Wood Cellulose Nanofibrils Research Articles

Effects of Chemical Pretreatments of Wood Cellulose Nanofibrils on Protein Adsorption and Biological Outcomes.

Wood-based nanocellulose is emerging as a promising nanomaterial in the field of tissue engineering due to its unique properties and versatile applications. Previously, we used TEMPO-mediated oxidation (TO) and carboxymethylation (CM) as chemical pretreatments prior to mechanical fibrillation of wood-based cellulose nanofibrils (CNFs) to produce scaffolds with different surface chemistries. The aim of the current study was to evaluate the effects of these chemical pretreatments on serum protein adsorption on 2D and 3D configurations of TO-CNF and CM-CNF and then to investigate their effects on cell adhesion, spreading, inflammatory mediator production in vitro, and the development of foreign body reaction (FBR) in vivo. Mass spectrometry analysis revealed that the surface chemistry played a key role in determining the proteomic profile and significantly influenced the behavior of periodontal ligament fibroblasts and osteoblast-like cells (Saos-2). The surface of TO-CNF 2D samples showed the highest protein adsorption followed by TO-CNF 3D samples. CM-CNF 2D samples adsorbed a higher number of proteins than their 3D counterparts. None of the CNF scaffolds showed toxicity in vitro or in vivo. However, carboxymethylation pretreatment negatively affected the adhesion, morphology, and spreading of both cell types. Although the CNF materials displayed clear differences in surface chemistry and proteomic profiles, both triggered the same foreign body response after being subcutaneously implanted in rats for 90 days. This observation highlights that the degradation rate of CNF scaffolds plays a central role in maintaining the foreign body response in vivo. It is imperative to comprehend the impact of chemical pretreatments of CNFs on protein adsorption and their interaction with diverse host cell types prior to the investigation of potential modifications. This knowledge is indispensable for the advancement of CNFs in regenerative applications within tissue engineering.

The influence of drying routes on the properties of anisotropic all-cellulose composite foams from post-consumer cotton clothing.

Biopolymer-based functional materials are essential for reducing the carbon footprint and providing high-quality lightweight materials suitable for packaging and thermal insulation. Here, cellulose nanocrystals (CNCs) were efficiently upcycled from post-consumer cotton clothing by TEMPO-mediated oxidation and HCl hydrolysis with a yield of 62% and combined with wood cellulose nanofibrils (CNFs) to produce anisotropic foams by unidirectional freeze-casting followed by freeze drying (FD) or supercritical-drying (SCD). Unidirectional freeze-casting resulted in foams with aligned macropores irrespective of the drying method, but the particle packing in the foam wall was significantly affected by how the ice was removed. The FD foams showed tightly packed and aligned CNC and CNF particles while the SCD foams displayed a more network-like structure in the foam walls. The SCD compared to FD foams had more pores smaller than 300 nm and higher specific surface area but they were more susceptible to moisture-induced shrinkage, especially at relative humidities (RH) > 50%. The FD and SCD foams displayed low radial thermal conductivity, and the FD foams displayed a higher mechanical strength and stiffness in compression in the direction of the aligned particles. Better understanding how drying influences the structural, thermal, mechanical and moisture-related properties of foams based on repurposed cotton is important for the development of sustainable nanostructured materials for various applications.

Improving the degree of polymerization of cellulose nanofibers by largely preserving native structure of wood fibers

The degree of polymerization (DP) of cellulose plays an essential role in unlocking the superior mechanical potential of wood cellulose nanofibrils (CNFs). However, severe degradation of cellulose chains during the chemical pulping is a big challenge to obtain CNFs with high DP. In this work, we tend to improve the DP of wood CNFs by significantly preserving the native structure of wood fibers in an industrial method. Wood sticks are first pretreated with hydrothermal treatment to partially remove hemicellulose, thus leading to an increased porous structure that facilitates the penetration of cooking liquid and lignin removal during delignification, and dilute-alkali-sulfate pulping is then employed to obtain wood fibers with highest viscosity average DP (DPV) of nearly 2400. After that, the as-prepared wood fibers with high DP are separated into CNFs with highest average DPV of 1333. Finally, we demonstrate the potential application of wood CNFs with improved DPV in the fabrication of strong and tough isotropic films and macrofibers.

Highlights on the mechanical pre-refining step in the production of wood cellulose nanofibrils

Highlights on the mechanical pre-refining step in the production of wood cellulose nanofibrils

Changes to the Contour Length, Molecular Chain Length, and Solid-State Structures of Nanocellulose Resulting from Sonication in Water.

Sonication in water reduced the average contour lengths of nanocellulose prepared from wood cellulose fiber and microcrystalline cellulose. Most of the kinks in the wood cellulose nanofibrils were formed during the initial 10 min of sonication. Fragmentation occurred at the kinks and rigid segments associated with depolymerization during subsequent sonication for 10-120 min, resulting in the formation of cellulose nanocrystals with low aspect ratios. Solid-state cross-polarization magic angle sample spinning 13C-nuclear magnetic resonance revealed that the original crystalline regions of the cellulose were partly transformed to fibril surfaces or disordered regions by both pretreatment and the subsequent fragmentation of molecular chains during sonication. The nanocellulose prepared from microcrystalline cellulose had different fragmentation behavior with regard to molecular chain length following sonication. The results indicated that on average the hexagonal 36 cellulose chain structure formed the cross-section of each wood cellulose microfibril.

Low cost membrane of wood nanocellulose obtained by mechanical defibrillation for potential applications as wound dressing

Large wounds are characterized by clinical and surgical challenges, requiring numerous searches on demand for inexpensive biocompatible materials that produce the best quality of cutaneous healing. Cellulose is a biopolymer of greatest abundance, good biocompatibility and wide application due to its chemical and physical properties. This study was aimed to develop and characterize low cost membranes of wood cellulose nanofibrils for potential application as a wound dressing in comparison to a commercial porous regenerating membrane. An inexpensive mechanical method was used to defibrillate cellulose, and later the membranes were obtained from the nanofibrils by filtering and drying under mild pressure. The techniques employed for characterization included scanning electron microscopy, physical testing, application in vivo and cost-effectiveness analysis. The membranes presented promising physical properties for application as cutaneous dressing, with characteristic translucency allowing the evaluation of the wound without the need of removal and exchange of the dressing. Wood nanocellulose dressing seems to be promising for wound care since it presented good adhesion to the moist wound surfaces thus promoting the most efficient repitialization in the first 4 days. No allergic reaction or inflammatory response to wood nanocellulose dressings was observed. The wood nanocellulose membranes stand out as a potential wound dressing, as it shows similar efficacy of bacterial cellulose dressing. Besides the efficacy, the membrane developed in this study presents a simpler, faster and cheaper manufacturing process, which may reduce the production cost by 99%.

Relationship of Distribution of Carboxy Groups to Molar Mass Distribution of TEMPO-Oxidized Algal, Cotton, and Wood Cellulose Nanofibrils.

Distributions of carboxy groups among the molecules in 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibrils (TOCNs) prepared from wood, cotton, and algal celluloses were investigated. Most C6-carboxy groups in TOCNs were esterified with anthracene-methyl (-CH2C14H9) groups, showing an ultraviolet light (UV) absorption peak at 365 nm. The anthracene-methylated TOCNs were dissolved in 8% (w/w) lithium chloride/N,N-dimethylacetamide (LiCl/DMAc). After dilution to 1% LiCl/DMAc, the solutions were subjected to size-exclusion chromatography with multiangle laser-light scattering, refractive index, and UV detection. For algal TOCN, C6-carboxy group-rich molecules were present predominantly in the low-molar-mass region, which was consistent with the core-clad cellulose chain packing structures in individual algal cellulose microfibrils and partial depolymerization of the oxidized cellulose molecules. In contrast, wood and cotton TOCNs had almost homogeneous distributions of C6-carboxy groups in all molar mass regions, which could not be explained in terms of the simple core-clad cellulose chain packing structures.

Nanocellulose as a colorimetric biosensor for effective and facile detection of human neutrophil elastase

Nanocellulose has functionalities suitable for efficient sensor transducer surface design including crystallinity, biocompatible and high specific surface area. Here we explore two forms of nanocellulose as transducer surfaces to enable colorimetric detection of human neutrophil elastase (HNE), and a wide range of inflammatory diseases. A deep eutectic solvent (DES) was utilized to mediate formation of cotton cellulose nanocrystals (DCNCs) employed to prepare a peptide-cellulose conjugate as a protease sensor of HNE. The tetrapeptide-cellulose analog on DCNC is contrasted with an analogous derivative of TEMPO-oxidized wood cellulose nanofibrils (WCNFs). DCNCs showed greater degree of substitution of HNE tetrapeptide and sensitivity to the elastase than WCNFs, despite the smaller surface area and pore sizes. XRD models revealed the higher crystallinity and larger crystallite sizes of DCNCs, indicating the well-arranged cellulose chains for immobilization of the tetrapeptide on (110) lattice reflections of cellulose crystals. The sensitivity of DCNCs-based colorimetric sensor was less than 0.005 U/mL, which would provide a convenient, sensitive sensor applicable for improved colorimetric point of care protease biomarker detection.

Producing ultrapure wood cellulose nanofibrils and evaluating the cytotoxicity using human skin cells

Wood cellulose nanofibrils (CNF) have been suggested as a potential wound healing material, but its utilization is limited by FDA requirements regarding endotoxin levels. In this study a method using sodium hydroxide followed by TEMPO mediated oxidation was developed to produce ultrapure cellulose nanofibrils, with an endotoxin level of 45 endotoxin units/g (EU/g) cellulose. Scanning transmission electron microscopy (S(T)EM) revealed a highly nanofibrillated structure (lateral width of 3.7±1.3nm).Assessment of cytotoxicity and metabolic activity on Normal Human Dermal Fibroblasts and Human Epidermal Keratinocytes was done. CNF-dispersion of 50μg/ml did not affect the cells. CNF-aerogels induced a reduction of metabolic activity by the fibroblasts and keratinocytes, but no significant cell death. Cytokine profiling revealed no induction of the 27 cytokines tested upon exposure to CNF. The moisture-holding capacity of aerogels was relatively high (∼7500%), compared to a commercially available wound dressing (∼2500%), indicating that the CNF material is promising as dressing material for management of wounds with a moderate to high amount of exudate.

Mechanical properties of cellulose nanomaterials studied by contact resonance atomic force microscopy

Quantification of the mechanical properties of cellulose nanomaterials is key to the development of new cellulose nanomaterial based products. Using contact resonance atomic force microscopy we measured and mapped the transverse elastic modulus of three types of cellulosic nanoparticles: tunicate cellulose nanocrystals, wood cellulose nanocrystals, and wood cellulose nanofibrils. These modulus values were calculated with different contact mechanics models exploring the effects of cellulose geometry and thickness on the interpretation of the data. While intra-particle variations in modulus are detected, we did not observe a measureable difference in modulus between the three types of cellulose particles. Improved practices and experimental complications for the characterization of cellulosic nanomaterials with atomic force microscopy are discussed.

An Ultrastrong Nanofibrillar Biomaterial: The Strength of Single Cellulose Nanofibrils Revealed via Sonication-Induced Fragmentation

We report the mechanical strength of native cellulose nanofibrils. Native cellulose nanofibrils, purified from wood and sea tunicate, were fully dispersed in water via a topochemical modification of cellulose nanofibrils using 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO) as a catalyst. The strength of individual nanofibrils was estimated based on a model for the sonication-induced fragmentation of filamentous nanostructures. The resulting strength parameters were then analyzed based on fracture statistics. The mean strength of the wood cellulose nanofibrils ranged from 1.6 to 3 GPa, depending on the method used to measure the nanofibril width. The highly crystalline, thick tunicate cellulose nanofibrils exhibited higher mean strength of 3-6 GPa. The strength values estimated for the cellulose nanofibrils in the present study are comparable with those of commercially available multiwalled carbon nanotubes.

Zeta Potential Time Dependence Reveals the Swelling Dynamics of Wood Cellulose Nanofibrils

In this paper, we present the swelling dynamics of individual wood cellulose nanofibrils (CNFs) following solvent substitution into various organic solvents and drying, by employing the time dependence of the zeta potential (ζ). We succeeded in smoothly redispersing the coaggregating CNFs dried in solvents, including acetone, acetonitrile, DMSO, ethanol, and t-butanol into water. ζ-t plots of the redispersed CNFs measured in a 1 mM KCl solution indicated different values of Δζ (volume fraction of hydration capacity), corresponding to the dielectric constant of the substituted solvents. Differential scanning calorimetry confirmed that the redispersed CNFs swell to different degrees, corresponding to Δζ. This swelling behavior is characterized by expansion of hemicelluloses, the amorphous polysaccharides located on the CNF surface, with a different degree of aggregation during drying. The specific swelling ratio, radius, and diameter of the CNFs in water were calculated using the values of ζ(0) and ζ(∞) by introducing surface chemical analysis. The calculated diameters of the CNFs at t = 0 coincided well with the median diameters measured directly by transmission electron microscope. Swellability of hemicelluloses exponentially increased with the decrease in dielectric constant of solvent during drying. The analysis method combining zeta potential time dependence and a surface chemical approach proved useful for specifically evaluating the swelling dynamics of polymers on a bulk surface.

Wood cellulose nanofibrils prepared by TEMPO electro-mediated oxidation

A softwood bleached kraft pulp (SBKP) was subjected to electro-mediated oxidation in water with TEMPO or 4-acetamido-TEMPO without any chlorine-containing oxidant. Solid recovery ratios of water-insoluble fractions of the oxidized SBKPs were more than 80%, and C6-carboxylate contents increased up to approximately 1 mmol g−1 after oxidation for 48 h. Significant amounts of C6-aldehyde groups (0.17–0.38 mmol g−1) were also formed in the oxidized SBKPs. The degree of polymerization decreased from 2,200 to 520 and 1,400 by the oxidation for 48 h with TEMPO at pH 10 and 4-acetamido-TEMPO at pH 6.8, respectively. The original cellulose I crystal structure and crystallinity of SBKP were maintained after the oxidation, indicating that all C6-oxidized groups were selectively formed on crystalline cellulose microfibril surfaces. The oxidized SBKPs with carboxylate contents of more than 0.9 mmol g−1 were convertible to individual cellulose nanofibrils in yields of more than 80% by disintegration in water.

A METHOD FOR ISOLATING CELLULOSE NANOFIBRILS FROM WOOD AND THEIR MORPHOLOGICAL CHARACTERISTICS

Toward exploiting cellulose nanofibrils with high aspect ratio and nano-order-unit interconnected web-like structure from poplar wood,a novel route was demonstrated,which combined the usual chemical procedures with high intensity ultrasonic treatment of the material in the water-swollen state. Firstly,lignin in the sample was removed using an acidified sodium chlorite solution. Secondly,the sample was treated with potassium hydroxide in order to leach hemicellulose. Lastly,the sample was processed with high intensity ultrasonication. Never-dried holocellulose,never-dried purified cellulose and wood cellulose nanofibrils (WCNF) were obtained,respectively. The changes of WCNF on the chemical composition,crystalline structure,crystallinity and morphologies during the preparation process were characterized by means of Fourier transform infrared spectroscopy (FTIR),X-ray diffraction (XRD) and scanning electron microscopy (SEM), and the diameter distribution of WCNF was further calculated and analyzed by image analysis method. The results showed that the main composition of WCNF was cellulose with crystalline structure of Ⅰ type,and the crystallinity of WCNF was 65. 68% ,12. 33% higher than that of the raw material wood. The diameters,lengths and aspect ratio of WCNF were about 5 ～ 32 nm,longer than 10 μm and larger than 300,respectively. The nanofibrils of WCNF were also interconnected into unique web-like structure. The characteristics including high crystallinity,high aspect ratio,nano-order-scale,web-like entangled structure,and so on,indicate that WCNF is a perfect reinforcing and toughening material.