Exploring the impact of water on the morphology and crystallinity of xylan hydrate nanotiles.

There has been a resurgence of studies on xylan particles describing various properties and exploring new applications. The aim of this study was to analyze xylan hydrate crystals in the wet state and after air-drying using state-of-art imaging techniques in order to assess the impact of water on both crystallinity and particle morphology. Xylan from esparto grass (Stipa tenacissima) was crystallized and formed convex platelets, termed 'nanotiles'. Fully hydrated xylan crystals were examined in a layer of vitreous ice by cryogenic electron microscopy. Selected area electron diffraction of the xylan hydrate crystals revealed an oriented crystalline core, unlike the dried crystals that showed no orientation. The surface topographies and thickness of wet and air-dried xylan nanotiles were observed using atomic force microscopy imaging in both liquid and in air. X-ray diffraction was used to assess the crystallinity of xylan nanotiles after drying to varying levels. Air-dried crystals gave diffraction maxima corresponding to xylan hydrate, while wet crystals gave diffraction maxima corresponding to xylan dihydrate. This study offers new insight into xylan hydrate particles, focusing on the role of water on their crystallinity, ultrastructure, and orientation of the crystalline layers.

Size-controlled synthesis of xylan micro / nanoparticles by self-assembly of alkali-extracted xylan.

Valorization of underutilized biobased feedstocks like hetero-polysaccharides is critical for the development of the biorefinery concept. Towards this goal, highly uniform xylan micro/nanoparticles with a particle size ranging from 400 nm to 2.5 µm in diameter were synthesized by a facile self-assembly method in aqueous solutions. Initial concentration of the insoluble xylan suspension was utilized to control the particle size. The method utilized supersaturated aqueous suspensions formed at standard autoclaving conditions without any other chemical treatments to create the resulting particles as solutions cooled to room temperature. Processing parameters of the xylan micro/nanoparticles were systematically studied and correlated with both the morphology and size of xylan particles. By adjusting the crowding of the supersaturated solutions, highly uniform dispersions of xylan particles were synthesized of defined size. The xylan micro/nanoparticles prepared by self-assembly have a quasi-hexagonal shape, like a tile, and depending upon solution concentrations xylan nanoparticles with a thickness of <100 nm were achieved at high concentrations. Based on the usefulness of polysaccharide nanoparticles, like cellulose nanocrystals, these particles have potential for unique structures for hydrogels, aerogels, drug delivery, and photonic materials. This study highlights the formation of a diffraction grating film for visible light with these size-controlled particles.

Functional Lignin Building Blocks: Reactive Vinyl Esters with Acrylic Acid.

Introducing vinyl groups onto the backbone of technical lignin provides an opportunity to create highly reactive renewable polymers suitable for radical polymerization. In this work, the chemical modification of softwood kraft lignin was pursued with etherification, followed by direct esterification with acrylic acid (AA). In the first step, phenolic hydroxyl and carboxylic acid groups were derivatized into aliphatic hydroxyl groups using ethylene carbonate and an alkaline catalyst. The lignin was subsequently fractionated using a downward precipitation method to recover lignin of defined molar mass and solubility. After recovery, the resulting material was then esterified with AA, resulting in lignin with vinyl functional groups. The first step resulted in approximately 90% of phenolic hydroxyl groups being converted into aliphatic hydroxyls, while the downward fractionation resulted in three samples of lignin with defined molar masses. For the esterification reaction, the weight ratio of reagents, reaction temperature, and reaction time were evaluated as factors that would influence the modification efficacy. 13C NMR spectroscopy analysis of lignin samples before and after esterification showed that the optimized reaction conditions could reach approximately 40% substitution of aliphatic hydroxyl groups. Both steps only used lignin and the modifying reagent (no solvent), with the possibility of recovery and reuse of the reagent by dilution and distillation. An additional second esterification step of the resulting lignin sample with acetic acid or propionic acid converted 90% of remaining hydroxyl groups into short-chain carbon aliphatic esters, making a hydrophobic material suitable for further copolymerization with synthetic hydrophobic monomers.

Revisiting the Molar Mass and Conformation of Derivatized Fractionated Softwood Kraft Lignin.

The limited utilization of reliable tools and standards for determination of the softwood kraft lignin molar mass and the corresponding molecular conformation hampers elucidation of the structure-property relationships of lignin. At issue, conventional size exclusion chromatography (SEC) is unable to robustly measure the molar mass because of a lack of calibration standards with a similar structure to lignin. In the present work, the determination of the absolute molar mass of acetylated technical lignin was revisited utilizing SEC combined with multi-angle light scattering with a band pass filter to suppress the fluorescence. Fractionated lignin isolated using sequential techniques of solvent and membrane methods was used to enhance the clarity of light-scattering profiles by narrowing the molar mass distribution of lignin fractions. Further information on the molecular conformation of derivatized samples was studied utilizing a differential viscometer, and chemical structures were identified by NMR spectroscopy analysis. Through the help of fractionation, intrinsic viscosity values were determined for the different fractions as a function of molecular weight cut-off membranes. The derivatized acetone-soluble lignin was found to possess a lower molecular weight and an extremely compact structure relative to the derivatized acetone-insoluble fraction based on a significantly lower "α" value in the Mark-Houwink-Sakurada plot (0.15 acetone-soluble vs 0.33 acetone-insoluble). The differences in geometry were supported by the linkage analysis from NMR showing the acetone-soluble part containing fewer native linkages. In both of these examples, kraft lignin behaved like a solid sphere, limiting the ability to provide entanglements between molecular chains. From this standpoint, macroscopic properties of lignin are justified with this knowledge of a dense and extremely compact structure.

Aqueous Dispersions of Esterified Lignin Particles for Hydrophobic Coatings.

An aqueous biopolymer dispersion coating system was synthesized utilizing softwood kraft lignin and a long chain organic acid. The chemical treatment of lignin was a two-step procedure, which first consisted of hydroxyethylation of the phenolic groups on lignin utilizing ethylene carbonate and an alkaline catalyst. This first step resulted in the lignin containing more than 80% aliphatic hydroxyl functionality (1H NMR). Following this step, oleic acid was reacted with hydoxyethyl lignin in order to form ester derivatives. With nearly a total reduction in absorbance in the hydroxyl stretching region, FT-IR analysis showed the majority of the hydroxyl groups was esterified forming an ethyl oleate derivative. Semi-quantitative 13C NMR analysis of the lignin revealed 88% substitution of the lignin hydroxyl groups. This derivative was soluble in organic solvent such as toluene and tetrahydrofuran. Solutions of lignin derivatives were slowly precipitated through dialysis, resulting in a stable dispersion of lignin microparticles in distilled water. The 1-2 µm average diameter size of the precipitated particles was found with dynamic light scattering of the suspensions. Spray and spin coating were used to apply the lignin derivative dispersion to different surfaces. For both coating methods, the lignin-based particles enhanced the hydrophobicity of all the substrates tested, resulting in increased water contact angles for glass, kraft pulp sheets and solid wood. Benign reagents involved in the coating synthesis utilized natural compounds that are known to repel water in nature. Combined with the avoidance of volatile organic solvents during application, this process provided a low environmental footprint solution for synthesis of hydrophobic coatings.

Functionalizing Cellulose Nanocrystals with Click Modifiable Carbohydrate-Binding Modules.

Functionalized cellulose nanocrystals (CNC) have unique properties that make them attractive in various applications such as drug delivery, hydrogels, and emulsions. However, the predominant chemical methods currently used to functionalize cellulose nanocrystals have a large environmental footprint. Although greener methods are desirable, the relatively inert nature of cellulose crystals presents a major challenge to their potential modification in aqueous media. In the work reported here, carbohydrate binding modules (CBMs) were used to introduce new functionality to cellulose surfaces. CBM2a, which has a strong affinity for crystalline cellulose, was functionalized with an alkyne at the terminal amine position. The alkyne group, which was introduced onto the cellulose surface with CBM2a, underwent a Click reaction with polyethylene glycol (PEG) to modify CNC surfaces. This provided a strong, non-covalent modification of cellulose surfaces that was carried out in a one-pot reaction in aqueous media. The CBM-PEG modification of cellulose surfaces increased CNC redispersion after drying and improved suspension stability based on steric interactions. It was apparent that hybrid polysaccharide-protein, self-assembled nanoparticles could be effectively produced, with potential for nanomedicine, immunoassay, and drug delivery applications.