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Lead ion is very harmful to the environment, so it is very important to study its detection methods. In this study, a novel electrochemical sensor was constructed by modifying deoxyribonucleic acid (DNA) on the electrode, which can be used for the detection of Pb 2+ in the environment. Part of the mixed solution of chitosan (CS) and Pb 2+ template ions was dropped onto the surface of a glassy carbon electrode. CS-Pb 2+ film was cross-linked through sodium tripolyphosphate. And a novel DNA-imprinted sensor was prepared by electrodepositing CS-Pb 2+ thin film with gold nanoparticles (AuNPs), removing Pb 2+ templates, and immobilizing specific double-stranded DNA. The electroactive area, surface morphology, sensitivity, and electrochemical reaction mechanism of the DNA-imprinted sensor were analyzed. The elementary reaction steps were studied through electrochemical reaction kinetics analysis. The experimental results indicate that the DNA-imprinted electrochemical biosensor can quantitatively detect Pb 2+ in the range of 10-100 μM (R 2  = 0.9935), and its detection limit is 6.5074 μM (3σ/slope). The sensitivity of the electrochemical biosensor is 1.55233 × 10 -6  A/μM, and its active areas is 6.233 cm 2 . The desorption mechanism and adsorption mechanism have been explored through dynamic parameter analysis. The novel DNA imprinted electrochemical biosensor developed in this paper provides a robust method for detecting lead ions in solution. Additionally, it establishes a solid groundwork for detecting other metal ions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

pH-responsive nanogels have played an increasingly momentous role in tumor treatment. The focus of this study is to design and develop pH-responsive benzimidazole-chitosan quaternary ammonium salt (BIMIXHAC) nanogels for the controlled release of doxorubicin hydrochloride (DOX) while enhancing its hydrophilicity. BIMIXHAC is crosslinked with carboxymethyl chitosan (CMC), hyaluronic acid sodium salt (HA), and sodium alginates (SA) using an ion crosslinking method. The chemical structure of chitosan derivatives was verified by 1 H NMR and FT-IR techniques. Compared to hydroxypropyl trimethyl ammonium chloride chitosan (HACC)-based nanogels, BIMIXHAC-based nanogels exhibit better drug encapsulation efficiency and loading capacity (BIMIXHAC-D-HA 91.76 %, and 32.23 %), with pH-responsive release profiles and accelerated release in vitro. The series of nanogels formed by crosslinking with three different polyanionic crosslinkers have different particle size potentials and antioxidant properties. BIMIXHAC-HA, BIMIXHAC-SA and BIMIXHAC-CMC demonstrate favorable antioxidant capability. In addition, cytotoxicity tests showed that BIMIXHAC-based nanogels have high biocompatibility. BIMIXHAC-based nanogels exhibit preferable anticancer effects on MCF-7 and A549 cells. Furthermore, the BIMIXHAC-D-HA nanogel was 2.62 times less toxic than DOX to L929 cells. These results suggest that BIMIXHAC-based nanogels can serve as pH-responsive nanoplatforms for the delivery of anticancer drugs., Competing Interests: Declaration of competing interest All authors declared no conflict of interest., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The present study focused on the design and preparation of acid-responsive benzimidazole-chitosan quaternary ammonium salt (BIMIXHAC) nanogels for a controlled, slow-release of Doxorubicin HCl (DOX.HCl). The BIMIXHAC was crosslinked with sodium tripolyphosphate (TPP) using the ion crosslinking method. The method resulted in nanogels with low polydispersity index, small particle size, and positive zeta potential values, indicating the good stability of the nanogels. Compared to hydroxypropyl trimethyl ammonium chloride chitosan-Doxorubicin HCl-sodium tripolyphosphate (HACC-D-TPP) nanogel, the benzimidazole-chitosan quaternary ammonium salt-Doxorubicin HCl-sodium tripolyphosphate (BIMIXHAC-D-TPP) nanogel show higher drug encapsulation efficiency and loading capacity (BIMIXHAC-D-TPP 93.17 ± 0.27% and 31.17 ± 0.09%), with acid-responsive release profiles and accelerated release in vitro. The hydroxypropyl trimethyl ammonium chloride chitosan-sodium tripolyphosphate (HACC-TPP), and benzimidazole-chitosan quaternary ammonium salt-sodium tripolyphosphate (BIMIXHAC-TPP) nanogels demonstrated favorable antioxidant capability. The assay of cell viability, measured by the MTT assay, revealed that nanogels led to a significant reduction in the cell viability of two cancer cells: the human lung adenocarcinoma epithelial cell line (A549) and the human breast cancer cell line (MCF-7). Furthermore, the BIMIXHAC-D-TPP nanogel was 2.96 times less toxic than DOX.HCl to the mouse fibroblast cell line (L929). It was indicated that the BIMIXHAC-based nanogel with enhanced antioxidant and antitumor activities and acidic-responsive release could serve as a potential nanocarrier.

In this study, a multifunctional nanofiber dressing that can promote antibacterial, analgesic and healing was prepared by electrospinning technology. Hydrophobic polycaprolactone (PCL)/chitosan (CS)/lidocaine hydrochloride (LID) and epidermal growth factor (EGF) were used as scaffold materials and dissolved in trifluoroacetic acid to prepare spinning solution. The morphology of PCEL dressing was observed by scanning electron microscopy. The fiber structure was dense and the average diameter was 297.0 nm. The water absorption capacity test and water contact angle measurement showed that the fiber had good water absorption and hydrophilicity (1302 %, 139.258°). Drug release was 84 % within 60 h. In the results of antibacterial experiment, the dressing showed certain antibacterial properties. The results of cell experiments show that the dressing can promote cell proliferation. In addition, coagulation experiments showed that the dressing could quickly coagulate the blood within 4 min. In addition, PCEL dressing promoted collagen deposition and vascularization through animal models of pressure sores. Therefore, multifunctional dressing can be used as an ideal auxiliary means for the treatment of pressure sores, and it is a promising alternative to chronic wound healing., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

A total of 16 novel carboxymethyl chitosan derivatives bearing quinoline groups in four classes were prepared by different synthetic methods. Their chemical structures were confirmed by Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), and elemental analysis. The antioxidant experiment results in vitro (including DPPH radical scavenging ability, superoxide anion radical scavenging ability, hydroxyl radical scavenging ability, and ferric reducing antioxidant power) demonstrated that adding quinoline groups to chitosan (CS) and carboxymethyl chitosan (CMCS) enhanced the radical scavenging ability of CS and CMCS. Among them, both N , O -CMCS derivatives and N -TM- O -CMCS derivatives showed DPPH radical scavenging over 70%. In addition, their scavenging of superoxide anion radicals reached more than 90% at the maximum tested concentration of 1.6 mg/mL. Moreover, the cytotoxicity assay was carried out on L929 cells by the MTT method, and the results indicated that all derivatives showed no cytotoxicity (cell viability > 75%) except O -CMCS derivative 1a, which showed low cytotoxicity at 1000 μg/mL (cell viability 50.77 ± 4.67%). In conclusion, the carboxymethyl chitosan derivatives bearing quinoline groups showed remarkable antioxidant ability and weak cytotoxicity, highlighting their potential use in food and medical applications.

Herein, imidazole acids grafted chitosan derivatives were synthesized, including HACC, HACC derivatives, TMC, TMC derivatives, amidated chitosan and amidated chitosan bearing imidazolium salts. The prepared chitosan derivatives were characterized by FT-IR and 1 H NMR. The tests evaluated the biological antioxidant, antibacterial, and cytotoxic activities of chitosan derivatives. The antioxidant capacity (DPPH radical, superoxide anion radical and hydroxyl radical) of chitosan derivatives was 2.4-8.3 times higher than that of chitosan. The antibacterial capacity against E. coli and S. aureus of cationic derivatives (HACC derivatives, TMC derivatives, and amidated chitosan bearing imidazolium salts) was more active than only imidazole-chitosan (amidated chitosan). In particular, the inhibition effect of HACC derivatives on E. coli was 15.625 μg/mL. Moreover, the series of chitosan derivatives bearing imidazole acids showed certain activity against MCF-7 and A549 cells. The present results suggest that the chitosan derivatives in this paper seem to be promising carrier materials for use in drug delivery systems., Competing Interests: Declaration of competing interest All authors declared no conflict of interest., (Copyright © 2023. Published by Elsevier Ltd.)

In present study, several chitosan derivatives grafted with rosmarinic acid，including chitosan-rosmarinic acid conjugate (CS-RA), chitosan rosmarinic acid salt (CSRA), N,N,N-trimethylated chitosan rosmarinic acid salt (TMCRA), and N-[(2-hydroxy-3-trimethylammonium)propyl]chitosan rosmarinic acid salt (HACRA), were prepared and the effects of different grafting methods on bioactivity of these derivatives were investigated. The structural characterization was identified by FTIR and 1 H NMR spectroscopy. The chitosan derivatives were also evaluated biologically for antioxidant, cytotoxic, and anti-inflammatory activities. Derivatives CSRA, TMCRA, and HACRA prepared through ion exchange method exhibited significant antioxidant ability. All derivatives remarkably inhibited lipopolysaccharide-induced nitric oxide and TNF-α production in RAW 264.7 cells without cytotoxicity, especially derivative TMCRA, whose inhibition rate was >50 % at only 250 μg/mL. The results suggested that chitosan quaternary ammonium derivatives grafted with rosmarinic acid possessed better antioxidant and anti-inflammatory properties than chitosan, which could be used as drug materials against oxidative and inflammation-related pathological processes., Competing Interests: Declaration of competing interest The authors have declared no conflicts of interest., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

In the present study, four new chitosan oligosaccharide derivatives bearing quinolinyl urea groups were synthesized by reaction between 2-methoxyformylated chitosan oligosaccharide and aminoquinoline. The chitosan oligosaccharide derivatives were characterized by Fourier Transform Infrared (FTIR) and 1 H Nuclear Magnetic Resonance ( 1 H NMR) spectroscopy. The obtained results confirmed that chitosan oligosaccharide quinolinyl urea derivatives were successfully synthesized. Meanwhile, the antioxidant activities of different chitosan oligosaccharide derivatives were examined in vitro. Experimentally, it was demonstrated that chitosan oligosaccharide quinolinyl urea derivatives had superior antioxidant activity compared with chitosan oligosaccharide and the antioxidant effects were concentration-dependent. Especially, when the concentration was 1.6 mg/mL, their superoxide anion radical scavenging rates could reach to 72.35 ± 0.49%, 100.00 ± 0.21%, 84.63 ± 0.49%, and 87.22 ± 0.32%, respectively. And the hydroxyl radical scavenging rates could reach to 100.00 ± 0.82%, 98.49 ± 4.08%, 100.00 ± 5.76%, and 92.07 ± 5.10%. In addition, the cytotoxic activity of the prepared chitosan derivatives against L929 cells was determined by CCK-8 assay. The cell survival rates were all higher than 90%, which intuitively indicated that the samples had almost no cytotoxicity. The findings indicated that the enhanced antioxidant property and biocompatibility of these chitosan oligosaccharide quinolinyl urea derivatives could enlarge the scope of the application of chitosan oligosaccharide, particularly as an antioxidant in food packaging, biomedical, pharmaceutical, cosmetics industries and other fields., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Amino functionalized chitosan has attracted much attention because of the fascinated bioactivities. In our study, a novel water-soluble amino functionalized chitosan bearing free amino group at C-2 and quaternary ammonium moiety contained free amino group at C-6 (5c) was prepared by a four-step method. The structural characterization was identified by FTIR and 1 H NMR spectroscopy. The water-solubility and antioxidant activities against hydroxyl, DPPH radicals and reducing power were estimated. The results displayed that amino functionalized chitosan 5c exhibited improved water-solubility and antioxidant ability, especially its DPPH scavenging rate reached about 90 % at the minimum test concentration of 0.10 mg/mL. Besides, antibacterial tests showed that amino functional chitosan 5c had best antibacterial activities, which indicated that amino group made main contribution to the enhanced bioactivities. In short, the novel chitosan 5c possessed enhanced water-solubility and excellent antioxidant and antibacterial activities, which could provide novel strategy for the development of antioxidant and antibacterial agents in biomedicine and food fields., (Copyright © 2022. Published by Elsevier B.V.)

In this work, chitosan derivatives modified with Schiff base bearing benzenoid/heterocyclic moieties were successfully prepared via amidation reaction. Specific structural characterization was implemented using FTIR and 1 H NMR, and the DS of chitosan derivatives were quantitatively calculated by ratio of hydrogen proton integral. Meanwhile, the antifungal activity against two common plant pathogenic fungi (Fusarium oxysporum f. sp. cubense and Glomerella cingulata) was assayed in vitro by hyphal measurement, and data proved that the introduction of functional groups including benzene/heterocyclic compounds and Schiff base groups greatly enhanced the antifungal activity. Besides, the antioxidant efficiency was investigated in vitro, and all chitosan derivatives exhibited significantly increased antioxidant activity. Specially, the scavenging effect of 2SATCS was 96.62% at 1.6 mg/mL, which was close to the positive control VC (98.84%). These results indicated that chitosan derivatives with enhanced antifungal and antioxidant activities could serve as potential biomaterial for antifungal and antioxidant applications., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Hydroxypropyltrimethyl ammonium chloride chitosan (HACC) is one of the most important water-soluble chitosan derivatives; its derivatives have gained growing attention due to their potential biomedical applications. Here, hydroxypropyltrimethyl ammonium chitosan derivatives bearing thioctate (HACTs), with different degrees of substitution of thioctate, were prepared using HACC and α-lipoic acid as the reaction precursors, using an ion exchange method. The structural characteristics of the synthesized derivatives were confirmed by FTIR, 1 H NMR, and 13 C NMR spectroscopy. In addition, their antioxidant behaviors were also investigated in vitro by the assays of reducing power, and scavenging activities against hydroxyl radicals and DPPH radicals. The antioxidant assay indicated that HACTs displayed strong antioxidant activity compared with HACC, especially in terms of reducing power. Besides, the antioxidant activities of the prepared products were further enhanced with the increase in the test concentration and the degrees of substitution of thioctate. At the maximum test concentration of 1.60 mg/mL, the absorbance value at 700 nm of HACTs, under the test conditions, was 4.346 ± 0.296, while the absorbance value of HACC was 0.041 ± 0.007. The aforementioned results support the use of HACTs as antioxidant biomaterials in food and the biomedical field.

In this study, chitosan nanoparticles (HF-CD NPs) were synthesized by an ionic gelation method using negatively charged carboxymethyl-β-cyclodextrin and positively charged 2-hydroxypropyltrimethyl ammonium chloride chitosan bearing folic acid. The surface morphology of HF-CD NPs was spherical or oval, and they possessed relatively small particle size (192 ± 8 nm) and positive zeta potential (+20 ± 2 mV). Meanwhile, doxorubicin (Dox) was selected as model drug to investigate the prepared nanoparticles' potential to serve as a drug delivery carrier. The drug loading efficiency of drug-loaded nanoparticles (HF-Dox-CD NPs) was 31.25%. In vitro release profiles showed that Dox release of nanoparticles represented a pH-sensitive sustained and controlled release characteristic. At the same time, the antioxidant activity of nanoparticles was measured, and chitosan nanoparticles possessed good antioxidant activity and could inhibit the lipid peroxidation inside the cell and avoid material infection. Notably, CCK-8 assay testified that the nanoparticles were safe drug carriers and significantly enhanced the antitumor activity of Dox. The nanoparticles possessed good antioxidant activity, pH-sensitive sustained controlled release, enhanced antitumor activity, and could be expected to serve as a drug carrier in future with broad application prospects.

In this study, to investigate the influence of glyoxylate bearing Schiff base on bioactivity to chitosan quaternary ammonium salts, different chitosan derivatives were synthesized by ion exchange of glyoxylate bearing Schiff base with chitosan quaternary ammonium salts (TMCI and HACC). For this purpose, glyoxylate was prepared by Schiff base reaction of glyoxylic acid and amino heterocycles and it was further ionization to substitute iodide ions and chloride ions. After structural characterization by FTIR and 1 H NMR, the antifungal and antioxidant activities were measured. Results indicated that glyoxylate bearing Schiff base could improve the bioactivity of TMCI and HACC obviously. Specifically, anionic TMCI with Schiff base of amino pyridines possessed best antioxidant activity >92.40% at 1.6 mg/mL against DPPH radicals. Meanwhile, they showed antifungal activity >84.88% at 1.0 mg/mL against G. cingulate. Furthermore, the cytotoxicity was evaluated, and all samples showed good cell viability >80.14% at 1000 μg/mL., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Hydrogels, possessing high biocompatibility and adaptability to biological tissue, show great usability in medical applications. In this research, a series of novel cross-linked chitosan quaternary ammonium salt loading with gentamicin sulfate (CTMCSG) hydrogel films with different cross-linking degrees were successfully obtained by the reaction of chitosan quaternary ammonium salt (TMCS) and epichlorohydrin. Fourier transform infrared spectroscopy (FTIR), thermal analysis, and scanning electron microscope (SEM) were used to characterize the chemical structure and surface morphology of CTMCSG hydrogel films. The physicochemical property, gentamicin sulphate release behavior, cytotoxicity, and antibacterial activity of the CTMCSG against Escherichia coli and Staphylococcus aureus were determined. Experimental results demonstrated that CTMCSG hydrogel films exhibited good water stability, thermal stability, drug release capacity, as well as antibacterial property. The inhibition zone of CTMCSG hydrogel films against Escherichia coli and Staphylococcus aureus could be up to about 30 mm. Specifically, the increases in maximum decomposition temperature, mechanical property, water content, swelling degree, and a reduction in water vapor permeability of the hydrogel films were observed as the amount of the cross-linking agent increased. The results indicated that the CTMCSG-4 hydrogel film with an interesting physicochemical property, admirable antibacterial activity, and slight cytotoxicity showed the potential value as excellent antibacterial wound dressing.

Tremendous awareness of determination of chitosan content accurately is increasing, due to it has great significance to the quality control of chitosan. In this article, two kinds of chitosan-Schiff base derivatives (BCSB and PCSB) were synthesized by the different average degrees of deacetylation (DD) of chitosan with benzaldehyde or propanal, respectively. The total mass of Schiff base derivative product was dried and obtained without washing and loss. Then, a certain amount of the prepared Schiff base compound was taken to hydrolyze into glucosamine hydrochloride (GAH) in strong hydrochloric acidic environment, whose concentration was quantified by HPLC, and the mass of GAH contained in hydrolysis solution could be calculated. Subsequently, the total quality of GAH obtained by hydrolysis of all of the Schiff base product was calculated and obtained, and then the theoretical mass of chitosan could be deduced and calculated by further converse calculation. Finally, the chitosan content was obtained by combining the sample mass used in Schiff base reaction and the theoretical mass of chitosan. This method was accurate and convenient, providing a preeminent idea and method for the determination of chitosan content., (Copyright © 2021 Elsevier B.V. All rights reserved.)

In this study, a series of chitosan derivatives bearing active halogenated aromatic imines were successfully synthesized via Schiff bases with the high degrees of substitution. Detailed structural characterization was carried out using Fourier transform infrared (FTIR) spectroscopy, solid-state 13 C nuclear magnetic resonance (NMR) spectroscopy, and elemental analysis. Besides, the antifungal activity against three common plant pathogenic fungi, including Botrytis cinerea, Fusarium oxysporum f. sp. cucumerinum, and Fusarium oxysporum f. sp. niveum, was investigated using in vitro hyphal measurements. The results showed that double Schiff bases of chitosan derivatives exhibited enhanced antifungal activity compared with chitosan, especially at 1.0 mg/mL. The double Schiff bases of chitosan bearing halogeno-benzenes showed >95% inhibitory indices at 1.0 mg/mL against Botrytis cinereal since halogens had the stronger electron-withdrawing property. The higher degree of substitution was another positive effect to improve the antifungal activity. This study provides a practical strategy to synthesize new double Schiff bases of chitosan derivatives bearing halogeno-benzenes, which could be developed into stronger antifungal agents., Competing Interests: Declaration of competing interest The authors have declared no conflicts of interest., (Copyright © 2021 Elsevier B.V. All rights reserved.)

As one of the most promising biopolymers for a variety of potential applications, chitosan has attracted much attention because of its unique biological, chemical, and physical properties. The functionalization of chitosan has been adopted to synthesize novel chitosan derivatives with improved water-solubility and excellent biological activities. In this paper, chitosan was functionalized with a triphenylphosphonium group by means of the copper (I) catalyzed azide-alkyne "click" reaction and has been investigated as potential polymer for agricultural antifungal biomaterial. The influence of chemical modification on the structural characteristics and water-solubility of chitosan was investigated by FTIR spectroscopy, 1 H NMR spectroscopy, elemental analysis, and UV-vis spectrum. Furthermore, the antifungal property of target chitosan derivative against four plant threatening fungal pathogens was evaluated and in vitro investigation demonstrated that triphenylphosphonium salt incorporated chitosan backbone had excellent antifungal property compared with chitosan and intermediate chitosan derivative. Notably, target chitosan derivative displayed relatively strongest antifungal effect with over 80% inhibitory index against Botrytis cinerea at 1.0 mg/mL. The results of a detailed antifungal study indicated that cationic chitosan derivative bearing 1,2,3-triazole and triphenylphosphonium moieties provided a promising platform for preparation of novel cationic antifungal biomaterials in the field of agriculture., Competing Interests: Declaration of competing interest All authors declared no conflict of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The determination of chitosan is a significant topic that has been growing in importance for a variety of fields. To quantify chitosan, various analytical methods can be used. When high performance liquid chromatographic (HPLC) is used for quantitative analysis of chitosan, the chitosan is mainly hydrolyzed into glucosamine salts, which are determined by HPLC. Average deacetylation degree (DD) has an effect on acid hydrolysis of chitosan. In this paper, chitosan with different average DDs was hydrolyzed to observe its effect on the determination of chitosan content, and that the study of combining acid hydrolysis rates of chitosan (α) with different average DDs and chitin (β) standard to form ratio coefficients (γ) to quantify chitosan was designed. Then, the table about γ values within certain average DD ranges of chitosan was obtained. By using γ and α, the actual content of chitosan could be obtained simply and accurately., Competing Interests: Declaration of competing interest The authors have declared no conflicts of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

In this paper, several novel chitosan derivatives bearing benzenoid / heterocyclic moieties were synthesized via introducing aminobenzene and heterocyclic compounds onto carboxymethyl chitosan. The specific structures of chitosan derivatives were confirmed by FTIR, 1 H NMR, and elemental analysis. Meanwhile, the antioxidant efficiencies of chitosan derivatives were assayed in vitro. In particular, all chitosan derivatives showed significant improvement in superoxide-radical scavenging activity and DPPH radical scavenging activity. Their antifungal activities against two plant pathogenic fungi (Colletotrichum lagenarium and Phomopsis asparagi) were estimated in vitro by hyphal measurement, and all products exhibited excellent antifungal activity. Besides, the cytotoxicity of them was also measured by CCK-8 in vitro on L929 cells, and all samples showed low cytotoxicity. The good biocompatibility and enhanced biological activity of new synthetic chitosan derivatives might be obvious advantages, while applied in wide range of applications as antifungal agents or antioxidants in food, medicine, cosmetics, and other fields., (Copyright © 2020. Published by Elsevier Ltd.)

A class of phenolic-chitosan quaternary ammonium derivatives have been designed and synthesized. Three chitosan derivatives possess effective structure of hydroxycinnamic acid have been obtained through chemical modification to get chitosan derivatives owning high antioxidant activity and antitumor activity. In this study, the scavenging ability of DPPH, hydroxyl (•OH), and superoxide (O 2 •-) free radical and reducing power have been tested to evaluate the antioxidant activity of the synthesized chitosan derivatives. Base on the value of IC 50 , the chitosan derivatives have the best inhibitory property of 0.019 mg/mL (DPPH), 0.016 mg/mL (•OH), and 0.008 (O 2 •-), respectively; and the chitosan derivatives with conjugate structure of ferulic acid and sinapic acid (4b and 4c) show promising antitumor activity toward A549 cells with the IC 50 of 0.046 and 0.052 mg/mL. These data indicate that the chitosan derivatives with phenolic group give much stronger antioxidant activity and antitumor activity. On the other hand, the synthesized chitosan derivatives show no cytotoxicity for L929 cells at the testing concentrations. These results demonstrate that the introduction of phenol group improves the antioxidant activity of chitosan obviously, and the antioxidant or free radical scavenger based on nature polymers and phenol shows potentials application., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

In our previous work, cationic functionalized chitosan was chemically conjugated with superoxide dismutase (SOD) to yield a unique nanoparticle-like conjugate O-HTCC-SOD that has demonstrated superior potential in treating reactive oxygen species (ROS)-related disorders to SOD. Considering contribution of ROS to pathogenesis of osteoarthritis, O-HTCC-SOD was firstly measured for effect on rat chondrocytes exposure to monoiodoacetate (MIA). O-HTCC-SOD was nontoxic to chondrocytes and had more long-acting and intracellular protection effects on chondrocytes against MIA-induced oxidative damage due to its superior elimination of intracellular ROS to SOD. Pharmacokinetic analysis demonstrated that O-HTCC-conjugated SOD significantly prolonged half-life and residence in rat joint cavity, and improved bioavailability compared with unmodified SOD. Intra-articular injection of O-HTCC-SOD significantly attenuated mechanical allodynia in MIA-induced osteoarthritis rats, dramatically suppressed gross morphological and histological lesions of articular cartilage, and greatly enhanced in vivo antioxidant capacity and anti-inflammatory effect. But native SOD had no obvious therapeutic effects. Consequently, the nanoparticle-like conjugate O-HTCC-SOD of the excellent efficacy resulted from its targeted intracellular ROS clearance capability and improved pharmacokinetic profiles, opening up a novel avenue for disease-modifying osteoarthritis drugs., (Copyright © 2020 Elsevier B.V. All rights reserved.)

In this study, a new class of chitosan derivatives possessing sulfonium salts was synthesized, and characterized by FT-IR, 1 H NMR, 13 C NMR, and elemental analyses. IR spectra, 1 H NMR and 13 C NMR of the structural units of these polymers validated the designed chitosan derivatives were successfully synthesized. In addition, the antioxidant potential of chitosan and chitosan derivatives was assessed in vitro, screened by 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging, hydroxyl radical scavenging, and superoxide radical scavenging, respectively. Results revealed that designed chitosan derivatives could effectively scavenge DPPH radical, hydroxyl radical, and superoxide radical with inhibition rate of more than 90% at 1.6 mg/mL, higher than chitosan. Moreover, in the cytotoxicity assay, no cytotoxicity was observed for the L929 cells with chitosan and its derivatives at all the testing concentrations. These results indicated that the acetylated chitosan derivatives containing sulfonium salts may be a promising natural antioxidant for the pharmaceutics, food, cosmetics and agriculture management., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

In this study, 2-urea-chitosan oligosaccharide derivatives (2-urea-COS derivatives) and 2,6-diurea-chitosan oligosaccharide derivatives (2,6-diurea-COS derivatives) were successfully designed and synthesized via intermediate 2-methoxyformylated chitosan oligosaccharide. All samples were characterized and compared based on FT-IR, 1 H NMR spectroscopy, and elemental analysis. The antifungal effects of COS derivatives were tested against Fusarium oxysporum f. sp. niveum, Phomopsis asparagus, and Botrytis cinereal. Their antioxidant properties, including superoxide radicals' scavenging activity, hydroxyl radicals' scavenging activity, and DPPH radicals' scavenging activity were also explored within different concentrations. COS derivatives bearing urea groups showed improved bioactivity compared with pristine COS and 2,6-diurea-COS derivatives had a higher biological activity than 2-urea-COS derivatives in tested concentrations. Additionally, L929 cells were used to carry out cytotoxicity test of COS and COS derivatives by CCK-8 assay. The results indicated that some of samples showed low cytotoxicity. These findings offered a suggestion that COS derivatives bearing urea groups are promising biological materials., Competing Interests: Declaration of Competing Interest The authors have declared no conflicts of interest., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Chitosan is an active biopolymer, and the combination of it with other active groups can be a valuable method to improve the potential application of the resultant derivatives in food, cosmetics, packaging materials, and other industries. In this paper, a series of N , N , N -trimethyl- O -(ureidopyridinium)acetyl chitosan derivatives were synthesized. The combination of chitosan with ureidopyridinium group and quaternary ammonium group made it achieve developed water solubility and biological properties. The structures of chitosan and chitosan derivatives were confirmed by FTIR, 1 H NMR spectra, and elemental analysis. The prepared chitosan derivatives were evaluated for antioxidant property by 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging ability, hydroxyl radical scavenging ability, and superoxide radical scavenging ability. The results revealed that the synthesized chitosan derivatives exhibited improved antioxidant activity compared with chitosan. The chitosan derivatives were also investigated for antifungal activity against Phomopsis asparagus as well as Botrytis cinerea , and they showed a significant inhibitory effect on the selected phytopathogen. Meanwhile, CCK-8 assay was used to test the cytotoxicity of chitosan derivatives, and the results showed that most derivatives had low toxicity. These data suggested to develop analogs of chitosan derivatives containing ureidopyridinium group and quaternary ammonium group, which will provide a new kind of promising biomaterials having decreased cytotoxicity as well as excellent antioxidant and antimicrobial activity.

Polysaccharide-based biodegradable films have been considered as the promising candidates for food packaging industry instead of petroleum-based packaging materials. Here, we reported a class of edible composite films based on chitosan ascorbate and methylcellulose prepared by mixing different ratios (1,0, 4:1, 2:1, 1:1, 1:2, 1:4, and 0:1) of the biopolymers using the casting technique. Their physicochemical properties as well as the DPPH radical scavenging ability and reducing power were investigated. All physicochemical properties and antioxidant activities were significantly affected by the chitosan ascorbate/methylcellulose ratio in the matrix. The increases in tensile strength and elongation at break values, maximum decomposition temperatures, whitish index, compactness, moisture content, and a reduction in water vapor permeability were observed as the proportion of methylcellulose increased in the matrix. But the composite films containing a greater proportion of chitosan ascorbate exhibited the better barrier properties against UV-vis light and the stronger DPPH radical scavenging effect and reducing power. The chitosan ascorbate/methylcellulose composite films with interesting physicochemical properties and strong antioxidant action showed the potential value as biodegradable and edible biomaterials for food packaging., (Copyright © 2019. Published by Elsevier B.V.)

In the current study, five novel urea-functionalized chitosan derivatives were synthesized via condensation reactions of chloroacetyl chitosan (CTCS) with urea groups bearing nitrogen-containing heterocycles. In order to identify the structure characteristics of chitosan derivatives, FT-IR, 1 H NMR spectroscopy, and elemental analysis were carried out. The antifungal activity of the derivatives against four species of phytopathogen (Fusarium oxysporum f. sp. niveum, Phomopsis asparagus, Fusarium oxysporum f. sp. cucumebrium Owen, and Botrytis cinerea) was evaluated. Furthermore, the antioxidant activity of chitosan derivatives was tested by hydroxyl-radical scavenging and superoxide-radical scavenging assays. The results indicated that chitosan derivatives bearing urea groups displayed superior bioactivity compared with chitosan. Besides, L929 cells were adopted for cytotoxicity test of chitosan and synthesized samples by CCK-8 assay and all samples showed decreased cytotoxicity. These results suggested that the novel urea-functionalized chitosan derivatives could be an ideal biomaterial for antifungal and antioxidant applications., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Chemical modification is one of the prominent methods used to improve the water solubility and bioactivity of chitosan. In this paper, a series of quaternary ammonium chitosan derivatives based on 6-O-chloroacetylated chitosan (CAClC) were successfully designed and synthesized. Detailed structural characterization was carried out by means of FT-IR, 1 H NMR spectroscopy, and elemental analysis. Furthermore, the antifungal activity against Botrytis cinerea, Gibberella zeae, and Physalospora piricola Nose was estimated using in vitro hypha measurements. Most of the quaternary ammonium chitosan derivatives showed an inhibitory index of >90% at 1.0 mg/mL and exhibited enhanced antifungal activity when compared to chitosan. On one hand, the higher density of positive charge contributed to the antifungal action. In addition, the inhibitory activity decreased roughly in the order of TriM [(CH 3 ) 3 ] > TriE [(CH 2 CH 3 ) 3 ] > TriP [(CH 2 CH 2 CH 3 ) 3 ] > TriB [(CH 2 CH 2 CH 2 CH 3 ) 3 ]; NNTE [(CH 3 ) 2 (CH 2 CH 3 )] > NNTB [(CH 3 ) 2 (CH 2 CH 2 CH 2 CH 3 )] > NNTK [(CH 3 ) 2 ((CH 2 ) 9 CH 3 )] at 1.0 mg/mL. The antifungal properties of all the quaternary ammonium chitosan derivatives against the targeted fungi decreased upon increasing the alkyl chain length., (Copyright © 2018. Published by Elsevier B.V.)

Chitosan ascorbates with different substitution degrees were synthesized on the basis of salification of chitosan and ascorbic acid at various molar ratios in water and were successfully used to prepare antioxidative films by casting for the first time. Fourier transform infrared and 1 H nuclear magnetic resonance spectra recorded the structural characteristics of all chitosan ascorbates; meanwhile, physicochemical property and antioxidant activity of the produced chitosan ascorbate films were characterized, with chitosan acetate film serving as the control, and these properties were also measured for comparison. The results revealed that salification of chitosan with ascorbic acid not only improved the total color difference, chroma, opacity, capacity for blocking ultraviolet-visible light, and water solubility of chitosan-based films but also decreased water content, swelling degree, and water vapor permeability compared to chitosan acetate film. Also, as was expected, the antioxidant activity assays showed that incorporation of ascorbate into the chitosan matrix effectively enhanced the scavenging activity against the DPPH radical and reducing power. Cs 2 Vc 8 and Cs 2 Vc 6 especially exhibited the strongest scavenging capacities against the DPPH radical (EC 50 < 0.025 mg/mL). These findings offered a suggestion that the prepared chitosan ascorbate films can be applied as novel green oxidation-resistant materials in the food packaging industry.

In this paper, a series of 6-O-imidazole-based quaternary ammonium chitosan derivatives via 6-O-chloroacetyl chitosan (CAClC) were successfully designed and synthesized. Detailed structural characterization was carried out by means of FT-IR and 1 H NMR spectroscopy, and elemental analysis. Furthermore, the antioxidant property against hydroxyl radicals, superoxide radicals, and DPPH radicals was evaluated in vitro. 2-(N,N,N-trimethyl)-6-O-(2-aminobenzimidazole)acetyl chitosan chloride (2NPhMC) and 2-(N,N,N-trimethyl)-6-O-(1-butylimidazole)acetyl chitosan chloride (NBMC) showed more than 90% scavenging indices at 1.6 mg/mL. Besides, the antifungal activity against Botrytis cinerea and Gibberella zeae was estimated using in vitro MIC and hypha measurements. Most of the quaternized chitosan derivatives especially with the long length alkyl chain and primary amino group showed an inhibitory index of > 85% at 1.0 mg/mL against Botrytis cinerea. Besides, the cytotoxicity of chitosan and all the quaternized chitosan derivatives was evaluated in vitro on HaCaT cells and all the quaternized chitosan derivatives bearing 6-O-imidazole exhibited low cytotoxicity. These results suggested that chitosan derivatives bearing 6-O-imidazole-based quaternary ammonium salts may be used as good biomaterials., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

In this work, quaternary ammonium group was introduced into chitosan backbone by cuprous-catalyzed azide-alkyne cycloaddition (CuAAC) to synthesize the cationic chitosan derivative bearing 1,2,3-triazole. The products were identified structurally by FTIR, 1 H NMR spectroscopy, XRD, and elemental analysis. The water solubility of chitosan derivatives at different pH values was determined by a turbidity measurement. The antifungal properties of cationic chitosan derivatives against Botryis cinerea, Phomopsis asparagi, Fusarium oxysporum f. sp. niveum, and Fusarium oxysporum f. sp. cucumerium were evaluated using the radial growth assay. Besides, the antioxidant activities of them were also tested by superoxide-radical scavenging and reducing power assays. Compared to chitosan, cationic chitosan derivative bearing 1,2,3-triazole showed the good water solubility especially at alkaline condition, excellent antifungal action with over 70% inhibitory indices against tested fungi at 1.0 mg/mL, and enhanced antioxidant activity with complete scavenging efficiency against superoxide-radical at 1.6 mg/mL because of the introduction of 1,2,3-triazole and quaternary ammonium moieties. These excellent biological properties present a promising prospect for this chitosan derivative in antifungal and antioxidant biomaterials., (Copyright © 2018. Published by Elsevier B.V.)

Chitosan, possessing excellent properties, has been drawing broad attention. For the further utilization of chitosan, chemical modification is performed in improving its water solubility and the bioactivities. In the current study, four N,N,N-trimethyl chitosan salts, including N,N,N-trimethyl chitosan citrate (TMCSCi), N,N,N-trimethyl chitosan acetylsalicylate (TMCSAc), N,N,N-trimethyl chitosan ascorbate (TMCSAs), and N,N,N-trimethyl chitosan gallate (TMCSGa), were prepared via N,N,N-trimethyl chitosan iodide (TMCSI). The as-prepared products were characterized by FT-IR and 1 H NMR. Meanwhile, the degrees of substitution were calculated by elemental analysis results. Furthermore, scavenging activities (against DPPH radicals and superoxide radicals) test and reducing power test were selected to evaluate the antioxidant property of N,N,N-trimethyl chitosan salts in vitro. The results indicated that TMCSAs and TMCSGa displayed excellent activity, probably due to the enhancement of ascorbate and gallate in antioxidant activity. However, because of the weak antioxidant property of citrate and acetylsalicylate, the activity was lower for TMCSCi and TMCSAc. For example, in the DPPH radicals scavenging assay, the scavenging rates of chitosan, TMCSI, TMCSCi, TMCSAc, TMCSAs, and TMCSGa were 25.22, 84.11, 6.90, 2.70, 94.92, and 96.75% at 0.4 mg/mL, respectively. Generally, TMCSAs and TMCSGa could be regarded as a potential source of antioxidants., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Hydroxypropyltrimethyl ammonium chitosan halogenated acetates were successfully synthesized from six different haloacetic acids and hydroxypropyltrimethyl ammonium chloride chitosan (HACC) with high substitution degree, which are hydroxypropyltrimethyl ammonium chitosan bromacetate (HACBA), hydroxypropyltrimethyl ammonium chitosan chloroacetate (HACCA), hydroxypropyltrimethyl ammonium chitosan dichloroacetate (HACDCA), hydroxypropyltrimethyl ammonium chitosan trichloroacetate (HACTCA), hydroxypropyltrimethyl ammonium chitosan difluoroacetate (HACDFA), and hydroxypropyltrimethyl ammonium chitosan trifluoroacetate (HACTFA). These chitosan derivatives were synthesized by two steps: first, the hydroxypropyltrimethyl ammonium chloride chitosan was synthesized by chitosan and 3-chloro-2-hydroxypropyltrimethyl ammonium chloride. Then, hydroxypropyltrimethyl ammonium chitosan halogenated acetates were synthesized via ion exchange. The structures of chitosan derivatives were characterized by Fourier transform infrared spectroscopy (FTIR), ¹H Nuclear magnetic resonance spectrometer (¹H NMR), 13 C Nuclear magnetic resonance spectrometer ( 13 C NMR), and elemental analysis. Their antifungal activities against Colletotrichum lagenarium , Fusarium graminearum , Botrytis cinerea , and Phomopsis asparagi were investigated by hypha measurement in vitro. The results revealed that hydroxypropyltrimethyl ammonium chitosan halogenated acetates had better antifungal activities than chitosan and HACC. In particular, the inhibitory activity decreased in the order: HACTFA > HACDFA > HACTCA > HACDCA > HACCA > HACBA > HACC > chitosan, which was consistent with the electron-withdrawing property of different halogenated acetates. This experiment provides a potential idea for the preparation of new antifungal drugs by chitosan.

As an abundant and renewable polysaccharide, chitosan has been drawing broad attention due to its natural properties. For the further utilization of chitosan, chemical modification can be applied in improving its water solubility and the bioactivities. In this study, four chitosan derivatives were synthesized by the reaction of chloracetyl chitosan derivative with quaternary ammonium salt (CTCS) and urea groups bearing 4-amino-pyridine, including BCTCS, 2CBCTCS, 3CBCTCS, and 4CBCTCS. The structure characteristics of synthesized products were established based on FT-IR spectroscopy, 1 H NMR, and elemental analysis. Their antifungal activities against Fusarium oxysporum f. sp. niveum, Phomopsis asparagus, Fusarium oxysporum f. sp. cucumebrium Owen, and Botrytis cinerea were estimated by hyphal measurement in vitro. Generally, the inhibition ratio of most products was higher than 80% at 1.0mg/mL. Their inhibitory activity decreased roughly in the order: 4CBCTCS>3CBCTCS>2CBCTCS>BCTCS>CTCS>chitosan, resulted from the different degrees of substitution of the effectively active groups-urea groups. Meanwhile, the effects on beneficial soil microbes, including Bacillus cereus, Bacillus subtilis, and Sinorhizobium saheli LMG7837, of these synthesized chitosan derivatives were evaluated by disk diffusion method. The results showed that these substances do not inhibit the growth of beneficial bacteria and some of them could be employed as green antifungal biomaterials., (Copyright © 2017 Elsevier B.V. All rights reserved.)

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, 13 C 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., Competing Interests: The authors declare no conflict of interest.

In this paper, novel cationic chitosan derivative possessing 1,2,3-triazolium and pyridinium groups was synthesized conveniently via cuprous-catalyzed azide-alkyne cycloaddition (CuAAC) and methylation. FTIR, 1 H NMR, and elemental analysis examined the structural characteristics of the synthesized derivatives. The antifungal efficiencies of chitosan derivatives against three plant-threatening fungi were assayed by hypha measurement in vitro. The determination showed that chitosan derivative bearing 1,2,3-triazolium and pyridinium displayed tremendously enhanced antifungal activity as compared with chitosan and chitosan derivative bearing 1,2,3-triazole and pyridine. Notably, the inhibitory indices of it against Colletotrichum lagenarium attained 98% above at 1.0mg/mL. The results showed that N-methylation of 1,2,3-triazole and pyridine could effectively enhance antifungal activity of the synthesized chitosan derivatives. Besides, the prepared chitosan derivatives showed non-toxic effect on cucumber seedlings. This synthetic strategy might provide an effective way and notion to prepare novel cationic chitosan antifungal biomaterials., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

We synthesized 6-amino-6-deoxychitosan (NCS) through a series of reactions from chitosan (CS). The antioxidant ability of CS and NCS were investigated in vitro, including that of DPPH-radical and hydrogen peroxide, reducing power, chelating abilities and inhibition of lipid peroxidation. As expected, after the introduction of amino groups, antioxidant ability had improved significantly. Especially, scavenging effect against DPPH-radical and hydrogen peroxide of NCS were 97% and 92% at 1.6mg/mL, respectively. Moreover, inhibition of lipid peroxidation was 57% at 0.1mg/mL. And the reducing power of NCS was 0.68 at 0.8mg/mL. Meanwhile, inhibitory effects against four fungi were also tested. Antifungal activity of NCS were better than those of CS and antifungal activity had improved more than 20% at 0.5mg/mL against these four kinds of plant pathogens. Based on the above results, it was reasonable to speculate that the obtained antioxidant ability and antifungal activity of NCS might benefit from amino groups on chitosan backbone. These in vitro results suggest the possibility that NCS as antioxidant compound could be effectively alleviate oxidative stress and thus inhibit the oxidative mechanisms that lead to degenerative diseases., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Two novel chitosan derivatives modified with quaternary phosphonium salts were successfully synthesized, including tricyclohexylphosphonium acetyl chitosan chloride (TCPACSC) and triphenylphosphonium acetyl chitosan chloride (TPPACSC), and characterized by FTIR, 1 H NMR, and 13 C NMR spectra. The degree of substitution was also calculated by elemental analysis results. Their antifungal activities against Colletotrichum lagenarium, Watermelon fusarium, and Fusarium oxysporum were investigated in vitro using the radial growth assay, minimal inhibitory concentration, and minimum bactericidal concentration assay. The fungicidal assessment revealed that the synthesized chitosan derivatives had superior antifungal activity compared with chitosan. Especially, TPPACSC exhibited the best antifungal property with inhibitory indices of over 75% at 1.0mg/mL. The results obviously showed that quaternary phosphonium groups could effectively enhance antifungal activity of the synthesized chitosan derivatives. Meanwhile, it was also found that their antifungal activity was influenced by electron-withdrawing ability of the quaternary phosphonium salts. The synthetic strategy described here could be utilized for the development of chitosan as antifungal biomaterials., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Different forms of biomaterials, including microspheres, sponges, hydrogels and nanofibres have been broadly used in cartilage regeneration; however, effects of internal structures of biomaterials on chondrogenesis of mesenchymal stem cells (MSCs) remain largely unexplored. Here we investigated the effect of physical microenvironments of sponges and hydrogels on chondrogenic differentiation of MSCs. MSCs, cultured in these two scaffold systems, were induced with TGF-β3 in chondrogeneic differentiation medium and the chondrogenic differentiation was evaluated and compared after three weeks. MSCs in the sponges clustered with spindle morphologies, while they distributed homogenously with round morphologies in the hydrogel. The MSCs proliferated faster in the sponge compared to that in the hydrogel. Significantly higher glycosaminoglycan and collagen II were found in the sponges but not in the hydrogels. The different tissue formation ability of MSCs in these two systems could be attributed to the different metabolic requirements and the cellular events prerequisite in the chondrogenic process of MSCs. It is reasonable to conclude that sponges with relatively active microenvironments that facilitate cell-cell contacts and cell-matrix interaction are optimal for early stage of chondrogeneic differentiation.

Based on the enhancing effect of chitosan (CS) on luminol-dissolved oxygen chemiluminescence (CL) reaction, a flow injection (FI) luminol-CS CL system was established. It was found that the increase of CL intensity was proportional to the concentrations of CS ranging from 0.7 to 10.0 μmol l(-1). In the presence of chlortoluron (CTU), the CL intensity of luminol-CS system could be obviously inhibited and the decrements of CL intensity were linearly proportional to the logarithm of CTU concentrations ranging from 0.01 to 70.0 ng ml(-1), giving the limit of detection 3.0 pg ml(-1) (3σ). At a flow rate of 2.0 ml min(-1), the whole process including sampling and washing could be accomplished within 36 s, offering a sample throughput of 100 h(-1). The proposed FI-CL method was successfully applied to the determination of CTU in soil samples with recoveries ranging from 95.0 % to 105.3 % and the relative standard deviations (RSDs) of less than 4.0 %.

Salinity is an obstacle to global agriculture, as it affects plant growth and development. Chitosan (CTS) has been suggested as a plant growth regulator to alleviate environmental stresses. In this study, the morphological and biochemical responses of chitosan application (75 mg L−1) on maize seedling growth under salt stress (150 mM) were conducted with a hydroponic experiment. The results exhibited that CTS application effectively recovered salt-inhibited biomass accumulation and root architecture by increasing chlorophyll content and photosynthetic assimilation and reducing sodium content in shoots and roots by 25.42% and 5.12% compared with NaCl treatment. Moreover, salt-induced oxidative stress was alleviated by CTS application by increasing the activities of antioxidant enzymes of superoxide dismutase, catalase, ascorbate peroxidase, peroxidase and content of ascorbate. Correlation analysis and partial least squares (PLS) analysis revealed that root morphology and ascorbate play key roles for maize seedlings in response to salt stress. Based on these results, CTS application is recommended as an effective approach to enhance the tolerance of maize seedlings under salt stress. [ABSTRACT FROM AUTHOR]

In this study, five new chitosan oligosaccharide quaternary ammonium derivatives bearing quinoline are synthesized by reaction between 6‐O‐chloroacetyl‐2‐N, N, N‐trimethyl quaternary ammonium salt chitosan oligosaccharide (CTCOS, compound 1) and quinoline derivatives. The derivatives are characterized by analytical techniques including Fourier Transform Infrared (FTIR), 1H Nuclear Magnetic Resonance (1H NMR) spectroscopy, and elemental analysis. The obtained results confirm that quinoline groups are successfully introduced into the CTCOS molecule. Meanwhile, the antioxidant activities of the prepared chitosan oligosaccharide derivatives are evaluated in vitro. The experimental results show that the derivatives have excellent free radical scavenging ability. The free radical scavenging abilities are all over 75% at the concentration of 1.6 mg mL−1. Moreover, antibacterial tests show that derivative 2e has the best antibacterial activities. Its minimum inhibitory concentration (MIC) value and minimum bactericidal concentration (MBC) value against Staphylococcus aureus and Escherichia coli are 0.0625 and 0.03125 mg mL−1, respectively. In addition, the cytotoxicity of chitosan oligosaccharide and its derivatives is examined by MTT colorimetric assay in RAW 264.7 macrophages, observing that all derivatives are non‐cytotoxic. Consequently, the findings indicate that the enhanced antioxidant activity, antibacterial activity, and biocompatibility of these chitosan oligosaccharide derivatives can enlarge the scope of the application of chitosan oligosaccharides, particularly as antioxidant and antibacterial agents in food packaging, pharmaceutical, cosmetics industries, and other fields. [ABSTRACT FROM AUTHOR]

As a reactive intermediate, chloracetyl chitosan oligosaccharide (CACS) can be nucleophilic substituted by some bioactive groups to give novel derivatives of chitosan oligosaccharide (COS). The Schiff bases of pyridine‐4‐aldehyde are grafted onto CACS to give four COS derivatives in this paper. Specific structural characterization is implemented by fourier‐transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). The degree of substitution (DS) of COS derivatives is quantitatively calculated by ratio of hydrogen proton integral. Their antioxidant property is evaluated using free radical scavenging assay towards 1,1‐diphenyl‐2‐picrylhydrazyl (DPPH) and superoxide anion radicals, and the antibacterial activity against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) is also investigated. The results revealed that the pyridine‐4‐aldehyde Schiff bases grafted chloracetyl chitosan oligosaccharide derivatives showed better antioxidant activity as well as antibacterial activity than COS and CACS, which may be related to the positive charge of these derivatives. Among all final products, derivative BPCACS with the highest DS has the best bioactivity with scavenging rate of 91.49% for the DPPH assay and inhibition diameter of 39.25 mm for S. aureus inhibitory assay, respectively. These results indicated that COS derivatives with enhanced biological activities could serve as potential biomaterial for antioxidant and antibacterial applications. [ABSTRACT FROM AUTHOR]

To improve the solubility and bioactivity of chitosan, a new class of carboxymethyl chitosan derivatives possessing sulfonium salts was successfully designed and synthesized, including Methyl sulfide carboxymethyl chitosan (MCMCS), Ethyl sulfide carboxymethyl chitosan (ECMCS), Propyl sulfide carboxymethyl chitosan (PCMCS), and Butyl sulfide carboxymethyl chitosan (BCMCS). To determine the structure of the new class of the derivatives, methods of the Fourier transform infrared spectroscopy (FT-IR), 1H nuclear magnetic resonance spectrometer (1H NMR), and 13C nuclear magnetic resonance spectrometer (13C NMR) were used. Moreover, the antioxidant activity of the derivatives for three types of free radicals, i.e., hydroxyl radical, superoxide radical, and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical was evaluated in vitro. In addition, the L929 cells were adopted to test the cytotoxicity of chitosan and its derivatives by CCK-8 assay. The class of the carboxymethyl chitosan derivatives showed a strong scavenging ability against the three free radicals at 1.6 mg/mL, with scavenging rate of over 70% and some up to 100%. At this high rate, the overall cell viability in the toxicity test reached more than 80%, indicating that the synthetic derivative had a little cytotoxicity. The results show that the introduction of carboxymethyl group to chitosan increased the water-solubility of chitosan, and the combination of sulfonate ions with different chain lengths further enhanced the antioxidant activity of chitosan. Therefore, the sulfonium-containing carboxymethyl chitosan derivatives had excellent bioactivity with good application prospects in food, biomedicine, and medical fields. [ABSTRACT FROM AUTHOR]

Eight novel chitosan derivatives bearing urea groups are designed and synthesized. Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance spectrometer, and elemental analysis are performed to confirm the structural characteristics of chitosan derivatives. The antioxidant activities, including superoxide radicals' scavenging activity, 1,1‐diphenyl‐2‐picrylhydrazyl radicals' scavenging activity, and hydroxyl radical' scavenging activity, of the derivatives are explored within different concentrations in the reaction system. In vitro fungicidal activity of these compounds is further tested against Fusarium oxysporum f. sp. niveum, Phomopsis asparagus, F. oxysporum f. sp. cucumebrium Owen, and Botrytis cinerea, respectively, particularly compounds exhibit significant control effect at 1.0 mg mL−1. The experimental results indicate that the products bearing urea groups show enhanced antifungal property and antioxidant activity compared with pristine chitosan. Meanwhile, their bioactivities follow some regularity on the whole, that is, they are related to the electron‐withdrawing property of the different substituted groups of urea. Derivatives with stronger electron‐withdrawing property will have higher biological activities. L929 cells are used to carry out cytotoxicity test of chitosan and chitosan derivatives by Cell Counting Kit‐8 assay. The results indicate that some of the samples show low cytotoxicity. This research will be helpful to broaden the application of chitosan in materials. [ABSTRACT FROM AUTHOR]

Chitosan (CTS) constitutes a promising area in treatment of nose-related diseases as a nasal drug delivery carrier. Astragalus polysaccharide (APS) significantly attenuates eosinophils and neutrophil-dominant airway inflammation, and it has a potential pharmaceutical application in the treatment of severe asthma. The purpose of this work was to prepare APS/CTS microspheres intended for nasal drug delivery by the spray-drying method. The characteristics of APS/CTS microspheres were evaluated by a scanning electron microscope, Fourier transform infrared spectroscopy, differential scanning calorimetry, and in vitro drug release. The effect of APS/CTS microspheres on rats with allergic rhinitis (AR) was investigated by eosinophil and neutrophil counts in nasal lavage fluid. Results of SEM showed that microspheres were spherical and wrinkled. In vitro release showed that 67.48–93.76% APS was released from APS/CTS microspheres at pH 6.8 within 24 h. The effects showed that APS/CTS microspheres alleviated allergic symptoms and reduced eosinophils infiltration and the expression of interleukin-4 in the nasal mucosa tissue of rats that had no liver and kidney toxicity by hematoxylin-eosin staining observation. In conclusion, these results indicated that APS/CTS microspheres had excellent characteristics for the treatment of AR. [ABSTRACT FROM AUTHOR]

Amino functionality has been paid growing attention in chemical modification of polysaccharides due to their potential biomedical applications. Here, the preparation of novel antioxidant materials based on chitosan derivatives bearing amino-containing groups equipped with 1,2,3-triazole and 1,2,3-triazolium by Cuprous-catalyzed azide-alkyne cycloaddition and N -methylation was described for the first time. The structural characteristics of the synthesized derivatives were examined by FTIR, 1 H NMR, and elemental analysis. The antioxidant activities of the chitosan derivatives were assessed in vitro . The results indicated that chitosan derivatives bearing 1,2,3-triazoles displayed superior antioxidant activity over pristine chitosan, especially against superoxide anion radical. Moreover, antioxidant efficiency of chitosan derivatives further enhanced after N -methylation of 1,2,3-triazole moieties with iodomethane, which is comparative to that of ascorbic acid. Notably, of all chitosan derivatives bearing 1,2,3-triazole or 1,2,3-triazolium moieties, acylhydrazine-functionalized and amino-functionalized chitosan showed the stronger antioxidant capacity than hydroxyl-modified chitosan at the test concentration. Besides, the cytotoxicities of them were also evaluated in vitro on HaCaT cells. These results suggested that amino and acylhydrazine-functionalized chitosan derivatives with 1,2,3-triazolium could be used as novel antioxidant biomaterials. [ABSTRACT FROM AUTHOR]

Chemical modification of chitosan is one of effective methods to improve the biological activity of chitosan. In this paper, aminoethyl chitosan quaternary ammonium salts, including N‐trimetyl quaternary ammonium salt chitosan (TMC), 6‐O‐(aminoethyl)‐2‐trimethyl quaternary ammonium chitosan derivative (ONC), and 6‐N‐(aminoethyl)‐2‐trimethyl quaternary ammonium chitosan derivative (NNC), are successfully designed, synthesized, and characterized by FT‐IR, 1H NMR, and elemental analyses. Moreover, three kinds of antifungal activities, including B. cinerea Pers., Gibberella zea, and P. asparagi, are all tested by hyphal measurement in vitro. The results show that all chitosan derivatives have better antifungal activities than chitosan. And the antifungal activity decrease in the order: NNC>ONC >TMC>chitosan at 1.0 mg mL−1. Furthermore, the inhibitory indices of NNC and ONC against three kinds of phytopathogens are higher than 75% at 1.0 mg mL−1. Especially, the inhibitory index of NNC against B. cinerea Pers. attain even 90% at 1.0 mg mL−1. These data demonstrate that the aminated chitoan derivative could remarkably improve the antifungal activity of chitosan. On the one hand, the higher positive charge would interact with the anionic components to damage the cell wall. On the other hand, based on the “permeability” point, the aminoethyl as lipophilic group might pass the oil film into the cell. [ABSTRACT FROM AUTHOR]

Here, α-lipoic acid (LA) was grafted onto chitosan via EDC/NHS to improve the antioxidant effect. Chitosan acetate was innovatively used as precursor replaced pristine chitosan to synthesize α -lipoic acid grafted chitosan derivatives with different grafting ratios. The grafting ratio of LA-g-CS conjugates could be controlled by adjusting the reaction temperature, reaction time, and feed ratio of α-lipoic acid to anhydroglucose unit, and the feed ratio is the main factor on the grafting efficiency. The antioxidant results (superoxide anion, hydroxyl, and DPPH radicals scavenging activities, and reducing power) indicated that LA-g-CS displayed significantly enhanced antioxidant activity over pristine chitosan. Moreover, antioxidant efficiency of LA-g-CS showed an ascending tendency with the increasing of the grafting degree. The present study provided a novel synthesis strategy for preparation of α-lipoic acid grafted chitosan derivatives that could be a potential antioxidant biomaterial in food and biomedical industries. [Display omitted] • α-Lipoic acid was successfully grafted onto chitosan via EDC/NHS coupling method. • Chitosan acetate was firstly prepared to synthesize conjugates instead of chitosan. • The feed ratio of LA to AGU is the main factor on the grafting efficiency. • Grafting of α -lipoic acid could significantly improve the antioxidant activities. • Antioxidant ability was enhanced with test concentrations and grafting ratios. [ABSTRACT FROM AUTHOR]