Zwitterionic Cellulose Research Articles

Zwitterionic Cellulose-Based Polymer Electrolyte Enabled by Aqueous Solution Casting for High-Performance Solid-State Batteries.

Polyethylene oxide (PEO)-based solid-state batteries hold great promise as the next-generation batteries with high energy density and high safety. However, PEO-based electrolytes encounter certain limitations, including inferior ionic conductivity, low Li+ transference number, and poor mechanical strength. Herein, we aim to simultaneously address these issues by utilizing one-dimensional zwitterionic cellulose nanofiber (ZCNF) as fillers for PEO-based electrolytes using a simple aqueous solution casting method. Multiple characterizations and theoretical calculations demonstrate that the unique zwitterionic structure imparts ZCNF with various functions, such as disrupting PEO crystallization, dissociating lithium salts, anchoring anions through cationic groups, accelerating Li+ migration by anionic groups, as well as its inherent reinforcement effect. As a result, the prepared PL-ZCNF electrolyte exhibits remarkable ionic conductivity (5.37×10-4 S cm-1) and Li+ transference number (0.62) at 60 °C without sacrificing mechanical strength (9.2 MPa), together with high critical current density of 1.1 mA cm-2. Attributed to these merits of PL-ZCNF, the LiFePO4|PL-ZCNF|Li solid-state full-cell delivers exceptional rate capability and cycling performance (900 cycles at 5 C). Notably, the assembled pouch-cell can maintain steady operation over 1000 cycles with an impressive 93.7 % capacity retention at 0.5 C and 60 °C, highlighting the great potential of PL-ZCNF for practical applications.

Zwitterionic Cellulose‐Based Polymer Electrolyte Enabled by Aqueous Solution Casting for High‐Performance Solid‐State Batteries

AbstractPolyethylene oxide (PEO)‐based solid‐state batteries hold great promise as the next‐generation batteries with high energy density and high safety. However, PEO‐based electrolytes encounter certain limitations, including inferior ionic conductivity, low Li+ transference number, and poor mechanical strength. Herein, we aim to simultaneously address these issues by utilizing one‐dimensional zwitterionic cellulose nanofiber (ZCNF) as fillers for PEO‐based electrolytes using a simple aqueous solution casting method. Multiple characterizations and theoretical calculations demonstrate that the unique zwitterionic structure imparts ZCNF with various functions, such as disrupting PEO crystallization, dissociating lithium salts, anchoring anions through cationic groups, accelerating Li+ migration by anionic groups, as well as its inherent reinforcement effect. As a result, the prepared PL‐ZCNF electrolyte exhibits remarkable ionic conductivity (5.37×10−4 S cm−1) and Li+ transference number (0.62) at 60 °C without sacrificing mechanical strength (9.2 MPa), together with high critical current density of 1.1 mA cm−2. Attributed to these merits of PL‐ZCNF, the LiFePO4|PL‐ZCNF|Li solid‐state full‐cell delivers exceptional rate capability and cycling performance (900 cycles at 5 C). Notably, the assembled pouch‐cell can maintain steady operation over 1000 cycles with an impressive 93.7 % capacity retention at 0.5 C and 60 °C, highlighting the great potential of PL‐ZCNF for practical applications.

Zwitterionic cellulose nanofibers-based hydrogels with high toughness, ionic conductivity, and healable capability in cryogenic environments

Extreme environmental conditions often lead to irreversible structural failure and functional degradation in hydrogels, limiting their service life and applicability. Achieving high toughness, self-healing, and ionic conductivity in cryogenic environments is vital to broaden their applications. Herein, we present a novel approach to simultaneously enhance the toughness, self-healing, and ionic conductivity of hydrogels, via inducing non-freezable water within the zwitterionic cellulose-based hydrogel skeleton. This approach enables resulting hydrogel to achieve an exceptional toughness of 10.8 MJ m−3, rapid self-healing capability (98.9 % in 30 min), and high ionic conductivity (2.9 S m−1), even when subjected to −40 °C, superior to the state-of-the-art hydrogels. Mechanism analyses reveal that a significant amount of non-freezable water with robust electrostatic interactions is formed within zwitterionic cellulose nanofibers-modified polyurethane molecular networks, imparting superior freezing tolerance and versatility to the hydrogel. Importantly, this strategy harnesses the non-freezable water molecular state of the zwitterionic cellulose nanofibers network, eliminating the need for additional antifreeze and organic solvents. Furthermore, the dynamic Zn coordination within these supramolecular molecule chains enhances interfacial interactions, thereby promoting rapid subzero self-healing and exceptional mechanical strength. Demonstrating its potential, this hydrogel can be used in smart laminated materials, such as aircraft windshields.

Novel in-situ zwitterionization of carbon quantum dots on membrane surface for oil/water separation

Industrial growth led to an increase in the release of hazardous oily wastewater that seriously threatens human health and the ecosystem. Developing polymeric membranes for treating such wastewater has garnered significant attention, yet their fouling resistance remains a challenge. In this study, an anti-fouling zwitterionic cellulose acetate (CA) membrane, called ZQDs-g-CA, was fabricated by grafting carbon quantum dots (CQDs) on the surface of the CA membrane, followed by zwitterionization of CQDs (Zwitterionic carbon quantum dots, ZQDs). The grafting of ZQDs increased the hydrophilicity and oleophobicity of the membrane due to the hydrophilic functional groups present in the nanomaterial. The surface roughness was increased, allowing a greater surface area for contact between water molecules and the membrane. The modified CA membrane demonstrated excellent water flux (602.2 ± 30.2 L m−1 h−1 bar−1 (LMHB)) and oil/water emulsion separation performance, with a permeation flux of 426.1 ± 9.6 LMHB and oil rejection of 99.4 %. Additionally, the anti-fouling tests demonstrated remarkable performance with more than 96 % flux recovery ratio (FRR), 30.35 % reversible fouling ratio (Rr), and 3.05 % irreversible fouling ratio (Rir). The results showed that the in-situ ZQDs on the CA membrane exceeded the 96 % rejection rate for different oil/water emulsions. ZQDs were successfully applied on the CA membrane, which would provide a reference for the application of ZQDs-g-CA in oil/water separation.

Preparation of zwitterionic cellulose nanofibers with betaine-oxalic acid DES and its multiple performance characteristics

Preparation of zwitterionic cellulose nanofibers with betaine-oxalic acid DES and its multiple performance characteristics

Lysine functionalized cellulose for a zwitterion-based immobilization of laccase enzyme and removal of commercial dyes from aqueous media

The zwitterion functionalization of cellulose with lysine was achieved in a two-step synthesis. The cellulose modification in each step of the synthesis was corroborated by FTIR and solid state 13C NMR spectroscopy. The zwitterionic character in the modified cellulose was determined by its isoelectric point using a titration curve vs. pH. The dye adsorption performance of the modified cellulose was evaluated with malachite green and indigo carmine solutions. Cellulose modification increases laccase immobilization almost 10-fold compared to unmodified cellulose. Ionic and hydrophobic interactions are involved in immobilization, stabilizing laccase and the zwitterionic cellulose system. A novel theoretical approach of this immobilization is also proposed involving the interaction energies of the specific ionic moieties and supported by hydrophobic interactions shared between the enzyme and the zwitterionic cellulose interface. Moreover, immobilization did not affect the bioactivity of the enzyme, but on the contrary increased it by 29%. The laccase and zwitterionic cellulose system (Laccase-Lys-Cel) was tested against malachite green and indigo carmine in a 96-h experiment. The best removal results of about 93% from aqueous solution were observed for indigo carmine after 1 h and 99% after 72 h. Finally, Laccase-Lys-Cel combines two mechanisms: (1) dye adsorption in the early stages and (2) final dye degradation by the enzyme.

Synthesis of Polyanionic Cellulose Carbamates by Homogeneous Aminolysis in an Ionic Liquid/DMF Medium.

Polyanionic cellulose carbamates were synthesized by rapid and efficient homogeneous aminolysis of cellulose carbonate half-esters in an ionic liquid/DMF medium. Cellulose bis-2,3-O-(3,5-dimethylphenyl carbamate), as a model compound, reacted with different chloroformates to cellulose carbonates. These intermediates were subjected to aminolysis, for which both the reactivity of different chloroformates towards C6-OH and the reactivity/suitability of the respective carbonate half-ester in the aminolysis were comprehensively studied. Phenyl chloroformate and 4-chlorophenyl chloroformate readily reacted with C6-OH of the model cellulose derivative, while 4-nitrophenyl chloroformate did not. The intermediate 4-chlorophenyl carbonate derivative with the highest DS (1.05) was then used to evaluate different aminolysis pathways, applying three different amines (propargyl amine, β-alanine, and taurine) as reactants. The latter two zwitterionic compounds are only sparingly soluble in pure DMF as the typical reaction medium for aminolysis; therefore, several alternative procedures were suggested, carefully evaluated, and critically compared. Solubility problems with β-alanine and taurine were overcome by the binary solvent system DMF/[EMIM]OAc (1:1, v/v), which was shown to be a promising medium for rapid and efficient homogeneous aminolysis and for the preparation of the corresponding cellulose carbamate derivatives or other compounds that are not accessible by conventional isocyanate chemistry. The zwitterionic cellulose carbamate derivatives presented in this work could be promising chiral cation exchangers for HPLC enantiomer separations.

Use of a new zwitterionic cellulose derivative for removal of crystal violet and orange II from aqueous solutions

This study describes the synthesis of a new bioadsorbent with zwitterionic characteristics and its successful application for removal of a cationic dye (crystal violet, CV) and an anionic dye (orange II, OII) from single component aqueous systems. The new bi-functionalized cellulose derivative (MC3) was produced by chemical modification of cellulose with succinic anhydride and choline chloride to introduce carboxylic and quaternary ammonium functional groups on the cellulose surface. MC3 was characterized by several wet chemical and spectroscopic methods. The effects of solution pH, contact time, and initial solute concentration on removal of CV and OII by MC3 were investigated. Studies of the desorption and re-adsorption of the dyes were also carried out. The isotherms for adsorption of CV and OII on MC3 were satisfactorily fitted using the Konda and Langmuir models. MC3 showed experimental maximum adsorption capacities of 2403 mg g-1 for CV and 201 mg g-1 for OII. The desorption and re-adsorption results showed that MC3 could be reused in successive adsorption cycles, which is essential for minimizing process costs and waste generation. The findings showed that MC3 is a versatile biosorbent capable of efficiently removing both cationic and anionic dyes.

Zwitterionic cellulose as a promising sorbent for anionic and cationic dyes

This work aimed to develop zwitterionic cellulose with a versatile potential for removing anionic and cationic dyes. A grafting degree of 22% in a 3:2 ratio of the anionic and cationic groups was determined by elemental analysis. Spectroscopic characterization by carbon 13 Nuclear Magnetic Resonance (13C NMR) confirmed the zwitterionic functionalization of cellulose. Removal tests showed that zwitterionic cellulose could interact with different dyes (Congo red, Crystal violet, Mordant blue 9, Malachite green, Xylidine ponceau, and Reactive black 5), achieving from 2 to 14-fold of removal at tested conditions.

Synthetic Phosphoethanolamine Cellobiose Promotes Escherichia coli Biofilm Formation and Congo Red Binding.

Urinary tract infections (UTIs) are caused by bacteria growing in complex, multicellular enclosed aggregates known as biofilms. Recently, a zwitterionic cellulose derivative produced in Escherichia coli (E. coli) was determined to play an important role in the formation and assembly of biofilms. In order to produce a minimal, yet structurally defined tool compound to probe the biology of the naturally occurring polymer, we have synthesized a zwitterionic phosphoethanolamine cellobiose (pEtN cellobiose) and evaluated its biofilm activity in the Gram-negative bacterium E. coli, a pathogen implicated in the pathogenesis of UTIs. The impact of synthetic pEtN cellobiose on biofilm formation was examined via colorimetric assays which revealed an increase in cellular adhesion to an abiotic substrate compared to untreated samples. Additionally, Congo red binding assays indicate that culturing E. coli in the presence of pEtN cellobiose enhances Congo Red binding to bacterial cells. These results reveal new opportunities to study the impact glycopolymers have on cellular adhesion in Gram-negative pathogens.

A Simplified Method of Synthesis to Obtain Zwitterionic Cellulose under Mild Conditions with Active Ionic Moieties.

A simplified procedure to synthesize zwitterionic cellulose by means of N-protected aspartic anhydride under mild conditions was developed. The preparation of modified cellulose samples was carried out under heterogeneous, aqueous conditions by reacting NH4OH-activated cellulose with aspartic anhydrides N-protected with trifluoroacetyl (TFAc) and carbobenzyloxy (Cbz). Modified cellulose samples Cel-Asp-N-TFAc and Cel-Asp-N-Cbz were characterized by Fourier Transform Infrared (FTIR) and 13C solid state Nuclear Magnetic Resonance (NMR) spectroscopy. The functionalization degree of each cellulose sample was determined by the 13C NMR signal integration values corresponding to the cellulose C1 vs. the Cα of the aspartate residue and corroborated by elemental analysis. In agreement, both analytical methods averaged a grafting degree of 20% for Cel-Asp-N-TFAc and 16% for Cel-Asp-N-Cbz. Conveniently, Cel-Asp-N-TFAc was concomitantly partially N-deprotected (65%) as determined by the ninhydrin method. The zwitterion character of this sample was confirmed by a potentiometric titration curve and the availability of these amino acid residues on the cellulose was inspected by adsorption kinetics method with a 100 mg L−1 cotton blue dye solution. In addition, the synthesis reported in the present work involves environmentally related advantages over previous methodologies developed in our group concerning to zwitterionic cellulose preparation.

Zwitterionic Cellulose Nanofibrils with High Salt Sensitivity and Tolerance.

To improve the salt tolerance/sensitivity of cellulose nanofibrils (CNFs), zwitterionic cellulose nanofibrils (ZCNFs) were prepared from softwood bleached kraft pulp fibers via a sequential process of anionic modification with 2,2,6,6-tetramethylepiperidin-1-oxyl (TEMPO)-mediated oxidation, cationic modification with (2,3-epoxypropyl) trimethylammonium chloride (EPTMAC), and high-pressure homogenization. To produce ZCNFs with different contents of cation group, EPTMAC loadings of 0.15 to 1.15 g/g fiber were explored during cationization. The obtained ZCNFs were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectra (XPS), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and rheological measurements. The salt tolerance of the ZCNFs was investigated by adding mixed salts into the ZCNF dispersions. The results demonstrated that the ZCNFs with both anionic and cationic charges were produced. Compared with the TEMPO-mediated oxidized cellulose nanofibrils (TOCNFs), the ZCNFs exhibited an excellent "salt-thickening" behavior under the studied salt concentrations (2-24% w/w). Moreover, increasing the content of the cation group increased the salt tolerance/sensitivity of ZCNFs. This work demonstrated that introducing cationic charges to the anionic charged TOCNFs imparts the produced ZCNFs with excellent salt sensitivity and tolerance, which could expand the application of nanocellulose in oil recovery or wastewater treatment.

Direct preparation of gels from herbal medicinal plants by using a low toxicity liquid zwitterion

Gels containing the medicinal ingredients of licorice were formed by dissolving herbal medicinal plants into a biocompatible zwitterionic cellulose solvent and successive precipitation. The licorice gels gradually released glycyrrhizic acid, the main medicinal ingredient in licorice, within 3 h. Although the licorice gels were mechanically weak, the gel strength was improved just by the addition of cellulose during the preparation of the gels. Gels containing the medicinal ingredients of licorice were formed by dissolving herbal medicinal plants into a biocompatible zwitterionic cellulose solvent and successive precipitation. The licorice gels gradually released glycyrrhizic acid, the main medicinal ingredient in licorice, within 3 h. Although the licorice gels were mechanically weak, the gel strength was improved just by the addition of cellulose during the preparation of the gels.

Production of zwitterionic cellulose by citric acid and triethanolamine hydrochloride for various end uses

ABSTRACTZwitterionic cellulose was produced by the reaction of citric acid (CA) and triethanolamine hydrochloride (HTEA) on cotton fabrics with the pad–dry–cure method. The wrinkle resistance, dye affinity to anionic dye, antimicrobial properties, and zwitterionic properties were considerably improved. The fixation of CA and HTEA in cotton was confirmed by the wrinkle recovery angle, thermogravimetric analysis, and Fourier transform infrared spectroscopy. Elemental analysis and anionic dye sorption testing also substantiated the HTEA fixation. The X‐ray diffraction and scanning electron microscopy results suggest that CA and HTEA were fixed in the amorphous region of cotton with little surface deposition. The zwitterionic properties of the treated cotton was studied with a cationic dye at various pHs. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46840.

A Spherical Zwitterionic Cellulose Acetate/ Graphene Oxide Composite Adsorbent for Efficient Removal of Cu2+ and Cd2+ from Aqueous Solution

A novel composite adsorbent was prepared by using cellulose acetate modified with zwitterion, for zwitterionic cellulose acetate (ZCA), then blended with graphene oxide (GO). The adsorbent was prepared by sol-gel method and used to remove Cu2+ and Cd2+ from aqueous solution. The morphologies, surface chemical structures, and crystallinity of the obtained adsorbents were characterized by field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), and X-ray diffractometer (XRD), respectively. N2 adsorption-desorption measurements revealed that the surface area and pore volume were 45.3 m2g-1 and 0.249 cm3g-1. For adsorption, effect of time, and pH, adsorbate concentration was investigated; different adsorption models were also evaluated. The results showed that the maximum adsorption capacity was 32.0 mg/g for Cu2+ and 27.6 mg/g for Cd2+, observed at pH 5.5 and 298 K. Simultaneously, the adsorption isotherms were well-fitted to the Langmuir model, and kinetics study showed that the adsorption process was fitted well by the pseudo-second-order model. Further regeneration experiments revealed that the adsorption of ZCA/GO was about 90% of the initial saturation adsorption capacity after repeated use 5 times, indicating that they are promising absorbents for practical application in industry.

Surfactant controlled zwitterionic cellulose nanofibril dispersions

Zwitterionic cellulose nanofibrils (ZCNFs) with an isoelectric point of 3.4 were obtained by grafting glycidyltrimethylammonium chloride onto TEMPO/NaBr/NaOCl-oxidised cellulose nanofibrils. The ZCNF aqueous dispersions were characterized via transmission electron microscopy, rheology and small angle neutron scattering, revealing a fibril-bundle structure with pronounced aggregation at pH 7. Surfactants were successfully employed to tune the stability of the ZCNF dispersions. Upon addition of the anionic surfactant, sodium dodecyl sulfate, the ZCNF dispersion shows individualized fibrils due to electrostatic stabilization. In contrast, upon addition of the cationic species dodecyltrimethylammonium bromide, the dispersion undergoes charge neutralization, leading to more pronounced flocculation.

Exploration of zwitterionic cellulose acetate antifouling ultrafiltration membrane for bovine serum albumin (BSA) separation

This study focused on the preparation of a new kind of membrane material, zwitterionic cellulose acetate (ZCA), via a three-step procedure consist of oxidization, Schiff base and quaternary amination reaction, and the fabrication of antifouling ZCA ultrafiltration membrane by the non-solvent-induced phase separation method (NIPS). The morphologies, surface chemical structures and compositions of the obtained CA and ZCA membranes were thoroughly characterized by field emission scanning electron microscopy (FE-SEM) with energy dispersive X-ray (EDX) spectroscopy, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS), respectively. Meanwhile, the thermal stability, porosity and average pore size of two investigated membranes were also studied. As a result, the ZCA membrane displayed significantly improved hydrophilicity and water permeability compared with those of the reference CA membrane, despite a slight decrease in the protein rejection ratio. According to the cycle ultrafiltration performance of bovine serum albumin (BSA) solution and protein adsorption experiment, ZCA membrane exhibited better flux recovery property and fouling resistant ability, especially irreversible fouling resistant ability, suggesting superior antifouling performance. This new approach gives polymer-based membrane a long time life and excellent ultrafiltration performance, and seems promising for potential applications in the protein separation.

Synthesis of novel zwitterionic cellulose beads by oxidation and coupling chemistry in water

The design and synthesis of polysaccharide-based materials utilizing a systematic approach is essential to develop sustainable and biodegradable value added products. In this work, new zwitterionic cellulose beads of desired size range were prepared via spin drop atomization followed by sol gel transition technique. Carboxylic acid (COOH) and carbonyl (C=O) moieties were generated using NaClO2/NaClO/TEMPO mediated oxidation system under heterogenous reaction conditions. Coupling reaction between carboxymethyl trimethylammonium chloride hydrazide (Girard’s reagent T) and carbonyl functionalities on cellulose resulted in the formation of stable hydrazone groups. A variation in molar ratio of NaClO2, NaClO and TEMPO were studied to understand the effect of each reagent on the generation of oxidized products. COOH and C=O content was determined by conductometric titrations and oximation with hydroxylamine hydrochloride followed by elemental analysis, respectively. Evidence of functionalization was obtained with ATR-FTIR, Raman, solid state 13C NMR spectroscopic studies and ToF–SIMS analysis. Morphological changes were studied by FE-SEM. The increased porosity and hydrophilicity of zwitterionic beads provides a platform for the future application of these beads in separation of biomolecules, chiral molecules, immobilization of proteins and enzymes and encapsulation of zwitterionic drugs.

An Efficient, Regioselective Pathway to Cationic and Zwitterionic N-Heterocyclic Cellulose Ionomers.

Cationic derivatives of cellulose and other polysaccharides are attractive targets for biomedical applications due to their propensity for electrostatically binding with anionic biomolecules, such as nucleic acids and certain proteins. To date, however, relatively few practical synthetic methods have been described for their preparation. Herein, we report a useful and efficient strategy for cationic cellulose ester salt preparation by the reaction of 6-bromo-6-deoxycellulose acetate with pyridine or 1-methylimidazole. Dimethyl sulfoxide solvent favored this displacement reaction to produce cationic cellulose acetate derivatives, resulting in high degrees of substitution (DS) exclusively at the C-6 position. These cationic cellulose derivatives bearing substantial, permanent positive charge exhibit surprising thermal stability, dissolve readily in water, and bind strongly with a hydrophilic and anionic surface, supporting their potential for a variety of applications such as permeation enhancement, mucoadhesion, and gene or drug delivery. Expanding upon this chemistry, we reacted a 6-imidazolyl-6-deoxycellulose derivative with 1,3-propane sultone to demonstrate the potential for further elaboration to regioselectively substituted zwitterionic cellulose derivatives.