Cationization of eucalyptus kraft lignoboost lignin: preparation, properties, and potential applications

Current changes toward a more biobased economy have recently created tremendous renewed interest in using lignin as a valuable source for chemicals and materials. Here, we present a facile cationization approach aiming to impart kraft lignin water-solubility, with similar good features as lignosulfonates. Eucalyptus globulus kraft lignin obtained from a paper mill black liquor by applying the LignoBoost process was used as the substrate. Its reaction with 3-chloro-2-hydroxypropyl-trimethylammonium chloride (CHPTAC) in an aqueous alkaline medium was studied to assess the impact of different reaction conditions (temperature, time, educt concentration, molar CHPTAC-to-lignin ratio) on the degree of cationization. It has been shown that at pH 13, 10 wt % lignin content, 70 °C, and 3 h reaction time, a CHPTAC-to-lignin minimum molar ratio of 1.3 is required to obtain fully water-soluble products. Elemental analysis (4.2% N), size-exclusion chromatography (M w 2180 Da), and quantitative 13C NMR spectroscopy of the product obtained at this limit reactant concentration suggest introduction of 1.2 quaternary ammonium groups per C9 unit and substitution of 75% of the initially available phenolic OH groups. The possible contribution of benzylic hydroxyls to the introduction of quaternary ammonium moieties through a quinone methide mechanism has been proposed. Since both molecular characteristics and degree of substitution, and hence solubility or count of surface charge, of colloidal particles can be adjusted within a wide range, cationic kraft lignins are promising materials for a wide range of applications, as exemplarily demonstrated for flocculation of anionic dyes.publishe

Hydrogels Of Chiral–Nematic Cellulose Nanocrystals And Nanochitin

The mechanical strength of hydrogels and aerogels produced from inorganic nano- and microparticles has been out of limits for those based on organic counterparts. Control over the nanoscale architecture of such materials is a possible answer to this challenge, which can even expand properties and functions, including mechano-optical activity. Here we show unprecedented levels of strength by controlling the assembly architecture of cellulose nanocrystals (CNC) and nanochitin (NCh), nanoscaled building blocks presenting anisometry and high intrinsic strength. High yield (\u3e85%) and low-energy deconstruction of never-dried residual marine biomass is proposed following partial deacetylation and microfluidization. This process results in NCh of ultrahigh axial size that produce highly entangled networks upon pH shift. Viscoelastic and strong hydrogels are formed by ice templating upon freezing and thawing with simultaneous cross-linking. Slow supercooling and ice nucleation at −20 °C make ice crystals grow slowly and exclude nanochitin and cross-linkers, becoming spatially confined at the interface. At a NCh concentration as low as 0.4 wt %, highly viscoelastic hydrogels are formed, at least an order of magnitude larger compared to those measured for the strongest chitin-derived hydrogels reported so far. The water absorption capacity of the hydrogels reaches a value of 466 g/g. Moreover, our results demonstrate that chiral-nematically ordered hydrogels can lead to aerogels with controlled meso- and microstructures that replicate the liquid crystalline phase transitions of the hydrogels. The obtained architectures are feasible by systematically varying the long-range order of the aqueous CNC dispersions, from mostly isotropic to completely anisotropic. The resultant aerogels display strong coupling between the mesopore fraction and selective light reflection (iridescence) as a function of mechanical load. Specifically, we find that the mechanical performance associated with pore compression under load is greatly enhanced by chiral nematic ordering. These new limits in the mechanical properties of CNC- and NCh-based hydrogels and aerogels point to new structural considerations for the synthesis of porous constructs that exploit the inherent long-range order of such unique building blocks

Precipitation of Hemicelluloses from DMSO/Water Mixtures Using Carbon Dioxide as an Antisolvent

Supercritical antisolvent precipitation is a relatively recent technology which can be used for controlled preparation of polymer particles from solutions. This is done by the addition of an antisolvent to a polymer solution causing supersaturation of the polymer, especially under supercritical conditions. The particle size of the precipitates can be adjusted mainly by the rate of supersaturation. Spherical xylan or mannan particles having a narrow particle size distribution were precipitated from hemicellulose solutions in dimethyl-sulfoxide (DMSO) or DMSO/water mixtures by carbon dioxide as an antisolvent. By depending on the type of hemicellulose, the DMSO/H2O ratio, and the precipitation conditions such as pressure and temperature, the resulting particle size can be adjusted within a wide range from less than 0.1 to more than 5 m. Nano- and microstructured native xylans and mannans as obtained can be used in many applications such as encapsulation of active compounds, slow release agents, or chromatographic separation materials

Transparent, flexible, and strong 2,3-dialdehyde cellulose films with high oxygen barrier properties

2,3-Dialdehyde cellulose (DAC) of a high degree of oxidation (92% relative to AGU units) prepared by oxidation of microcrystalline cellulose with sodium periodate (48 degrees C, 19 h) is soluble in hot water. Solution casting, slow air drying, hot pressing, and reinforcement by cellulose nanocrystals afforded films (similar to 100 mu m thickness) that feature intriguing properties: they have very smooth surfaces (SEM), are highly flexible, and have good light transmittance for both the visible and near-infrared range (89-91%), high tensile strength (81-122 MPa), and modulus of elasticity (3.4-4.0 GPa) depending on hydration state and respective water content. The extraordinarily low oxygen permeation ofPeer reviewe

Hemocompatibility of cellulose phosphate aerogel membranes with potential use in bone tissue engineering

Cellulose is an appealing material for tissue engineering. In an attempt to overcome some obstacles with cellulose II cell scaffolding materials related to insufficient biomineralization, lack of micron-size porosity, and deficiency in surface charge, respective solutions have been proposed. These included covalent phosphorylation of different cellulose materials targeting relatively low degrees of substitution (DS 0.18–0.23) and processing these cellulose derivatives into scaffolding materials by a dissolution/coagulation approach employing the hitherto rarely used TBAF/DMSO/H2O system for cellulose dissolution. Here, we report bioactivity and preliminary hemocompatibility testing of dual-porous cellulose phosphate aerogels (contrasted with the phosphate-free reference) obtained via coagulation (water/ethanol), solvent exchange and scCO2 drying. Deposition of hydroxyapatite from simulated body fluid (7 days of immersion) revealed good bioactivity (1.5–2.2 mg Ca2+ per mg scaffold). Incubation of the scCO2-dried and rehydrated scaffolding materials in heparin anticoagulated human whole blood was conducted to study selected parameters of hemostasis (prothrombin F1+2 fragment, PF4, count of thrombocyte-leukocyte conjugates) and inflammatory response (C5a fragment, leukocyte activation marker CD11b). Adhesion of leukocytes on the surface of the incubated substrates was assessed by scanning electron and fluorescence microscopy (DAPI staining). The results suggest that phosphorylation at low DS does not increase platelet activation. However, a significant increase in platelet activation and thrombin formation was observed after a certain fraction of the negative surface charges had been compensated by Ca2+ ions. The combination of both phosphorylation and calcification turned out to be a potent means for controlling the inflammatory response, which was close to baseline level for some of the studied samples

False Morphology of Aerogels Caused by Gold Coating for SEM Imaging

The imaging of non-conducting materials by scanning electron microscopy (SEM) is most often performed after depositing few nanometers thick conductive layers on the samples. It is shown in this work, that even a 5 nm thick sputtered gold layer can dramatically alter the morphology and the surface structure of many different types of aerogels. Silica, polyimide, polyamide, calcium-alginate and cellulose aerogels were imaged in their pristine forms and after gold sputtering utilizing low voltage scanning electron microscopy (LVSEM) in order to reduce charging effects. The morphological features seen in the SEM images of the pristine samples are in excellent agreement with the structural parameters of the aerogels measured by nitrogen adsorption-desorption porosimetry. In contrast, the morphologies of the sputter coated samples are significantly distorted and feature nanostructured gold. These findings point out that extra care should be taken in order to ensure that gold sputtering does not cause morphological artifacts. Otherwise, the application of low voltage scanning electron microscopy even yields high resolution images of pristine non-conducting aerogels

Anisotropic nanocellulose gel–membranes for drug delivery: Tailoring structure and interface by sequential periodate–chlorite oxidation

International audienc

Solvolytic liquefaction of oil palm empty fruit bunch (EFB) fibres: analysis of product fractions using FTIR and pyrolysis-GCMS

Oil palm empty fruit bunch (EFB) fibers were subjected to solvolytic liquefaction to convert into liquid products using ethylene glycol (EG) as a supporting agent. The process was carried out at 250˚C for 60 min. The water-insoluble product fraction was exhaustively extracted with acetone (ASL fraction) to separate all less polar. FTIR and comparative analytical pyrolysis GC/MS of the parent EFB fiber and the ASL fraction confirmed the formation of larger amounts of long-chain lipophilic compounds under liquefaction conditions. Furthermore, a considerable amount of less polar thermal lignin degradation products were obtained comprising all of the three main lignin building blocks, i.e. 4-hydroxyphenyl- (P units), 4-hydroxy-3-methoxyphenyl- (G units) and 3,5-dimethoxy-4-hydroxyphenyl (S units) substituted compounds. 4-Prop-2-en-1-yl substituted phenolic compounds contributed mostly to the cumulated peak area of all lignin derived pyrolysis products obtained by analytical Curie point pyrolysis GC/MS at 600°C. The results of both instrumental-analytical methods confirm the formation of phenol and its derivatives, furan derivatives, organic acids, hydrocarbon, ester, benzene groups and alcohols

Ultralight-Weight Cellulose Aerogels from NBnMO-Stabilized Lyocell Dopes

Cellulose aerogels are intriguing new materials produced by supercritical drying of regenerated cellulose obtained by solvent exchange of solid Lyocell moldings. From N-methylmorpholine-N-oxide solutions with cellulose contents between 1 and 12%, dimensionally stable cellulose bodies are produced, in which the solution structure of the cellulose is largely preserved and transferred into the solid state. The specific density and surface of the obtained aerogels range from 0.05 to 0.26 g/cm3 and from 172 to 284 m2/g, respectively, depending on the cellulose content of the Lyocell dopes and regeneration procedure. A reliable extraction and drying procedure using supercritical carbon dioxide, the advantageous use of NBnMO as stabilizer for the Lyocell dopes, and selected physical properties of the materials is communicated

Peptide-Cellulose Conjugates on Cotton-Based Materials Have Protease Sensor/Sequestrant Activity

The growing incidence of chronic wounds in the world population has prompted increased interest in chronic wound dressings with protease-modulating activity and protease point of care sensors to treat and enable monitoring of elevated protease-based wound pathology. However, the overall design features needed for the combination of a chronic wound dressing that lowers protease activity along with protease detection capability as a single platform for semi-occlusive dressings has scarcely been addressed. The interface of dressing and sensor specific properties (porosity, permeability, moisture uptake properties, specific surface area, surface charge, and detection) relative to sensor bioactivity and protease sequestrant performance is explored here. Measurement of the material’s zeta potential demonstrated a correlation between negative charge and the ability of materials to bind positively charged Human Neutrophil Elastase. Peptide-cellulose conjugates as protease substrates prepared on a nanocellulosic aerogel were assessed for their compatibility with chronic wound dressing design. The porosity, wettability and absorption capacity of the nanocellulosic aerogel were consistent with values observed for semi-occlusive chronic wound dressing designs. The relationship of properties that effect dressing functionality and performance as well as impact sensor sensitivity are discussed in the context of the enzyme kinetics. The sensor sensitivity of the aerogel-based sensor is contrasted with current clinical studies on elastase. Taken together, comparative analysis of the influence of molecular features on the physical properties of three forms of cellulosic transducer surfaces provides a meaningful assessment of the interface compatibility of cellulose-based sensors and corresponding protease sequestrant materials for potential use in chronic wound sensor/dressing design platforms