Wood xylan and modified xylan - Solubilization, film formation and water interactions

Wood xylans are biopolymers that are valuable for future materials and renewable engineering solutions. In this study, xylan solubility in polar solvents and film formation were investigated. Most wood xylans are poorly soluble in polar solvents, such as water, and this can be a critical hindrance for facilitating new uses of xylan, especially in solution-based processes. Modification via oxidation using sodium periodate was selected as a potential prospect to improve xylan solubility. The influence of modification, such as the degree of oxidation, was investigated using solutions and thin films. Surface-sensitive analytics were used to quantify the properties of modified xylan as films and film additives, with a focus on their interaction with water. Furthermore, a correlation between film morphology and material solubility of modified xylan and unmodified xylan in blend systems was observed using atomic force microscopy. The findings expand the possibility of utilizing wood xylan in solution-based processes

Polysaccharide thin film studies - Adsorption of oxidized xylan on cellulose

Wood xylans are renewable natural materials that have potential for future use in bio-based products. However, their high price and low production capacity restrict their industrial use and current applications. This research aimed to explore the potential of wood xylans for film applications. Most xylans extracted from wood do not dissolve in water, which is a common solvent in many industries, such as the pulp and paper industry. Furthermore, bio-based materials are expected to be processed in a green approach, where water is a preferable solvent, and has benefit in terms of low-cost, and being an environmentally benign solvent. The poor water interaction of xylans hinders dissolution and film production, but can be overcome by chemical modification of xylan to alter its properties. Regioselective oxidation—a well-known modification in polysaccharides—can increase the flexibility and water interaction of xylans by opening their monosaccharide ring and equipping them with aldehyde groups. The research employed quartz crystal microbalance with dissipation monitoring (QCM-D) and surface plasmon resonance (SPR) to study the adsorption of macromolecules on film surfaces. The analytical combination was first established for studying protein adsorption on cellulose film with different morphology, and structure, and then oxidized xylan adsorption on nanocellulose films, which was the focus of this research. The influence of the molecular weight of oxidized xylan on adsorption in aqueous conditions, and its effect on film swelling were explored. The behavior of oxidized xylan in solution was observed using dynamic light scattering, showing that high molecular weight oxidized xylan formed larger aggregates when the concentration increased compared to low molecular weight oxidized xylan. The QCM-D and SPR investigations revealed that a high molecular weight grade adsorbed preferentially on a neutral cellulose surface, while both grades were adsorbed independently of molecular weight on a negatively charged surface. The impact of oxidized xylan on the swelling of cellulose films, regardless of molecular weight, was due to oxidized xylan bringing more water to the non-charged films, while the opposite was true of negatively charged films. Also, applying the combination of QCM-D and SPR techniques to oxidized xylan adsorption on cellulose, water content and adsorbed dry mass were obtained. This study provides a stepping-stone toward the future use of bio-based materials obtained from forest sources

Oxidized xylan additive for nanocellulose films – A swelling modifier

Polymeric wood hemicelluloses are depicted to join cellulose, starch and chitosan as key polysaccharides for sustainable materials engineering. However, the approaches to incorporate hemicelluloses in emerging bio-based products are challenged by lack of specific benefit, other than the biomass-origin, although their utilization would contribute to sustainable material use since they currently are a side stream that is not valorized. Here we demonstrate wood-xylans as swelling modifiers for neutral and charged nanocellulose films that have already entered the sustainable packaging applications, however, suffer from humidity sensitivity. The oxidative modification is used to modulate the water-solubility of xylan and hence enable adsorption in an aqueous environment. A high molecular weight grade, hence less water-soluble, adsorbed preferentially on the neutral surface while the adsorbed amount on a negatively charged surface was independent of the molecular weight, and hence, solubility. The adsorption of the oxidized xylans on a neutral cellulose surface resulted in an increase in the amount of water in the film while on the negatively charged cellulose the total amount of water decreased. The finding of synergy of two hygroscopic materials to decrease swelling in hydrophilic bio-polymer films demonstrates the oxidized macromolecule xylan as structurally functional component in emerging cellulose products

Modification of xylan via an oxidation-reduction reaction

Xylan is a biopolymer readily available from forest resources. Various modification methods, including oxidation with sodium periodate, have been shown to facilitate the engineering applications of xylan. However, modification procedures are often optimized for semicrystalline high molecular weight polysaccharide cellulose rather than for lower molecular weight and amorphous polysaccharide xylan. This paper elucidates the procedure for the periodate oxidation of xylan into dialdehyde xylan and its further reduction into a dialcohol form and is focused on the modification work up. The oxidation–reduction reaction decreased the molecular weight of xylan while increased the dispersity more than 50%. Unlike the unmodified xylan, all the modified grades could be solubilized in water, which we see essential for facilitating the future engineering applications of xylan. The selection of quenching and purification procedures and pH-adjustment of the reduction step had no significant effect on the degree of oxidation, molecular weight and only a minor effect on the hydrodynamic radius in water. Hence, it is possible to choose the simplest oxidation-reduction route without time consuming purification steps within the sequence.Peer reviewe

Potential of Wood Hemicelluloses and Their Derivates as Food Ingredients

A holistic utilization of all lignocellulosic wood biomass, instead of the current approach of using only the cellulose fraction, is crucial for the efficient, ecological, and economical use of the forest resources. Use of wood constituents in the food and feed sector is a potential way of promoting the global economy. However, industrially established food products utilizing such components are still scarce, with the exception of cellulose derivatives. Hemicelluloses that include xylans and mannans are major constituents of wood. The wood hemicelluloses are structurally similar to hemicelluloses from crops, which are included in our diet, for example, as a part of dietary fibers. Hence, structurally similar wood hemicelluloses have the potential for similar uses. We review the current status and future potential of wood hemicelluloses as food ingredients. We include an inventory of the extraction routes of wood hemicelluloses, their physicochemical properties, and some of their gastrointestinal characteristics, and we also consider the regulatory route that research findings need to follow to be approved for food solutions, as well as the current status of the wood hemicellulose applications on that route.Peer reviewe

Video Speed Switching of Plasmonic Structural Colors with High Contrast and Superior Lifetime

Abstract: Reflective displays or “electronic paper” technologies provide a solution to the high energy consumption of emissive displays by simply utilizing ambient light. However, it has proven challenging to develop electronic paper with competitive image quality and video speed capabilities. Here, the first technology that provides video speed switching of structural colors with high contrast over the whole visible is shown. Importantly, this is achieved with a broadband‐absorbing polarization‐insensitive electrochromic polymer instead of liquid crystals, which makes it possible to maintain high reflectivity. It is shown that promoting electrophoretic ion transport (drift motion) improves the switch speed. In combination with new nanostructures that have high surface curvature, this enables video speed switching (20 ms) at high contrast (50% reflectivity change). A detailed analysis of the optical signal during switching shows that the polaron formation starts to obey first order reaction kinetics in the video speed regime. Additionally, the system still operates at ultralow power consumption during video speed switching (<1 mW cm−2) and has negligible power consumption (<1 µW cm−2) in bistability mode. Finally, the fast switching increases device lifetime to at least 107 cycles, an order of magnitude more than state‐of‐the‐art

Morphology and swelling of thin films of dialcohol xylan

Polysaccharides are excellent network formers and are often processed into films from water solutions. Despite being hydrophilic polysaccharides, the typical xylans liberated from wood are sparsely soluble in water. We have previously suggested that an additional piece to the solubilization puzzle is modification of the xylan backbone via oxidative cleavage of the saccharide ring. Here, we demonstrate the influence of the degree of modification, i.e., degree of oxidation (DO) on xylan solubilization and consequent film formation and stability. Oxidized and reduced wood xylans (i.e., dialcohol xylans) with the highest DO (77 %) within the series exhibited the smallest hydrodynamic diameter (dh) of 60 nm in dimethylsulfoxide (DMSO). We transferred the modified xylans into films credit to their established solubility and then quantified the film water interactions. Dialcohol xylans with intermediate DOs (42 and 63 %) did not form continuous films. The films swelled slightly when subjected to humidity. However, the film with the highest DO demonstrated a significant moisture uptake that depended on the film mass and was not observed with the other modified grades or with unmodified xylan

Polymer Brushes on Silica Nanostructures Prepared by Aminopropylsilatrane Click Chemistry: Superior Antifouling and Biofunctionality

In nanobiotechnology, the importance of controlling interactions between biological molecules and surfaces is paramount. In recent years, many devices based on nanostructured silicon materials have been presented, such as nanopores and nanochannels. However, there is still a clear lack of simple, reliable, and efficient protocols for preventing and controlling biomolecule adsorption in such structures. In this work, we show a simple method for passivation or selective biofunctionalization of silica, without the need for polymerization reactions or vapor-phase deposition. The surface is simply exposed stepwise to three different chemicals over the course of ∼1 h. First, the use of aminopropylsilatrane is used to create a monolayer of amines, yielding more uniform layers than conventional silanization protocols. Second, a cross-linker layer and click chemistry are used to make the surface reactive toward thiols. In the third step, thick and dense poly(ethylene glycol) brushes are prepared by a grafting-to approach. The modified surfaces are shown to be superior to existing options for silica modification, exhibiting ultralow fouling (a few ng/cm2) after exposure to crude serum. In addition, by including a fraction of biotinylated polymer end groups, the surface can be functionalized further. We show that avidin can be detected label-free from a serum solution with a selectivity (compared to nonspecific binding) of more than 98% without the need for a reference channel. Furthermore, we show that our method can passivate the interior of 150 nm 7 100 nm nanochannels in silica, showing complete elimination of adsorption of a sticky fluorescent protein. Additionally, our method is shown to be compatible with modifications of solid-state nanopores in 20 nm thin silicon nitride membranes and reduces the noise in the ion current. We consider these findings highly important for the broad field of nanobiotechnology, and we believe that our method will be very useful for a great variety of surface-based sensors and analytical devices

Role of intrinsic and extrinsic xylan in softwood kraft pulp fiber networks

Xylan is primarily found in the secondary cell wall of plants providing strength and integrity. To take advantage of the reinforcing effect of xylan in papermaking, it is crucial to understand its role in pulp fibers, as it undergoes substantial changes during pulping. However, the contributions of xylan that is added afterwards (extrinsic) and xylan present after pulping (intrinsic) remain largely unexplored. Here, we partially degraded xylan from refined bleached softwood kraft pulp (BSKP) and adsorbed xylan onto BSKP. Enzymatic degradation of 1 % xylan resulted in an open hand sheet structure, while adsorption of 3 % xylan created a denser fiber network. The mechanical properties improved with adsorbed xylan, but decreased more significantly after enzymatic treatment. We propose that the enhancement in mechanical properties by adsorbed extrinsic xylan is due to increased fiber-fiber bonds and sheet density, while the deterioration in mechanical properties of the enzyme treated pulp is caused by the opposite effect. These findings suggest that xylan is decisive for fiber network strength. However, intrinsic xylan is more critical, and the same properties cannot be achieved by readsorbing xylan onto the fibers. Therefore, pulping parameters should be selected to preserve intrinsic xylan within the fibers to maintain paper strength

Design of Friction, Morphology, Wetting, and Protein Affinity by Cellulose Blend Thin Film Composition

Cellulose derivate phase separation in thin films was applied to generate patterned films with distinct surface morphology. Patterned polymer thin films are utilized in electronics, optics, and biotechnology but films based on bio-polymers are scarce. Film formation, roughness, wetting, and patterning are often investigated when it comes to characterization of the films. Frictional properties, on the other hand, have not been studied extensively. We extend the fundamental understanding of spin coated complex cellulose blend films via revealing their surface friction using Friction Force Microscopy (FFM). Two cellulose derivatives were transformed into two-phase blend films with one phase comprising trimethyl silyl cellulose (TMSC) regenerated to cellulose with hydroxyl groups exposed to the film surface. Adjusting the volume fraction of the spin coating solution resulted in variation of the surface fraction with the other, hydroxypropylcellulose stearate (HPCE) phase. The film morphology confirmed lateral and vertical separation and was translated into effective surface fraction. Phase separation as well as regeneration contributed to the surface morphology resulting in roughness variation of the blend films from 1.1 to 19.8 nm depending on the film composition. Friction analysis was successfully established, and then revealed that the friction coefficient of the films could be tuned and the blend films exhibited lowered friction force coefficient compared to the single-component films. Protein affinity of the films was investigated with bovine serum albumin (BSA) and depended mainly on the surface free energy (SFE) while no direct correlation with roughness or friction was found. BSA adsorption on film formed with 1:1 spinning solution volume ratio was an outlier and exhibited unexpected minimum in adsorption