Novel Lignin-Functionalized Waterborne Epoxy Composite Coatings with Excellent Anti-Aging, UV Resistance, and Interfacial Anti-Corrosion Performance.

Developing high-performance lignin anti-corrosive waterborne epoxy (WEP) coatings is conducive to the advancement of environmentally friendly coatings and the value-added utilization of lignin. In this work, a functionalized biomass waterborne epoxy composite coating is prepared using quaternized sodium lignosulfonate (QLS) as a functional nanofiller for mild carbon steel protection. The results showed that QLS has excellent dispersion and interface compatibility within WEP, and its abundant phenolic hydroxyl, sulfonate, quaternary ammonium groups, and nanoparticle structure endowed the coating with excellent corrosion inhibition and superior barrier properties. The corrosion inhibition efficiency of 100 mg L-1 QLS in carbon steel immersed in a 3.5 wt% NaCl solution reached 95.76%. Furthermore, the coating maintained an impedance modulus of 2.29 × 106 Ω cm2 (|Z|0.01 Hz) after being immersed for 51 days in the high-salt system. In addition, QLS imparted UV-blocking properties and thermal-oxygen aging resistance to the coating, as evidenced by a |Z|0.01 Hz of 1.04 × 107 Ω cm2 after seven days of UV aging while still maintaining a similar magnitude as before aging. The green lignin/WEP functional coatings effectively withstand the challenging outdoor environment characterized by high salt concentration and intense UV radiation, thereby demonstrating promising prospects for application in metal protection.

Atomistic Modeling of Quaternized Chitosan Head Groups: Insights into Chemical Stability and Ion Transport for Anion Exchange Membrane Applications.

The chemical stability and ion transport properties of quaternized chitosan (QCS)-based anion exchange membranes (AEMs) were explored using Density Functional Theory (DFT) calculations and all-atom molecular dynamics (MD) simulations. DFT calculations of LUMO energies, reaction energies, and activation energies revealed an increasing stability trend among the head groups: propyl trimethyl ammonium chitosan (C) < oxy propyl trimethyl ammonium chitosan (B) < 2-hydroxy propyl trimethyl ammonium chitosan (A) at hydration levels (HLs) of 0 and 3. Subsequently, all-atom MD simulations evaluated the diffusion of hydroxide ions (OH-) through mean square displacement (MSD) versus time curves. The diffusion coefficients of OH- ions for the three types of QCS (A, B, and C) were observed to increase monotonically with HLs ranging from 3 to 15 and temperatures from 298 K to 350 K. Across different HLs and temperatures, the three QCS variants exhibited comparable diffusion coefficients, underlining their effectiveness in vehicular transport of OH- ions.

Inhibiting Interfacial Diffusion in Heterojunction Perovskite Solar Cells by Replacing Low-Dimensional Perovskite with Uniformly Anchored Quaternized Polystyrene.

Surface heterojunction has been regarded as an effective method to improve the device efficiency of perovskite solar cells. Nevertheless, the durability of different heterojunction under thermal stress is rarely investigated and compared. In this work, benzylammonium chloride and benzyltrimethylammonium chloride are utilized to construct 3D/2D and 3D/1D heterojunctions, respectively. A quaternized polystyrene is synthesized to construct a three-dimensional perovskite/amorphous ionic polymer (3D/AIP) heterojunction. Due to the migration and volatility of organic cations, severe interfacial diffusion is found among 3D/2D and 3D/1D heterojunctions, in which the quaternary ammonium cations in the 1D structure are less volatile and mobile than the primary ammonium cations in the 2D structure. 3D/AIP heterojunction remains intact under thermal stress due to the strong ionic bond anchoring at the interface and the ultra-high molecular weight of AIP. Furthermore, the dipole layer formed by AIP can further reduce the voltage loss caused by nonradiative recombination at the interface by 0.088 V. Therefore, the devices based on the 3D/AIP heterojunction achieve a champion power conversion efficiency of 24.27% and maintain 90% of its initial efficiency after either thermal aging for 400 h or wet aging for 3000 h, showing a great promise for polymer/perovskite heterojunction towards real applications.

Preparation of composite monoliths of quaternized chitosan and diatom earth for protein separation.

In this study, composite monoliths with porous structures were prepared using quaternized chitosan and diatom earth for protein separation. Quaternized chitosan (N-[(2-hydroxy-3-trimethylammonium)propyl] chitosan chloride) dissolved in water was mixed with diatom earth and crosslinked with glutaraldehyde under low-temperature conditions to form a cryogel. Interconnected porous monoliths were obtained after removing ice crystals from the cryogel. The monoliths adsorbed bovine serum albumin selectively from the solution mixture of bovine serum albumin and bovine ɤ-globulin, and bovine ɤ-globulin was recovered in the flow-through fraction. The adsorption selectivity was enhanced by changing the solution pH from 6.8 to 5.5. The adsorption of bovine serum albumin by the monolith was replicated at least five times following its washing with a buffer containing 400 mM NaCl and subsequent regeneration with a 10 mM acetate buffer. The composited monolith is a promising adsorbent for the removal of acidic proteins, such as serum albumin contamination in neutral proteins, for example, ɤ-globulins, in bioproduction processes.

Light-Driven Tetra- and Octa-ß-substituted Cationic Zinc(II) Phthalocyanines for Eradicating Fusarium oxysporum Conidia.

Photodynamic inactivation (PDI) is an emerging therapeutic approach that can effectively inactivate diverse microbial forms, including vegetative forms and spores, while preserving host tissues and avoiding the development of resistance to the photosensitization procedure. This study evaluates the antifungal and sporicidal photodynamic activity of two water-soluble amphiphilic tetra- and octa-ß-substituted zinc(II) phthalocyanine (ZnPc) dyes with dimethylaminopyridinium groups at the periphery (ZnPcs 1, 2) and their quaternized derivatives (ZnPcs 1a, 2a). Tetra(1, 1a)- and octa(2, 2a)-ß-substituted zinc(II) phthalocyanines were prepared and assessed as photosensitizers (PSs) for their effects on Fusarium oxysporum conidia. Antimicrobial photoinactivation experiments were performed with each PS at 0.1, 1, 10, and 20 µM under white light irradiation at an irradiance of 135 mW·cm-2, for 60 min (light dose of 486 J·cm-2). High PDI efficiency was observed for PSs 1a, 2, and 2a (10 µM), corresponding to inactivation until the method's detection limit. PS 1 (20 µM) also achieved a considerable reduction of >5 log10 in the concentration of viable conidia. The quaternized PSs (1a, 2a) showed better PDI performance than the non-quaternized ones (1, 2), even at the low concentration of 1 µM, and a light dose of 486 J·cm-2. These cationic phthalocyanines are potent photodynamic drugs for antifungal applications due to their ability to effectively inactivate resistant forms, like conidia, with low concentrations and reasonable energy doses.

Interactions between Ionic Cellulose Derivatives Recycled from Textile Wastes and Surfactants: Interfacial, Aggregation and Wettability Studies.

Interactions between polymers (P) and surfactants (S) in aqueous solution lead to interfacial and aggregation phenomena that are not only of great interest in physical chemistry but also important for many industrial applications, such as the development of detergents and fabric softeners. Here, we synthesized two ionic derivatives-sodium carboxymethylcellulose (NaCMC) and quaternized cellulose (QC)-from cellulose recycled from textile wastes and then explored the interactions of these polymers with assorted surfactants-cationic (CTAB, gemini), anionic (SDS, SDBS) and nonionic (TX-100)-commonly used in the textile industry. We obtained surface tension curves of the P/S mixtures by fixing the polymer concentration and then increasing the surfactant concentration. In mixtures where polymer and surfactant are oppositely charged (P-/S+ and P+/S-), a strong association is observed, and from the surface tension curves, we determined the critical aggregation concentration (cac) and critical micelle concentration in the presence of polymer (cmcp). For mixtures of similar charge (P+/S+ and P-/S-), virtually no interactions are observed, with the notable exception of the QC/CTAB system, which is much more surface active than the neat CTAB. We further investigated the effect of oppositely charged P/S mixtures on hydrophilicity by measuring the contact angles of aqueous droplets on a hydrophobic textile substrate. Significantly, both P-/S+ and P+/S- systems greatly enhance the hydrophilicity of the substrate at much lower surfactant concentrations than the surfactant alone (in particular in the QC/SDBS and QC/SDS systems).

Investigation of the Antioxidant Properties of the Quaternized Chitosan Modified with a Gallic Acid Residue Using Peroxidase that Produces Reactive Oxygen Species.

Chitosan modified with a (2-hydroxy-3-trimethylammonium) propyl group and gallic acid residue, or quaternized chitosan with gallic acid (QCG), was synthesized. Antioxidant properties of the produced QCG have been investigated. Peroxidase in combination with NADH and salicyl hydroxamate (SHAM) caused consumption of oxygen and production of H2O2 in aqueous solution as a result of O2 reduction in the peroxidase-oxidase reactions. The rates of O2 consumption and H2O2 generation were reduced in the presence of QCG. The antioxidant propyl gallate (PG) and superoxide dismutase (SOD) had the same effect, but not the quaternized chitosan (QC) without gallic acid. The effect of chitosan derivatives on the production of reactive oxygen species (ROS) in the cells of pea leaf epidermis and on the cell death detected by the destruction of cell nuclei, was investigated. QCG, QC, and SOD had no effect, while PG decreased the rate of ROS generation in the cells of the epidermis, which was induced by NADH with SHAM or by menadione. QCG and QC prevented destruction of the guard cell nuclei in the pea leaf epidermis that was caused by NADH with SHAM or by KCN. SOD had no effect on the destruction of nuclei, while the effect of PG depended on the inducer of the cell death. Suppression of the destruction of guard cell nuclei by chitosan derivatives was associated not with their antioxidant effect, but with the disruption of the plasma membrane of the cells. The results obtained have shown that QCG exhibits antioxidant properties in solutions, but does not prevent generation of ROS in the plant cells. The mechanism of antioxidant effect of QCG is similar to that of PG and SOD.

Green Blends Based on Ionic Liquids with Improved Performance for Membrane Technology: Perspectives for Environmental Applications.

Present research was directed towards the development of new high-performance and cost-effective polysulfone membranes (PSFQ) by introducing ionic liquids (ILs-Cyphos 101 IL and Aliquat 336) into their matrix. Variation of ILs was performed with the aim to find the one that brings new properties and improves the functionality and selectivity of PSFQ membranes in ultrafiltration processes. Based on the obtained results of the rheological study, we established the compatibility of compounds and optimal content of the used ILs, namely 3 wt% and 15 wt% Cyphos 101 IL and compositions varying between 3 and 15 wt % Aliquat 336. Results indicated that the ILs acted as plasticizers when they were added to the system, a helpful aspect in processing membranes used in water decontamination. The efficiency and performance of the membranes were evaluated by their use in the treatment of diclofenac (DCF)-containing waters. Membranes obtained from PSFQ/Aliquat 336 solution containing 15 wt% IL exhibited a 97% removal degree of DCF in the treatment process of 50 mL solution containing 3 mg/L DCF. The separation efficiency was kept constant for four filtration/cleaning cycles. The results indicated an improvement in membrane performance as the amount of IL in their structure increased, which confirms the potential for application in water treatment processes.

Materials Based on Quaternized Polysulfones with Potential Applications in Biomedical Field: Structure-Properties Relationship.

Starting from the bactericidal properties of functionalized polysulfone (PSFQ) and due to its excellent biocompatibility, biodegradability, and performance in various field, cellulose acetate phthalate (CAP) and polyvinyl alcohol (PVA), as well as their blends (PSFQ/CAP and PSFQ/PVA), have been tested to evaluate their applicative potential in the biomedical field. In this context, because the polymer processing starts from the solution phase, in the first step, the rheological properties were followed in order to assess and control the structural parameters. The surface chemistry analysis, surface properties, and antimicrobial activity of the obtained materials were investigated in order to understand the relationship between the polymers' structure-surface properties and organization form of materials (fibers and/or films), as important indicators for their future applications. Using the appropriate organization form of the polymers, the surface morphology and performance, including wettability and water permeation, were improved and controlled-these being the desired and needed properties for applications in the biomedical field. Additionally, after antimicrobial activity testing against different bacteria strains, the control of the inhibition mechanism for the analyzed microorganisms was highlighted, making it possible to choose the most efficient polymers/blends and, consequently, the efficiency as biomaterials in targeted applications.

Synthesis of Xylan-Click-Quaternized Chitosan via Click Chemistry and Its Application in the Preparation of Nanometal Materials.

For the high-valued utilization of hemicelluloses and for realizing the controllable synthesis of NPs, this paper's aim is to combine xylan, chitosan and nanometal materials at the same time. In this research study, firstly, propargyl xylan was synthesized via nucleophilic substitution reaction between xylan and propargyl bromide in NaOH solution. On the other hand, a tosyl group was introduced onto the 6th position of synthesized quaternized chitosan (QCS), and the azide group replaced the tosyl group to obtain 6-amido-QCS (QCS-N3). The synthesis conditions of the above reactions were optimized. Subsequently, the novel xylan-click-QCS polymer was obtained via click reaction between terminal alkyne groups on the xylan chains and azide groups on QCS. Then, AgNPs and AuNPs were synthesized by adopting the xylan-click-QCS polymer as the reducing and stabilizing agent, and the reaction conditions were optimized to obtain well-dispersed and highly stable nanoparticles. There were two kinds of Ag nanomaterials, with diameters of 10~20 nm and 2~5 nm, respectively, indicating the formation of Ag nanoclusters, except for Ag nanoparticles, in this reaction. The diameter of the synthesized AuNPs was 20~30 nm, which possessed a more uniform size distribution. The Ag nanoclusters with a smaller size (2~5 nm) could inhibit MCF-7 cell proliferation effectively, indicating their application potential in cancer therapy. The study gives a new approach to the high-value utilization of biopolymers.

Antimicrobial Polymer-Based Assemblies: A Review.

An antimicrobial supramolecular assembly (ASA) is conspicuous in biomedical applications. Among the alternatives to overcome microbial resistance to antibiotics and drugs, ASAs, including antimicrobial peptides (AMPs) and polymers (APs), provide formulations with optimal antimicrobial activity and acceptable toxicity. AMPs and APs have been delivered by a variety of carriers such as nanoparticles, coatings, multilayers, hydrogels, liposomes, nanodisks, lyotropic lipid phases, nanostructured lipid carriers, etc. They have similar mechanisms of action involving adsorption to the cell wall, penetration across the cell membrane, and microbe lysis. APs, however, offer the advantage of cheap synthetic procedures, chemical stability, and improved adsorption (due to multipoint attachment to microbes), as compared to the expensive synthetic routes, poor yield, and subpar in vivo stability seen in AMPs. We review recent advances in polymer-based antimicrobial assemblies involving AMPs and APs.

Formulation of Quaternized Aminated Chitosan Nanoparticles for Efficient Encapsulation and Slow Release of Curcumin.

An effective drug nanocarrier was developed on the basis of a quaternized aminated chitosan (Q-AmCs) derivative for the efficient encapsulation and slow release of the curcumin (Cur)-drug. A simple ionic gelation method was conducted to formulate Q-AmCs nanoparticles (NPs), using different ratios of sodium tripolyphosphate (TPP) as an ionic crosslinker. Various characterization tools were employed to investigate the structure, surface morphology, and thermal properties of the formulated nanoparticles. The formulated Q-AmCs NPs displayed a smaller particle size of 162 ± 9.10 nm, and higher surface positive charges, with a maximum potential of +48.3 mV, compared to native aminated chitosan (AmCs) NPs (231 ± 7.14 nm, +32.8 mV). The Cur-drug encapsulation efficiency was greatly improved and reached a maximum value of 94.4 ± 0.91%, compared to 75.0 ± 1.13% for AmCs NPs. Moreover, the in vitro Cur-release profile was investigated under the conditions of simulated gastric fluid [SGF; pH 1.2] and simulated colon fluid [SCF; pH 7.4]. For Q-AmCs NPs, the Cur-release rate was meaningfully decreased, and recorded a cumulative release value of 54.0% at pH 7.4, compared to 73.0% for AmCs NPs. The formulated nanoparticles exhibited acceptable biocompatibility and biodegradability. These findings emphasize that Q-AmCs NPs have an outstanding potential for the delivery and slow release of anticancer drugs.

Detection of DNA methyltransferase activity using template-free DNA polymerization amplification based on aggregation-induced emission.

A sensitive and selective fluorescence assay for DNA methyltransferase (MTase) activity detection was designed based on aggregation-induced emission (AIE) and target initiated template-free DNA polymerization. Quaternized tetraphenylethene salt was synthesized as the AIE probe, which binds to single-stranded DNA by electrostatic interaction. A hairpin probe was designed with a specific sequence for DNA MTase. In the presence of DNA MTase, the methylation reaction initiated DNA polymerization with terminal deoxynucleotidyl transferase (TdT), which activated the fluorescence intensity through AIE. The designed DNA sensor displayed a linear response to concentrations of DNA adenine methyltransferase (Dam) MTase from 0.5 U·mL-1 to 100 U mL-1, with a limit of detection of 0.16 U mL-1. The assay was also effective for detection of DNA MTase activity in human serum and for showing the inhibitory effect of 5-fluorouracil on Dam MTase.

High-efficient and synergetic antibacterial nanocomposite hydrogel with quaternized chitosan/Ag nanoparticles prepared by one-pot UV photochemical synthesis.

Hydrogel dressings have significant advantages such as absorption of tissue exudate, maintenance of proper moist environment, and promotion of cell proliferation. However, facile preparation method and high-efficient antibacterial hydrogel dressings are still a great challenge. In this study, a facile approach to prepare antibacterial nanocomposite hydrogel dressing to accelerate healing was explored. The hydrogels consisted of quaternized chitosan and chemically cross-linked polyacrylamide, as well as silver nanoparticles (AgNPs) stabilized by chitosan. The synthesis of the hydrogels including the formation of AgNPs and polymerization of acrylamide was accomplished simultaneously under UV irradiation in 1 hour without adding initiator. The hydrogels showed favorable tensile strength of ∼100 kPa with elongation at break over 1000% and shear modulus of ∼104 Pa as well as suitable swelling ratio, which were appropriate for wound dressing. The combination of quaternized chitosan and AgNPs exhibited high-efficient and synergetic antibacterial performance with low cytotoxicity. In vivo animal experiments showed that the hydrogel can effectively prevent wound infection and promote wound healing. This study provides a facile method to produce antibacterial hydrogel wound dressing materials.

A Novel Anion Exchange Membrane for Bisulfite Anion Separation by Grafting a Quaternized Moiety through BPPO via Thermal-Induced Phase Separation.

Ion-exchange membranes are the core elements for an electrodialysis (ED) separation process. Phase inversion is an effective method, particularly for commercial membrane production. It introduces two different mechanisms, i.e., thermal induced phase separation (TIPS) and diffusion induced phase separation (DIPS). In this study, anion exchange membranes (AEMs) were prepared by grafting a quaternized moiety (QM,2-[dimethylaminomethyl]naphthalen-1-ol) through brominated poly (2,6-dimethyl-1,4-phenylene oxide) (BPPO) via the TIPS method. Those membranes were applied for selective bisulfite (HSO3-) anion separation using ED. The membrane surface morphology was characterized by SEM, and the compositions were magnified using a high-resolution transmission electron microscope (HRTEM). Notably, the membranes showed excellent substance stability in an alkali medium and in grafting tests performed in a QM-soluble solvent. The ED experiment indicated that the as-prepared membrane exhibited better HSO3- separation performance than the state-of-the-art commercial Neosepta AMX (ASTOM, Japan) membrane.

Enhanced phosphate removal using zirconium hydroxide encapsulated in quaternized cellulose.

Zirconium-based materials are efficient adsorbent for aqueous phosphate removal. However, current zirconium-based materials still show unsatisfied performance on adsorption capacity and selectivity. Here, we demonstrate a zirconium hydroxide encapsulated in quaternized cellulose (QC-Zr) for the selective phosphate removal. Zirconium hydroxide nanoparticles were simultaneously generated in situ with the QC framework and firmly anchored in the three-dimensional (3D) cross-linked cellulose chains. The maximum P adsorption capacity of QC-Zr was 83.6 mg P/g. Furthermore, the QC-Zr shows high P adsorption performance in a wide pH range, generally due to the electrostatic effects of quaternized cellulose. The enhanced adsorption of P was also achieved in the presence of competing anions (including Cl-, NO3-, SO42-, SO44-) and humic acid (HA) even at a molar ratio up to 20 levels. The column adsorption capacity of QC-Zr reached 4000 bed volumes (BV) at EBCT = 0.5 min as the P concentration decreased from 2.5 to 0.5 mg/L. Mechanism study revealed that both -N+(CH3)3 groups and zirconium hydroxide were involved in phosphate adsorption via electrostatic interactions between -N+(CH3)3 and phosphate, and the formation of zirconium hydrogen phosphate (Zr(HPO4)x). The 31P nuclear magnetic resonance (NMR) study implied that P surface-precipitated and inner-sphere complexed with zirconium hydroxide at a ratio of 3:1.

Antibacterial, Antibiofilm, and Antiadhesive Properties of Different Quaternized Chitosan Derivatives.

In the era of antimicrobial resistance, the identification of new antimicrobials is a research priority at the global level. In this regard, the attention towards functional antimicrobial polymers, with biomedical/pharmaceutical grade, and exerting anti-infective properties has recently grown. The aim of this study was to evaluate the antibacterial, antibiofilm, and antiadhesive properties of a number of quaternized chitosan derivatives that have displayed significant muco-adhesive properties and wound healing promotion features in previous studies. Low (QAL) and high (QAH) molecular weight quaternized chitosan derivatives were synthetized and further modified with thiol moieties or pendant cyclodextrin, and their antibacterial activity evaluated as minimal inhibitory concentrations (MIC) and minimal bactericidal concentrations (MBC). The ability of the derivatives to prevent biofilm formation was assessed by crystal violet staining. Both QAL and QAH derivatives exerted a bactericidal and/or inhibitory activity on the growth of P. aeruginosa and S. epidermidis. The same compounds also showed marked dose-dependent anti-biofilm activity. Furthermore, the high molecular weight derivative (QAH) was used to functionalize titanium plates. The successful functionalization, demonstrated by electron microscopy, was able to partially inhibit the adhesion of S. epidermidis at 6 h of incubation. The shown ability of the chitosan derivatives tested to both inhibit bacterial growth and/or biofilm formation of clinically relevant bacterial species reveals their potential as multifunctional molecules against bacterial infections.

Quaternized Zn(II) phthalocyanines for photodynamic strategy against resistant periodontal bacteria.

Photodynamic inactivation (PDI) has been featured as an effective strategy in the treatment of acute drug-resistant infections. The efficiency of PDI was evaluated against three periodontal pathogenic bacteria that were tested as drug-resistant strains. In vitro studies were performed with four water-soluble cationic Zn(II) phthalocyanines (ZnPc1-4) and irradiation of a specific light source (light-emitting diode, 665 nm) with three doses (15, 36 and 60 J/cm2). The well detectable fluorescence of ZnPcs allowed the cellular imaging, which suggested relatively high uptakes of ZnPcs into bacterial species. Complete photoinactivation was achieved with all studied ZnPc1-4 for Enterococcus faecalis (E. faecalis) at a light dose of 15 J/cm2. The photodynamic response was high for Prevotella intermedia (P. intermedia) after the application of 6 µM of ZnPc1 and a light dose of 36 J/cm2 and for 6 µM of ZnPc2 at 60 J/cm2. P. intermedia was inactivated with ZnPc3 (4 log) and ZnPc4 (2 log) with irradiation at an optimal dose of 60 J/cm2. Similar photoinactivation results (2 log) were achieved for Aggregatibacter actinomycetemcomitans (A. actinomycetemcomitans) treated with 6 µM ZnPc1 and ZnPc2 at a light dose of 60 J/cm2. The study suggested that PDI with quaternized Zn(II) phthalocyanines and specific light irradiation appears to be a very useful antimicrobial strategy for effective inactivation of drug-resistant periodontal pathogens.

Synthesis, Characterization, and Antifungal Activity of Pyridine-Based Triple Quaternized Chitosan Derivatives.

In this study, a series of triple quaternized chitosan derivatives, including 6-O-[(2-hydroxy-3-trimethylammonium)propyl]-2-N-(1-pyridylmethyl-2-ylmethyl)-N,N-dimethyl chitosan chloride (7), 6-O-[(2-hydroxy-3-trimethylammonium)propyl]-2-N-(1-pyridylmethyl-3-yl- methyl)-N,N-dimethyl chitosan chloride (8), and 6-O-[(2-hydroxy-3-trimethylammonium)propyl]- 2-N-(1-pyridylmethyl-4-ylmethyl)-N,N-dimethyl chitosan chloride (9) were successfully designed and synthesized via reacting epoxypropyl trimethylammonium chloride with the N-pyridinium double quaternized chitosan derivatives. Detailed structural characterization was carried out using FT-IR and ¹H-NMR spectroscopy, and elemental analysis. Besides, the activity of the triple quaternized chitosan derivatives against three common plant pathogenic fungi, Watermelon fusarium, Fusarium oxysporum, and Phomopsis asparagi, was investigated in vitro. The results indicated that the triple quaternized chitosan derivatives had enhanced antifungal activity when compared to double quaternized chitosan derivatives and chitosan, especially at 1.0 mg/mL, which confirmed the theory that the higher density of positive charge contributed to the antifungal activity. Moreover, 8 with an almost 99% inhibitory index showed the better antifungal activity against Watermelon fusarium. Moreover, the cytotoxicity of the products was also evaluated in vitro on 3T3-L1 cells and all the triple quaternized chitosan derivatives exhibited low cytotoxicity. These results suggested that triple quaternized chitosan derivatives may be used as good antifungal biomaterials.

Preparation and Characterization of Quaternized Chitosan Derivatives and Assessment of Their Antioxidant Activity.

Chitosan (CS) is an abundant and renewable polysaccharide that is reported to exhibit a great variety of beneficial properties. However, the poor solubility of chitosan in water limits its applications. In this paper, we successfully synthesized single N-quaternized (QCS) and double N-diquaternized (DQCS) chitosan derivatives, and the resulting quaternized materials were water-soluble. The degree of quaternization (DQ) of QCS and DQCS was 0.8 and 1.3, respectively. These derivatives were characterized by FTIR, ¹H NMR, 13C NMR, TGA, and SEM. Moreover, the antioxidant activity of the chitosan was evaluated by free radical scavenging ability (against DPPH-radical, hydroxyl-radical, and superoxide-radical) and ferric reducing power. Our results suggested that the antioxidant abilities were in the order of DQCS > QCS > CS, which was consistent with the number of quaternized groups. These data demonstrate that the number of quaternized groups of chitosan derivatives contributes to their antioxidant activity. Therefore, DQCS, with a higher number of quaternized groups and higher positive charge density, is endowed with high antioxidant activity, and can be used as a candidate material in food and pharmaceutical industries.