal stability was enhanced with increasing acetyl substitutions, independently of the type of mannan. Dynamic light scattering and atomic force microscopy revealed that the occurrence of galactosylation and a low degree of acetylation (similar to that of native acetylated galactoglucomannans) enhanced solubility/dispersibility of mannans, whereas the solubility/dispersibility decreased for higher degrees of acetylation. Mannan solubility influenced their interactions with cellulose at water-cellulose interfaces in terms of adsorbed mass and viscoelastic properties of the adsorbed mannan layers. Our results reveal that modulating the molecular motifs of plant beta-mannans influences their macromolecular conformation and physicochemical properties, with fundamental implications for their role in the plant cell wall and the design of wood-based materials.
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| 7. |
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| 8. |
- Berglund, Jennie
(författare)
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Wood Hemicelluloses - Fundamental Insights on Biological and Technical Properties
- 2018
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Hemicelluloses are a group of heterogeneous polysaccharides representing around 30 % of wood where the dominating types are xylans, glucomannans and xyloglucans. Hemicelluloses complex molecular structure makes it difficult to understand the relationship between structure and properties entirely, and their biological role is not yet fully verified. Additionally, hemicelluloses are sensitive to chemical processing and are not utilized to their full potentials for production of value-added products such as materials, additives to food and pharmaceutical products, etc. Increased knowledge regarding their functions is important for the development of both processes and products. The aim with this work has therefore been to increase the fundamental understanding about how the structure and properties of wood hemicelluloses are correlated, and properties such as flexibility, interaction with cellulose, solubility, resistance to chemical-, thermal-, and enzymatic degradation have been explored.Molecular dynamics (MD) simulations were used to, in detail, study the structures found in wood hemicelluloses. The flexibility was evaluated by comparing the impact of backbone sugars on the conformational space and also the impact of side groups was considered. Based on the conformational space of backbone glycosidic linkages the flexibility order of hemicelluloses in an aqueous environment was determined to be: xylan > glucomannan > xyloglucan. Additionally, the impact of xylan structure on cellulose interaction was evaluated by MD methods.Hemicelluloses were extracted from birch and spruce, and were used to fabricate different composite hydrogels with bacterial cellulose. These materials were studied with regards to mechanical properties, and it was shown that galactoglucomannans mainly contributed to an increased modulus in compression, whereas the most significant effect from xylan was increased strain under uniaxial tensile testing. Besides, other polysaccharides of similar structure as galactoglucomannans were modified and used as pure, well defined, models. Acetyl groups are naturally occurring decorations of wood hemicelluloses and can also be chemically introduced. Here, mannans with different degrees of acetylation were prepared and the influence of structure on solubility in water and the organic solvent DMSO were evaluated. Furthermore, the structure and water solubility influenced the interaction with cellulose. Acetylation also showed to increase the thermal and biological stability of mannans.With chemical pulping processes in mind, the degradability of spruce galactoglucomannans in alkaline solution were studied with regards to the structure, and the content of more or less stable structural regions were proposed.
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| 9. |
- Cederholm, Linnea, et al.
(författare)
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“Like Recycles Like” : Selective Ring-Closing Depolymerization of Poly(L-Lactic Acid) to L-Lactide
- 2022
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Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 61:33
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Tidskriftsartikel (refereegranskat)abstract
- Chemical recycling of poly(L-lactic acid) to the cyclic monomer L-lactide is hampered by low selectivity and by epimerization and elimination reactions, impeding its use on a large scale. The high number of side reactions originates from the high ceiling temperature (Tc) of L-lactide, which necessitates high temperatures or multistep reactions to achieve recycling to L-lactide. To circumvent this issue, we utilized the impact of solvent interactions on the monomer–polymer equilibrium to decrease the Tc of L-lactide. Analyzing the observed Tc in different solvents in relation to their Hildebrand solubility parameter revealed a “like recycles like” relationship. The decreased Tc, obtained by selecting solvents that interact strongly with the monomer (dimethyl formamide or the green solvent γ-valerolactone), allowed chemical recycling of high-molecular-weight poly(L-lactic acid) directly to L-lactide, within 1–4 h at 140 °C, with >95 % conversion and 98–99 % selectivity. Recycled L-lactide was isolated and repolymerized with high control over molecular weight and dispersity, closing the polymer loop.
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| 10. |
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