Cationic Cellulose Nanofibrils Research Articles

Production of highly substituted cationic cellulose nanofibrils through disk milling/high-pressure homogenization

Production of highly substituted cationic cellulose nanofibrils through disk milling/high-pressure homogenization

Anionic and cationic cellulose nanofibrils as a macronutrient-carrying vehicle

Anionic and cationic cellulose nanofibrils as a macronutrient-carrying vehicle

Fabrication of cationic cellulose nanofibrils/sodium alginate beads for Congo red removal

Congo red is hard to remove from dye wastewater due to its structure stability and high chemical oxygen demand. In this study, cationic cellulose nanofibrils (CCNF) prepared from herb residues was physically crosslinked with sodium alginate (SA) in the presence of calcium ions, and the obtained CCNF/SA beads were used to adsorb Congo red. Results showed that CCNF/SA beads with porous internal structure were beneficial to adsorption. The maximum adsorption capacity of Congo red could reach to 518.4mg/g, which was superior to most cellulose-based adsorption materials. Furthermore, the equilibrium adsorption isotherms and XPS analysis indicated the adsorption for Congo red was a physical process, and hydrogen bond and electrostatic adsorption were proposed as dominant adsorption mechanism. In addition, the Congo red removal efficiency of the beads was still higher than 70% after three cycles. Therefore, this high efficiency and green beads have great potential as adsorbents for anionic dyes removal.

Lignin nanoparticle-decorated nanocellulose cryogels as adsorbents for pharmaceutical pollutants

Adsorption is a relatively simple wastewater treatment method that has the potential to mitigate the impacts of pharmaceutical pollution. This requires the development of reusable adsorbents that can simultaneously remove pharmaceuticals of varying chemical structure and properties. Here, the adsorption potential of nanostructured wood-based adsorbents towards different pharmaceuticals in a multi-component system was investigated. The adsorbents in the form of macroporous cryogels were prepared by anchoring lignin nanoparticles (LNPs) to the nanocellulose network via electrostatic attraction. The naturally anionic LNPs were anchored to cationic cellulose nanofibrils (cCNF) and the cationic LNPs (cLNPs) were combined with anionic TEMPO-oxidized CNF (TCNF), producing two sets of nanocellulose-based cryogels that also differed in their overall surface charge density. The cryogels, prepared by freeze-drying, showed layered cellulosic sheets randomly decorated with spherical lignin on the surface. They exhibited varying selectivity and efficiency in removing pharmaceuticals with differing aromaticity, polarity and ionic characters. Their adsorption potential was also affected by the type (unmodified or cationic), amount and morphology of the lignin nanomaterials, as well as the pH of the pharmaceutical solution.Overall, the findings revealed that LNPs or cLNPs can act as functionalizing and crosslinking agents to nanocellulose-based cryogels. Despite the decrease in the overall positive surface charge, the addition of LNPs to the cCNF-based cryogels showed enhanced adsorption, not only towards the anionic aromatic pharmaceutical diclofenac but also towards the aromatic cationic metoprolol (MPL) and tramadol (TRA) and neutral aromatic carbamazepine. The addition of cLNPs to TCNF-based cryogels improved the adsorption of MPL and TRA despite the decrease in the net negative surface charge. The improved adsorption was attributed to modes of removal other than electrostatic attraction, and they could be π-π aromatic ring or hydrophobic interactions brought by the addition of LNPs or cLNPs. However, significant improvement was only found if the ratio of LNPs or cLNPs to nanocellulose was 0.6:1 or higher and with spherical lignin nanomaterials. As crosslinking agents, the LNPs or cLNPs affected the rheological behavior of the gels, and increased the firmness and decreased the water holding capacity of the corresponding cryogels. The resistance of the cryogels towards disintegration with exposure to water also improved with crosslinking, which eventually enabled the cryogels, especially the TCNF-based one, to be regenerated and reused for five cycles of adsorption-desorption experiment for the model pharmaceutical MPL. Thus, this study opened new opportunities to utilize LNPs in providing nanocellulose-based adsorbents with additional functional groups, which were otherwise often achieved by rigorous chemical modifications, at the same time, crosslinking the nanocellulose network.

Efficient Encapsulation and Controlled Release of N,N-Diethyl-3-methylbenzamide (DEET) from Oil-in-Water Emulsions Stabilized by Cationic Nanocellulose and Silica Nanoparticles

Oil-in-water emulsions containing N,N-diethyl-3-methylbenzamide (DEET) were developed aiming to extend the sustained release of the active compound, by using two oppositely charged nanomaterials, namely silica nanoparticles (SiNP) and cationic cellulose nanofibrils (CCNF), as stabilizers, and a mixture of food-grade nonionic surfactants to avoid precipitation by electrostatic aggregation. The formulations were stable for more than four months at room temperature, and strongly resistant to destabilization upon centrifugal and thermal stress. The results were correlated with the effect of SiNP on strengthening the network formation of CCNF in the aqueous phase by electrostatic interactions, which increased the viscosity of the external phase and, hence, emulsion stability. There was a significant size reduction of the internal oil phase containing DEET in the presence of CCNF, which was attributed to the increased viscosity in the external aqueous phase, as well as to interfacial stabilization. The combined action of CCNF and unmodified SiNP in the stabilization of the DEET-containing oil phase significantly decreased the release rate of the active compound, compared to non-emulsified DEET. Moreover, in the emulsions containing the CCNF/SiNP mixture there was a more sustained release for the period of 6 h, demonstrating the potential of these formulations for extended protection.

Salt-Responsive Pickering Emulsions Stabilized by Functionalized Cellulose Nanofibrils.

Oil-in-water emulsions have been stabilized by functionalized cellulose nanofibrils bearing either a negative (oxidized cellulose nanofibrils, OCNF) or a positive (cationic cellulose nanofibrils, CCNF) surface charge. The size of the droplets was measured by laser diffraction, while the structure of the shell of the Pickering emulsion droplets was probed using small-angle neutron scattering (SANS), confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM), and rheology measurements. Both OCNF- and CCNF-stabilized emulsions present a very thick shell (>100 nm) comprised of densely packed CNF. OCNF-stabilized emulsions proved to be salt responsive, influencing the droplet aggregation and ultimately the gel properties of the emulsions, while CCNF emulsions, on the other hand, showed very little salt-dependent behavior.

Study on the Multilayer Barrier Coating Using Cellulose Nanofibrils and Internal Sizing Agent

In this study, we tried to develop techniques to increase coat weight and improve water resistance at a lower number of multilayer barrier coatings with anionic and cationic cellulose nanofibrils (CNFs), which has been reported in previous research. The concentration of CNF slurry was adjusted to increase the coat weight, while alkyl ketene dimer (AKD) was added as an internal sizing agent to the anionic CNF slurry to impart hydrophobicity to the CNFs. After the preparation of CNF slurries, the multilayer barrier coating was applied on never-size base paper. The coat weight, air permeability, and Cobb size degree of the barrier-coated paper were subsequently measured, and the surface of the paper was analyzed via SEM. The coat weight and air permeability of the paper coated four times with CNF slurry at 1.4% concentration were similar to those of the paper coated six times with CNF slurry at 1.0% concentration. In addition, the Cobb size degree of the barrier-coated paper decreased as the AKD addition to anionic CNF at a concentration of 1.4% increased linearly. However, when the addition level of AKD increased more than 5.0%, the Cobb size degree of the barrier-coated paper increased due to the uneven distribution of AKD. Therefore, multilayer barrier coating can be carried out effectively with cationic and anionic CNFs at high concentrations, and AKD improves the water resistance of barrier-coated paper.

Cellulose Mesh with Charged Nanocellulose Coatings as a Promising Carrier of Skin and Stem Cells for Regenerative Applications.

Engineering artificial skin constructs is an ongoing challenge. An ideal material for hosting skin cells is still to be discovered. A promising candidate is low-cost cellulose, which is commonly fabricated in the form of a mesh and is applied as a wound dressing. Unfortunately, the structure and the topography of current cellulose meshes are not optimal for cell growth. To enhance the surface structure and the physicochemical properties of a commercially available mesh, we coated the mesh with wood-derived cellulose nanofibrils (CNFs). Three different types of mesh coatings are proposed in this study as a skin cell carrier: positively charged cationic cellulose nanofibrils (cCNFs), negatively charged anionic cellulose nanofibrils (aCNFs), and a combination of these two materials (c+aCNFs). These cell carriers were seeded with normal human dermal fibroblasts (NHDFs) or with human adipose-derived stem cells (ADSCs) to investigate cell adhesion, spreading, morphology, and proliferation. The negatively charged aCNF coating significantly improved the proliferation of both cell types. The positively charged cCNF coating significantly enhanced the adhesion of ADSCs only. The number of NHDFs was similar on the cCNF coatings and on the noncoated pristine cellulose mesh. However, the three-dimensional (3D) structure of the cCNF coating promoted cell survival. The c+aCNF construct proved to combine benefits from both types of CNFs, which means that the c+aCNF cell carrier is a promising candidate for further application in skin tissue engineering.

Rapid in-situ growth of gold nanoparticles on cationic cellulose nanofibrils: Recyclable nanozyme for the colorimetric glucose detection

Novel microwave-assisted green in-situ synthesis of positively charged gold nanoparticles (AuNPs) supported by cationic cellulose nanofibrils (C.CNF) within 30 s and devoid of additional reducing agent is reported. Peroxidase activity of these positive AuNPs was studied and that appeared to be superior over its negative charged counterpart. Further the AuNPs@C.CNF is casted into a film which makes it reusable. Using TMB substrate, simple and sensitive colorimetric detection methods for H2O2 and glucose were established. Under optimal conditions, the linear ranges were found to be 0.5–30 μM and 1–60 μM, and the detection limits were 0.30 and 0.67 μM for H2O2 and glucose, respectively. The film was potentially reused for the detection of glucose up to five cycles without a decrease in the activity. Further, this technique was employed to quantify glucose in human serum samples, and the obtained results were comparable with those of the standard GOD-POD method.

Cationization of Pulp Fibers as Pretreatment and Preparation of Cationic Cellulose Nanofibrils

Cationization of Pulp Fibers as Pretreatment and Preparation of Cationic Cellulose Nanofibrils

Study on the Quaternization Reaction Conditions for Cationic Cellulose Nanofibril

In this study, cationic cellulose nanofibrils (CNFs) were prepared from laboratory-made HwBKP CNFs via a quaternization reaction as a post-treatment using glycidyl methacrylate (GMA), and their major properties were investigated. The effects of adding GMA on the zeta potential and other main properties of cationic CNFs were analyzed to determine the minimum amount of GMA that must be added in order to acquire uniform cationic CNFs. The average zeta potential of cationic CNFs increased linearly in proportion to the amount of GMA added, and the distribution of zeta potential showed that the minimum amount of GMA that must be added to oven-dried CNF in order to acquire completely cationic CNFs is 0.6%. As the quaternization reaction proceeded, no significant change in low-shear viscosity and average particle size of cationic CNFs was observed. There was also no change in the fiber width of cationic CNFs, because no further fibrillation or fiber cleavage of CNFs occurred as a result of the quaternization reaction. It was concluded that uniform cationic CNF can be produced without any changes in physical properties when the quaternization reaction is carried out by post-treatment using 0.6% GMA.

Efficient entrapment and separation of anionic pollutants from aqueous solutions by sequential combination of cellulose nanofibrils and halloysite nanotubes

The synergistic combination of different nanomaterials for improved performance in environmental applications such as the removal of aqueous micropollutants has attracted increasing interest in recent years. This study demonstrates a novel sequential adsorption–aggregation concept that harnesses tubular halloysite nanotubes (HNTs) and flexible cellulose nanofibrils (CNFs) for the removal of a small, anionic dye molecule, chrome azurol S, from water. Hollow HNTs were first allowed to interact with the aqueous dye solution, after which the dye-loaded colloidal nanotubes were aggregated and separated from the water phase with cationized CNFs. The combination of 25 mg CNFs with 1 g HNTs at pH 7 resulted in efficient removal of dye (80%) and turbidity (~100%) and the removal of dye was further promoted in more acidic conditions (within the pH range of 6–8.5) because of the attractive electrostatic interactions. Cationic CNFs not only enabled the separation of dye-loaded clay particles from the water phase through a rapid aggregation but also participated in dye removal through adsorption (~20%). In comparison with nano-sized HNTs, the dye removal performance of micro-sized and chemically similar kaolin was poor (43%). Given the good availability of both HNTs and CNFs and the low consumption of the more expensive component (i.e., CNFs) in the process, the concept is straightforward, readily applicable, environmentally benign, and potentially cost-effective.

Production of cationic nanofibrils of cellulose by twin-screw extrusion

Cationization of cellulose fibers introduces positives charges and thus decreases the energy consumption to produce cellulose nanofibrils (CNF), improves their quality and confers them antimicrobial properties. In this study, cationic CNF at 17 wt% solid content were produced for the first time using an energy efficient process: the twin-screw extrusion (TSE). The production was compared to the production of enzymatic CNF using the same mechanical treatment and the efficiency of cationization was discussed. CNF produced were characterized using different techniques such as optical microscopy, atomic force microscopy, mechanical properties or transparency and finally classified using the quality index. Despite a slipping effect in the TSE which leads to intact residual fibers, highly transparent CNF with high Young’s modulus (10 GPa) and suitable quality index were obtained consuming only 1100 kW h/t. Activity of cationized CNF to limit bacteria proliferation has even been confirmed.

Anti-oxidative and UV-absorbing biohybrid film of cellulose nanofibrils and tannin extract

Cellulose and tannin are both abundant and biodegradable natural polymers. This study proposes a strategy to construct biohybrid films combining the characteristics of cationic cellulose nanofibrils (CCNFs) and tannin extract for film applications. Multi-functional biohybrid films with anti-oxidative and UV-adsorbing characteristics were successfully fabricated from CCNF and tannin mixtures with different mass ratios. The results indicated that pure CCNF could be endowed with multi-functionality by a small amount of introduced flavonoid-rich tannin extract. By adding 5% (w/w) of extract, CCNF-tannin film achieved good anti-oxidant and UV-shielding ability, and simultaneously obtained ca. 15% improved thermal stability and tensile strength of up to 160 ± 9 MPa. In addition, tannin extract was able to enhance the optical clarity of CCNF film with tailorable appearances. The biohybrid films essentially consisted of renewable materials, and they can potentially be exploited in sustainable applications such as biocomposites and packaging materials.

Cationic cellulose nanofibrils as a green support of palladium nanoparticles: catalyst evaluation in Suzuki reactions

Cationic cellulose nanofibrils (C-CNF) were used as a support for the growth and the immobilization of Pd NPs using PdCl2 as precursor. The ensuing Pd@C-CNF nanocomposite was tested as a catalyst for the Suzuki coupling reactions between aryl halides and arylboronic acid. Several characterization methods including TEM, HR-TEM, XRD, FT-IR, TGA and XPS were used to confirm the immobilization of Pd NPs onto the C-CNF surface and probe the surface composition after interaction with PdCl2. A quasi total coupling of phenyl boronic acid and 4-bromoacetophenone in DMF at 110 °C was found to occur after 4 h when only 0.02% of Pd@C-CNF of catalyst was used. Furthermore, the Pd@C-CNF could be easily recovered and reused for three consecutive Suzuki reaction cycles without significant loss of its catalytic activity and the loaded percent of palladium nanoparticles was maintained.

Understanding heat driven gelation of anionic cellulose nanofibrils: Combining saturation transfer difference (STD) NMR, small angle X-ray scattering (SAXS) and rheology

A novel mechanism of heat-triggered gelation for oxidised cellulose nanofibrils (OCNF) is reported. We demonstrate that a synergistic approach combining rheology, small-angle X-ray scattering (SAXS) and saturation transfer difference NMR (STD NMR) experiments enables a detailed characterisation of gelation at different length scales. OCNF dispersions experience an increase in solid-like behaviour upon heating as evidenced by rheological studies, associated with enhanced interfibrillar interactions measured using SAXS. Interactions result in an increased fibrillar overlap and increased population of confined water molecules monitored by STD NMR. In comparison, cationic cellulose nanofibrils (produced by reaction of cellulose with trimethylglycidylammonium chloride) were found to be heat-unresponsive.

Recyclable deep eutectic solvent for the production of cationic nanocelluloses

Deep eutectic solvents (DESs) are potential green systems that can be used as reagents, extraction agents and reaction media. DESs are often biodegradable, easy to prepare and have low toxicity. In this work, a recyclable DES formed from aminoguanidine hydrochloride and glycerol (AhG) was used as a reaction medium and reagent (aminoguanidine hydrochloride) for the production of cationic nanocelluloses. Under mild conditions (i.e., a reaction time of 10 min at 70 °C), dialdehyde celluloses (DACs) with two different aldehyde contents (2.18 and 3.79 mmol g−1) were cationized by AhG DES to form cationic dialdehyde celluloses (CDACs). Both CDACs achieved a similar high charge density of approximately 1.1 mmol g−1. At 80 °C (for 10 min), a very high cationic charge density of 2.48 mmol g−1 was obtained. The recyclability of AhG DES was demonstrated by reusing it five times without decreasing the reaction efficiency. In particular, due to the low consumption of amoniguanidine hydrochloride, high recycling efficiency could be achieved without the use of any additional chemicals. The cationized celluloses, CDACs, were further mechanically disintegrated to obtain cationic nanocelluloses. According to the initial aldehyde content of DACs, the morphology of the nanocellulose could be tailored to produce highly cationic cellulose nanofibrils (CNFs) or cellulose nanocrystals (CNCs). Transmission electron microscopy confirmed that individual CNFs and CNCs with an average width of 4.6 ± 1.1 nm and 5.7 ± 1.3 nm, respectively, were obtained. Thus, the results presented here indicate that the AhG DES is a promising green and recyclable way of producing cationized CNFs and CNCs.

Polyion complex hydrogels from chemically modified cellulose nanofibrils: Structure-function relationship and potential for controlled and pH-responsive release of doxorubicin

Herein, we report the fabrication of a polyion complex hydrogel from two oppositely charged derivatives of cellulose nanofibrils (CNF). CNF was produced from dissolving pulp through subsequent periodate oxidation, chemical modification, and microfluidization. Three different durations for periodate oxidation (30 min, 120 min, and 180 min) resulted in three different aldehyde contents. Further, two types of chemical modifications were introduced to react with the resulting aldehydes: chlorite oxidation to yield anionic CNF with carboxylic acid groups (DCC) and imination with Girard’s reagent T to yield cationic CNF containing quaternary ammonium groups (CDAC). Functional group contents were assessed using conductometric titration and elemental analysis, while nanofibril morphologies were assessed using atomic force microscopy (AFM). Longer durations of periodate oxidation did not yield different width profile but was found to decrease fibril length. The formation of self-standing hydrogel through mixing of DCC and CDAC dispersions was investigated. Oscillatory rheology was performed to assess the relative strengths of different gels. Self-standing hydrogels were obtained from mixture of DCC180 and CDAC180 dispersions in acetate buffer at pH 4 and 5 at a low concentration of 0.5% w/w that displayed approximately 10-fold increase in storage and loss moduli compared to those of the individual dispersions. Self-standing gels containing doxorubicin (an anticancer drug) displayed pH-responsive release profiles. At physiological pH 7.4, approximately 65% of doxorubicin was retained past a burst release regime, while complete release was observed within 5 days at pH 4. Biocompatibility of DCC180, CDAC180, and their mixture were investigated through quantification of the metabolic activity of NIH3T3 cells in vitro. No significant cytotoxicity was observed at concentrations up to 900 µg/mL. In short, the nanocellulose-based polyion complex hydrogels obtained in this study are promising nature-derived materials for biomedical applications. Statement of SignificanceWe demonstrate that polyion complex can be formed between two cellulose nanofibrils containing complementary charges. To the best of our knowledge, this is the first time that polyion complex formation between complementarily-modified cellulose nanofibrils has been reported, and the results may lead to new ideas on applications of the very promising nanocellulosic materials. The polyion complex helps form a self-standing network that is demonstrated to provide controlled and pH-responsive release of doxorubicin. Particularly, the report explores the connection between the physical properties of functionalizable nanocellulosic materials and their potential biomedical applications. Thus, the study encompasses several broad fields of materials science and engineering, chemistry, and biomedical science that we believe is in line with the readers’ interests.

Reinforcement Effects from Nanodiamond in Cellulose Nanofibril Films.

Although research on nanopaper structures from cellulose nanofibrils (CNFs) is well established, the mechanical behavior is not well understood, especially not when CNF is combined with hard nanoparticles. Cationic CNF (Q-CNF) was prepared and successfully decorated by anionic nanodiamond (ND) nanoparticles in hydrocolloidal form. The Q-CNF/ND nanocomposites were filtered from a hydrocolloid and dried. Unlike many other carbon nanocomposites, the Q-CNF/ND nanocomposites were optically transparent. Reinforcement effects from the nanodiamond were remarkable, such as Young's modulus (9.8 → 16.6 GPa) and tensile strength (209.5 → 277.5 MPa) at a content of only 1.9% v/v of ND, and the reinforcement mechanisms are discussed. Strong effects on CNF network deformation mechanisms were revealed by loading-unloading experiments. Scratch hardness also increased strongly with increased addition of ND.

Ultrastrong and flame-resistant freestanding films from nanocelluloses, self-assembled using a layer-by-layer approach

Nanosized cellulose nanofibrils (CNF) prepared from phosphorylated pulp fibers (P-CNF) are combined with CNF prepared from aminated fibers (cationic CNF) through a layer-by-layer (LbL) assembly to prepare a freestanding, transparent all-cellulose film. It is shown that the thermal stability and flame-retardant properties of the all CNF film are significantly improved when phosphorylated CNF is combined with cationic fibrils in an LbL assembled structure. The freestanding films also show a tensile strength of 160MPa and a Young's modulus of 9GPa, placing it among strongest freestanding LbL films fabricated so far, showing large promise for the use of these types of ultrathin films in advanced applications. The LbL build-up of the cationic CNF/P-CNF multilayer film is carefully studied by quartz crystal microbalance with dissipation (QCM-D) and atomic force microscopy (AFM). Hydrophobized silicon substrates are used for the LbL deposition and it is shown that the (cationic CNF/P-CNF)300 film, 2.3μm thick, can be easily detached from the substrate using tweezers. The thermal stability, combustion behavior and mechanical properties of the films are further studied by thermogravimetric analysis, combustion and tensile tests respectively.