Cationic Cellulose Nanocrystals Research Articles

Apple Pomace-Derived Cationic Cellulose Nanocrystals for PFAS Removal from Contaminated Water

Apple Pomace-Derived Cationic Cellulose Nanocrystals for PFAS Removal from Contaminated Water

Cr(VI) removal from fiber cement process waters: a techno-economic assessment

Accumulation of Cr(VI) in industrial fiber cement process water may compromise the product quality and cause health issues. Furthermore, it must be removed from process waters to avoid environmental risks. For this purpose, this work evaluates the potential of advanced nanocelluloses and compare it with the efficiency of conventional adsorbents. The analysis of the industrial process allowed to perform a techno-economic assessment on the long-scale implementation. Among the studied adsorbents, granular (GAC) and powdered activated carbons (PAC) and cationic cellulose nanocrystals (CCNCs) removed >99 % of Cr(VI) from real waters. CCNCs efficiency is linked to their large number of cationic groups. The CCNCs reached adsorption capacities up to 90 times higher than GAC in just 5 min by applying an order of magnitude lower dosages. The cost analysis of GAC adsorption revealed that the ultrafiltration and reverse osmosis treatment of backwashing water costed up to 9.5 US$·m−3. To minimize the generated hazardous wastes, the application of evaporation or a second UF and RO treatments reduced costs in 66 % and 71 %, respectively. The use of high-performance membranes and achieving discounts on GAC purchase, 1.6 US$·m−3 would be reached. This suggests that the CCNCs competitive price would be below 22 US$·kg−1.

Understanding the versatile roles of cellulose nanocrystals in α-amylase immobilization, starch hydrolysis, colloidal stability and printability towards advanced starch based bio-latex performance

Recently starch based bio-latexes are facing serious bottlenecks in their preparation and applications especially at the aspects of high concentration, high colloidal stability and high rheological performance. Starch paste for bio-latex production at high concentration would be prone to retrogradation and inevitably deteriorate its performance. The excessive and uncontrollable α-amylase hydrolysis behavior of starch granules at low concentration below 30 wt% could severely affect the strengthening or binding ability of bio-latex. Herein, this study proposes a practical and effective strategy by using cationic cellulose nanocrystals (CCNC) as versatile carriers of α-amylase for the preparation of starch based bio-latex (SBL) to improve starch hydrolysis efficiency even at 50 wt% concentration. CCNC immobilized α-amylase (CCNC/E) can effectively regulate starch hydrolysis behavior with controllable amylose/ amylopectin molecular weight/ distribution for enhanced colloidal stability and viscoelasticity. Furthermore, the multifunctional roles of CCNC as excellent dispersants, nano-fillers and enhancers within starch colloids could impart SBL excellent rheological property and printability in pigmented coating and printing performance, by improving the coating surface, higher printing density/ picking velocity, and lower dot gain phenomenon, compared with the control latex samples. This study proposes a promising and practical approach for efficient production of 50 wt% starch based bio-latex with advanced performance and further valorizes the cellulose nanocrystals in the starch based biomaterials applications.

Cationic cellulose nanocrystals as sustainable green material for multi biological applications via ξ potential

The present study aims to disclose the activity of cationic cellulose nanocrystals (CNCs) as a promising multifunctional green nanomaterial with applications in biological aspects. The basic reason behind multifunctional behavior is zeta potential and size distribution of nano biopolymers; exhibit a remarkable physical and biological activity compared to normal molecules. The preliminary characterized studied using absorption spectral analysis showed strong absorption peak indicating that spectrum curves can be screen by UV spectra at wavelength range 200–400nm. Ultrastructural studies (SEM-EDS and TEM), manifest that CNCs are elliptical particles in shape. Also, TEM show CNCs are the ideal illustration of zero-dimensional (0-D) NPs, less than 5.1 nm in diameter with Cationic charge and similar results in size distribution by TEM. Nonetheless, developed as antioxidant activity IC50 was 1467 ± 25.9 µg/mL, antimicrobial activity tested G−ve strains, but not affected on tested G+ve strains and tested fungi. Evaluating toxicity effect of cationic CNCs against human blood erythrocytes (RBCs) and Lymphocyte Proliferation and the end point evaluate by comet assay, which proven no cytotoxic effect. Also, a high dose 500 µg/mL of CNCs highly significant (p < 0.05) reduction in cell viability of Caco-2 cancer cells after 24 h. incubation time, whereas the IC50 was 1884 ± 19.46 µg/mL. Moreover, genotoxic assay indicates Caco-2 cells cause apoptosis with no fragmentation in DNA. Undoubtedly, the obtained results brought about by the interaction of layers carrying opposing charges. Additionally, there is a balance between hydrophilic contact and electrostatic attraction. That emphasizes how the cationic CNCs have excellent potential for use as antioxidants, antimicrobials, and anticancer agents.

Cationic CNC-stabilized Pickering emulsions of linseed oil for hydrophobic coatings.

Coating paper with polymers is an efficient way of awarding it with gas-tightness and moisture protection in food packaging applications, but it impedes the recyclability of the both paper and polymer. Cellulose nanocrystals were found to be excellent gas barrier materials, but their hydrophilicity forbids their straightforward application as protective coatings. To introduce hydrophobicity into a CNC coating, this work exploited the capability of cationic CNCs isolated in a one-step treatment with a eutectic medium to stabilize Pickering emulsions in order to include a natural drying oil in a dense layer of CNCs. This way, a hydrophobic coating with improved water vapor barrier properties was achieved.

Hexavalent Chromium Removal from Industrial Wastewater by Adsorption and Reduction onto Cationic Cellulose Nanocrystals

Cationic cellulose nanocrystals (CCNC) are lignocellulosic bio-nanomaterials that present large, specific areas rich with active surface cationic groups. This study shows the adsorption removal of hexavalent chromium (Cr(VI)) from industrial wastewaters by the CCNC. The CCNC were synthetized through periodate oxidation and Girard's reagent-T cationization. The high value of CCNCs cationic groups and anionic demand reveal probable nanocrystal-Cr(VI) attraction. Adsorption was performed with synthetic Cr(VI) water at different pH, dosage, Cr(VI) concentration and temperature. Fast removal of Cr(VI) was found while operating at pH 3 and 100 mg·L-1 of dosage. Nevertheless, a first slower complete removal of chromium was achieved by a lower CCNC dosage (40 mg·L-1). Cr(VI) was fully converted by CCNC into less-toxic trivalent species, kept mainly attached to the material surface. The maximum adsorption capacity was 44 mg·g-1. Two mechanisms were found for low chromium concentrations (Pseudo-first and pseudo-second kinetic models and continuous growth multi-step intraparticle) and for high concentrations (Elovich model and sequential fast growth-plateau-slow growth intraparticle steps). The Sips model was the best-fitting isotherm. Isotherm thermodynamic analysis indicated a dominant physical sorption. The Arrhenius equation revealed an activation energy between physical and chemical adsorption. CCNC application at selected conditions in industrial wastewater achieved a legal discharge limit of 40 min.

Injectable Hydrogels Based on Inter-Polyelectrolyte Interactions between Hyaluronic Acid, Gelatin, and Cationic Cellulose Nanocrystals.

The present work dealt with the development of physically cross-linked injectable hydrogels with potential applications in tissue engineering. The hydrogels were composed of a ternary mixture of a polyanion and a polyampholyte, hyaluronic acid (HA) and gelatin, respectively, bridged by cationic cellulose nanocrystals (cCNCs). A 3D network is formed by employing attractive electrostatic interactions and hydrogen bonding between these components under physiological conditions. The hydrogels demonstrated low viscosity at high stresses, enabling easy injection, structural stability at low stresses (<15 Pa), and nearly complete structure recovery within several minutes. Increasing the cCNC content (>3%) reduced hydrogel swelling and decelerated the degradation in phosphate-buffered saline as compared to that in pure HA and HA-gelatin samples. Biological evaluation of the hydrogel elutions showed excellent cell viability. The proliferation of fibroblasts exposed to elutions of hydrogels with 5% cCNCs reached ∼200% compared to that in the positive control after 11 days. Considering these results, the prepared hydrogels hold great potential in biomedical applications, such as injectable dermal fillers, 3D bioprintable inks, or 3D scaffolds to support and promote soft tissue regeneration.

Exploiting flocculation and membrane filtration synergies for highly energy-efficient, high-yield microalgae harvesting

High energy consumption during harvesting is one of the main bottlenecks for sustainable microalgae production. Membranes can efficiently separate microalgae from liquids with low energy consumption, but membrane fouling remains an important issue. Flocculation prior to membrane filtration can increase membrane fluxes and decrease fouling, thus offering a low-cost and efficient solution to harvest microalgae. Biobased cationic cellulose nanocrystals were successfully used as flocculants for microalgae and were effective over a wide pH-range and for both freshwater and marine microalgae. Such flocculation was for the first time combined with vibration-assisted filtration using a charged, surface patterned membrane, enabling operation at very high flux (95 L/m2 h) using a vibration frequency of only 1 Hz, and even under sub-optimal flocculation conditions. Intermittent vibration decreased energy consumption further while keeping excellent filtration performance to finally achieve a record-low energy consumption for the membrane filtration of only 6.7 Wh/m3, which is >25-times lower than that of normal membrane filtration. Interaction forces revealed that increasing particle size through flocculation prior to membrane filtration can significantly prevent microalgae attachment on the vibrating membrane surface. This work opens a new direction for sustainable microalgae harvesting with an ultra-low energy consumption, combined with a very high microalgae recovery, reduced use of chemicals, and lower membrane investment cost.

Preparation and stabilization of Pickering emulsions by cationic cellulose nanocrystals synthesized from deep eutectic solvent

In this work, short rod-like cationic cellulose nanocrystals (AH-CNCs) were prepared by sodium periodate oxidation combined with deep eutectic solvent method. The effects of different content AH-CNCs on the properties of the emulsion were studied. With the increase of AH-CNCs content, the diameter of emulsion droplets decreased and the stabilization time prolonged. The electrostatic attraction between the negative charge accumulated at the oil-water interface and AH-CNCs with positive charge improved the stability of the emulsion. Then, the rheological properties showed the interaction of nanocellulose in the continuous phase increased the viscosity of the emulsion. In addition, the droplet diameter of emulsion of 120 s was smaller at different ultrasonic time, the particle size distribution of emulsion changed from monodisperse to polydisperse with the increase of oil volume, the salt concentration had little effect on the droplet size of emulsion, and the preparation of emulsion under acidic conditions was more stable.

Size exclusion and affinity-based removal of nanoparticles with electrospun cellulose acetate membranes infused with functionalized cellulose nanocrystals

Membrane filtration and affinity-based adsorption are the two most used strategies in separation technologies. Here, µm-thick multifunctional and sustainable composite membranes of electrospun cellulose acetate (CA) infused with functionalized, anionic, and cationic cellulose nanocrystals (CNCs) with enhanced wettability, tensile strength, and excellent retention capacities were designed. CNCs could uniformly impregnate into the three-dimensional CA network to effectively improve its properties. The impregnation of cationic CNCs at 0.5 wt% concentration drastically increased the tensile strength (1669%) while maintaining high permeation flux of 9400 Lm-2h−1 which is remarkable with cellulose modified electrospun membranes. The membranes infused with anionic CNCs exhibited a particle retention efficiency of 96% for 500 nm and 77% for 100 nm latex beads whilst the cationic CNC membranes exhibited a combined particle retention strategy using selectivity and size exclusion with a retention of >81% with 100 nm latex beads and 80% with ∼50 nm silver nanoparticles. We envision that the developed multifunctional membranes can be utilized for affinity-based and size-exclusion filtration to selectively trap bacteria or substances of biological significance.

Multifunctional Nanocellulose/Carbon Nanotube Composite Aerogels for High-Efficiency Electromagnetic Interference Shielding

Bio-based specialized components have emerged as a promising trend to limit the use of petroleum derivatives. Conversely, the current use of electronic systems has conditioned the emission of electromagnetic waves that interfere with high-precision devices and harm human health. Thus, robust, ultralight, and conductive nanocellulose-based aerogels paired with carbon nanotubes appear as an electromagnetic interference (EMI) shielding biomaterial to reduce the dispersion of microwaves emitted or received from a device. This study proposes a reliable aerogel system to deflect radiation by integrating TEMPO-oxidized cellulose nanofibrils, cationic cellulose nanocrystals, and sodium alginate, with carbon nanotubes at various concentrations. After inducing gelation, the aerogels were obtained by freeze drying. According to zeta potential and FTIR analysis data of nanocellulose, the aerogel frame was induced by electrostatic attraction and hydrogen bonds between the cellulosic matrix and the nanofillers. Finally, lightweight (density < 0.075 g/cm3), highly porous (porosity > 95.47%), conductive (up to 26.2 S/m), mechanically resistant, and EMI-protective aerogels were obtained, proving their potential to be used as green and lightweight shielding elements against electromagnetic radiation.

Changes on Redox Status and Organelle Dynamics Caused by Cationic Cellulose Nanocrystals (CNCs)

Changes on Redox Status and Organelle Dynamics Caused by Cationic Cellulose Nanocrystals (CNCs)

Time-dependent Redox Response Induced by Engineered Cationic Cellulose Nanocrystals (CNCs)

Time-dependent Redox Response Induced by Engineered Cationic Cellulose Nanocrystals (CNCs)

Vascular and Blood Compatibility of Engineered Cationic Cellulose Nanocrystals in Cell-Based Assays.

An emerging interest regarding nanoparticles (NPs) concerns their potential immunomodulatory and pro-inflammatory activities, as well as their impact in the circulatory system. These biological activities of NPs can be related to the intensity and type of the responses, which can raise concerns about adverse side effects and limit the biomedical applicability of these nanomaterials. Therefore, the purpose of this study was to investigate the impact of a library of cationic cellulose nanocrystals (CNCs) in the human blood and endothelial cells using cell-based assays. First, we evaluated whether the cationic CNCs would cause hemolysis and aggregation or alteration on the morphology of red blood cells (RBC). We observed that although these nanomaterials did not alter RBC morphology or cause aggregation, at 24 h exposure, a mild hemolysis was detected mainly with unmodified CNCs. Then, we analyzed the effect of various concentrations of CNCs on the cell viability of human umbilical vein endothelial cells (HUVECs) in a time-dependent manner. None of the cationic CNCs caused a dose-response decrease in the cell viability of HUVEC at 24 h or 48 h of exposure. The findings of this study, together with the immunomodulatory properties of these cationic CNCs previously published, support the development of engineered cationic CNCs for biomedical applications, in particular as vaccine nanoadjuvants.

Layer-by-layer assembly of cationic guar gum, cellulose nanocrystals and hydroxypropyl methylcellulose based multilayered composite films

Eco-friendly sustainable materials provide an appealing template to replace contemporary synthetic-nonrenewable resource-based materials while maintaining the acceptable material properties to meet the performance requirements. Here, a layer-by-layer (LBL) self-assembly technique was used for fabricating multilayer composite films using all bio-based polymers/polysaccharides, i.e. cationic guar gum (CGg), carboxylated cellulose nanocrystals (cCNCs) and hydroxypropyl methylcellulose (HPMC). A five layered composite film was fabricated by depositing polymeric layers as follows: CGg→cCNCs→HPMC→cCNCs→CGg. The structural analysis of (CGg/cCNCs/HPMC)5 L multilayered composite films indicated the existence of electrostatic interaction as well as H-bonding between polymeric layers that resulted in homogenous, dense and compact film surface with improved smoothness and strength properties. As compared to pure CGg film, the (CGg/cCNCs/HPMC)5 L multilayered composite films showed improved tensile strength (84.8 % increment) and modulus (29.19 % improvement). Importantly, the deposition of HPMC layer contributed in achieving multilayer composite films with more flexible behavior (46.55 % improvement in elongation at break). Furthermore, owing to the high transparency (89.5 % transmittance), appreciable gas and oil barrier performance and resistance to various solvents (e.g. acetone, THF and DMAc), these multilayer films are promising candidates for various applications including renewable/sustainable packaging materials.

Water-resistant nanopaper with tunable water barrier and mechanical properties from assembled complexes of oppositely charged cellulosic nanomaterials

Owing to the intrinsic hydrophilicity of nanocellulose, films and nanopapers prepared from cellulosic nanomaterials exhibit weak mechanical strength when exposed to high-moisture conditions. In this study, an approach for designing a water resistant, assembled nanopaper through controlled and irreversible aqueous complexation of oppositely charged cellulose nanoconstituents, i.e., cationic cellulose nanocrystals (AH-CNC) and anionic cellulose nanofibers (TO-CNF), is proposed. The fabrication process and features of the nanopaper can be adjusted by altering of the AH-CNC/TO-CNF ratio. For example, the draining time during the filtration of a nanopaper decreased dramatically (480–10 min) when the dosage of nanocelluloses resulted in charge compensation. This dosage also reduced the swelling of the nanopaper. After all charged groups were neutralized, a nanopaper with a wet strength of 11 ± 3 MPa was obtained when immersed in water for 24 h. Furthermore, the electrostatic interaction between the charged nano-entities enhanced the mechanical properties of the nanopaper in dry state (the maximum of tensile strength was 174 ± 3 MPa) and resulted in improved water barrier properties (water vapor transmission rate of 1683 g μm m−2 d−1). This straightforward method based on simply aqueous mixing of two oppositely charged nanomaterials may provide a new pathway for the fabrication of various functionalized films and sheets with advanced characteristics from different type of charged nanoparticles and colloids.

Cationic cellulose nanocrystals for fast, efficient and selective heparin recovery

• Green and renewable cellulose nanocrystals were utilized for heparin recovery. • Polycationic side chains were grafted from cellulose nanocrystals. • Instantaneous heparin-capture in biological conditions reduced recovery efforts. • Selective heparin-recovery was achieved via salt concentration or pH adjustment. • Significantly higher heparin-recovery ability than Amberlite was achieved. Heparin is one of the most important anticoagulant agents used in clinical applications. Commercial heparin production includes an isolation from mucosa and an additional enrichment step by cationic resins. However, this process remains time-consuming while heparin is obtained in very low concentrations with the presence of macromolecular impurities, such as proteins. Therefore, an alternative with a fast, efficient and selective heparin-recovery performance is highly desirable. In this work, we utilized a biomass-derived cellulose nanocrystal colloid conjugated with cationic polyelectrolytes for heparin recovery. The high specific surface area and brush-like structure significantly increased the heparin-capture speed and efficiency under physiologically relevant conditions, which were demonstrated by the methylene blue binding assay and quartz crystal microbalance measurement. We also found that a selective heparin capture can be realized via adjusting salt concentration or pH. Finally, we showed that after several recycle rounds, the heparin-recovery ability of the cationic nanocrystals was largely retained and the majority of active heparin dose was recovered, showing a significantly higher heparin-recovery performance than the commercial Amberlite IRA-900 and demonstrating its applicability from an economic perspective. Therefore, the reported cellulose nanocrystal-polymer conjugate represents a promising candidate for a green and efficient heparin recovery.

Cationic Cellulose Nanocrystals-Based Nanocomposite Hydrogels: Achieving 3D Printable Capacitive Sensors with High Transparency and Mechanical Strength.

Hydrogel ionotronics are intriguing soft materials that have been applied in wearable electronics and artificial muscles. These applications often require the hydrogels to be tough, transparent, and 3D printable. Renewable materials like cellulose nanocrystals (CNCs) with tunable surface chemistry provide a means to prepare tough nanocomposite hydrogels. Here, we designed ink for 3D printable sensors with cationic cellulose nanocrystals (CCNCs) and zwitterionic hydrogels. CCNCs were first dispersed in an aqueous solution of monomers to prepare the ink with a reversible physical network. Subsequent photopolymerization and the introduction of Al3+ ion led to strong hydrogels with multiple physical cross-links. When compared to the hydrogels using conventional CNCs, CCNCs formed a stronger physical network in water that greatly reduced the concentration of nanocrystals needed for reinforcing and 3D printing. In addition, the low concentration of nanofillers enhanced the transparency of the hydrogels for wearable electronics. We then assembled the CCNC-reinforced nanocomposite hydrogels with stretchable dielectrics into capacitive sensors for the monitoring of various human activities. 3D printing further enabled a facile design of tactile sensors with enhanced sensitivity. By harnessing the surface chemistry of the nanocrystals, our nanocomposite hydrogels simultaneously achieved good mechanical strength, high transparency, and 3D printability.

Toward Biodegradable Electronics: Ionic Diodes Based on a Cellulose Nanocrystal-Agarose Hydrogel.

Bioderived cellulose nanocrystals (CNCs) are used to create light, flexible, biocompatible, and biodegradable electronic devices. Herein, surface modification of cellulose nanocrystals was employed to fabricate cationic and anionic CNCs. Subsequently, we demonstrated rectification behavior from a fixed junction between two agarose hydrogels doped with cationic and anionic cellulose nanocrystals. The current rectification ratio reaches 70 reproducibly, which is significantly higher than that for analogous diodes generated with microfibrillated cellulose (∼15) and the first polyelectrolyte gel diode (∼40). The current-voltage characteristics of the CNC-hydrogel diode are influenced by concentration, gel thickness, scanning frequency, and applied voltage. The high surface area of CNC resulted in high charge density after surface modification, which in turn resulted in good rectification behavior from only small amounts of dopant material.

Adsorptivity of cationic cellulose nanocrystals for phosphate and its application in hyperphosphatemia therapy

Nanocellulose has gained much attention because of its excellent properties. Cationic cellulose nanocrystals (cCNC) shows good adsorptivity toward negative ions and molecules. Phosphate binders are most used to treat hyperphosphatemia and it is significant to develop its alternatives with high specific and low cost in the clinic. Herein, we prepared cCNC and characterized it by FTIR, TEM, dynamic light scattering, and viscosity method. We simulated the binding process of cationic cellulose for phosphate and used it as phosphate binder for hyperphosphatemia therapy to study the phosphate binding effect and evaluate the oral toxicity. Cationic cellulose improved the conditions of mice models and efficiently decreased the level of phosphate in the serum. cCNC had a better binding effect than cationic microcrystalline cellulose both in vitro and in vivo. cCNC could be used as alternatives to phosphate binder for therapy of chronic renal failure and hyperphosphatemia.