Synthesis, characterization, and evaluation of antifungal and antioxidant properties of cationic chitosan derivative via azide-alkyne click reaction
Introduction
Chitosan, obtained from deacetylation of chitin, is one of the most abundant polyaminosaccharides [1]. Chitosan is a polycationic complex biopolymer that has an amino group at the 2-position of the glucosamine ring in a repeating glucosidic residue rather than a hydroxyl group compared with cellulose [2]. The concept of utilizing chitosan as an ideal biomaterial in the biomedical, pharmaceutical, agricultural, cosmetics, and food fields has received significant attention [3,4], due to its outstanding characteristics such as biocompatibility, biodegradability, and nontoxicity [[5], [6], [7]]. However, the main challenge in the wide utilization of chitosan is its insoluble nature in both organic and aqueous solvents at neutral pH [8,9]. To overcome this, tremendous efforts have been devoted to chemical modifications through the introduction of hydrophilic groups [4,10,11].
The modification of chitosan with cationic moieties has been performed by N,N,N-trialkylation of the amino group or by directly grafting cationic small molecules with covalent bond onto the primary amino and hydroxyl groups of chitosan backbone [12], because of cationic chitosan derivatives have particular characteristics such as improved water solubility over a broad pH range and excellent bioactivities such as antimicrobial and antioxidant activities [[13], [14], [15]]. Among the cationic chitosan derivatives, N,N,N-trimethyl chitosan and (2-hydroxy-3-trimethylammonium) propyl chitosan chloride have received particular attention [16]. The latter was usually prepared by etherification of chitosan and glycidyl trimethylammonium chloride in isopropyl alcohol or water [17]. Recently, the cuprous-catalyzed azide-alkyne cycloaddition (CuAAC) termed by Sharpless and coworkers [18] has been introduced into the chemical modification of chitosan due to its high specificity, modularity, tolerant to other functional groups [19,20]. Now our interest is in the preparation of cationic chitosan derivative by quaternization of amino group at C-2 and the introduction of N,N,N-trimethyl moiety into hydroxyl groups at C-3 or C-6 by CuAAC reaction simultaneously and its antifungal and antioxidant activities.
In the following, we aim to develop novel cationic chitosan derivative bearing 1,2,3-triazole via efficient CuAAC reaction. The chemical structure of cationic chitosan derivative was characterized in details by FTIR, 1H NMR, and elemental analysis. The water solubility of the synthesized chitosan derivatives were also evaluated by a turbidity measurement. The antifungal activity of the derivatives against the four plant-threatening fungi, Botryis cinerea (B. cinerea), Phomopsis asparagi (P. asparagi), Fusarium oxysporum f. sp. niveum (F. oxysporum f. sp. niveum), and Fusarium oxysporum f. sp. cucumerium (F. oxysporum f. sp. cucumerium), was evaluated by hypha measurement in vitro. Meanwhile, the antioxidant activity was also investigated by the assessment of superoxide-radical scavenging activity and reducing power.
Section snippets
Materials
Chitosan (molecular weight 200 kDa, the degree of deacetylation 83%) was supplied from Qingdao Baicheng Biochemical Corp. (Qingdao, China). 1,2-Dibromoethane (99%), iodomethane (98%), and propargyl bromide (80 wt% in toluene) were obtained from the Sigma-Aldrich Chemical Corp (Shanghai, China). Sodium azide (AR), magnesium sulfate (AR), trimethylamine (33 wt% in ethanol), sodium iodide (98%), sodium hydroxide (AR), triethylamine (AR), cuprous iodide (AR), N,N-dimethylformamide (DMF, AR),
Chemical synthesis and characterization
Cationic chitosan derivative bearing 1,2,3-triazole group was prepared via CuAAC reaction between cationic propargyl chitosan derivative 2 and N,N,N-trimethyl-N-(2-azido)-ethyl ammonium bromide (Scheme 1. Moreover, in order to improve the solubility and reaction efficiency of pristine chitosan in organic solvents, cationic propargyl chitosan derivative 2 was synthesized by N,N,N-trimethylation of amino group followed by propargylation of chitosan subsequently in the alkaline condition. And N,N,N
Conclusion
In present study, we successfully prepared cationic chitosan derivative bearing 1,2,3-triazole and N,N,N-trimethyl moieties using a facile cuprous-catalyzed azide-alkyne click chemistry approach. The synthesized cationic chitosan derivative showed the good water solubility over the entire pH values range at the concentration of 1.0 mg/mL. Moreover, the cationic chitosan derivative bearing 1,2,3-triazole exhibited enhanced antifungal activity against four kinds of plant threatening fungal
Acknowledgements
This work was supported by a grant from the National Natural Science Foundation of China (41576156), Natural Science Foundation of Shandong Province of China (ZR2017BD015), Science and Technology Service Network Initiative of Chinese Academy of sciences (KFJ-STS-ZDTP-023), and the Public Science and Technology Research Funds Projects of Ocean (No. 201505022-3).
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2021, International Journal of Biological MacromoleculesCitation Excerpt :The spectrum of CS exhibited a broad band centered at 3441 cm−1 attributed to the overlapping of OH and NH stretching of –OH and –NH2 groups, bands in 2920–2870 cm−1 region due to CH stretching of CH2 and CH3 groups, and bands at 1647 and 1605 cm−1 due to due to amide I and NH bending of –NH2 groups and amide II bonds [21,38]. Additionally, bands at 1457, 1381, 1158, and 1032 cm−1 are attributed to CH2 bending, CH3 symmetrical deformation, antisymmetric stretching, and skeletal stretching of C-O-C and CO bonds of the glucosamine ring [7]. For CS-N3, the broadband in the 3700–3000 cm−1 region becomes sharper and the band at 1605 cm−1 almost disappeared suggesting the partial consumption of the –NH2 groups of CS before the azidation reaction.