Elsevier

Carbohydrate Polymers

Volume 160, 15 March 2017, Pages 163-171
Carbohydrate Polymers

Novel 1,2,3-triazolium-functionalized starch derivatives: Synthesis, characterization, and evaluation of antifungal property

https://doi.org/10.1016/j.carbpol.2016.12.060Get rights and content

Highlights

  • Four starch derivatives bearing 1,2,3-triazole were synthesized via CuAAC.

  • Four starch derivatives bearing 1,2,3-triazolium were also obtained.

  • Starch derivatives bearing 1,2,3-triazolium showed superduper antifungal activity.

  • Alkyl chain length was an important determinant of antifungal activity.

Abstract

Four novel 1,2,3-triazolium-functionalized starch derivatives were synthesized by N-alkylating the precursor starch derivatives with 1,2,3-triazole with iodomethane based on cuprous-catalyzed azide-alkyne cycloaddition (CuAAC). The detailed structural characterization was investigated by means of FTIR, UV-vis, 1H NMR, and 13C NMR spectra. The antifungal activities of starch derivatives against Colletotrichum lagenarium, Fusarium oxysporum, and Watermelon fusarium, were then assayed by hypha measurement in vitro. The fungicidal assessment revealed that compared with starch and starch derivatives with 1,2,3-triazole, 1,2,3-triazolium-functionalized starch derivatives displayed tremendously enhanced antifungal activity. Especially, the inhibitory indices of 6-(4-hydroxymethyl-3-methyl-1,2,3-triazolium-1-yl)-6-deoxy starch iodine (2a) with against the tested plant threatening fungi attained 70% above at 1.0 mg/mL. It was also found that their antifungal activity profiles were dependent on the variation in alkyl chain length. As novel 1,2,3-triazolium-functionalized starch derivatives could be prepared efficiently and exhibited superduper antifungal activity, this synthetic strategy might provide an effective way and notion to prepare novel antifungal biomaterials.

Introduction

As the principal carbohydrate storage reserve for plants and the major source of energy in the human diet and animal feed, starch is composed of anhydroglucose units (AGU) linked together by α-glucosidic bonds (Fuentes et al., 2016). The increasing interest in starch-based biomaterials is due to its interesting properties such as cheap, renewable, biodegradable, and biocompatible (Li et al., 2017, Umar et al., 2016), which can facilitate a certain degree of applications of starch in biomedicine, biomaterials, and textile areas (Ahmed, Thomas, Taher, & Joseph, 2016; Nguyen Vu & Lumdubwong, 2016). However, chemical modification via introduction of the individual functional moieties to starch backbone is often necessary in order to further improve the bioactivity and broaden application scope of new valuable biomaterials based on starch (Adak & Banerjee, 2016; Biduski et al., 2017; Kapelko-Zeberska, Zieba, Spychaj, & Gryszkin, 2015).

1,2,3-Triazole moieties have recently gained an increasing interest due to their modular synthesis through cuprous-catalyzed azide-alkyne cycloaddition (CuAAC) (Kraljevic et al., 2016). The wide range of biological properties, such as antimicrobial, anticancer, and antimalarial (Kant, Singh, Nath, Awasthi, & Agarwal, 2016), have facilitated the chemical modification of starch with 1,2,3-triazole moieties to achieve the rapid growth of application scope of starch. Uliniuc et al. (2013) reported that the polycaprolactone-grafted starch copolymers obtained by click chemistry were able to form micelles in an aqueous solution and had potential to be used in controlled drug delivery and cosmetics. The antibacterial-starch biomaterials could be obtained by anchoring the strong electron-withdrawing groups onto the starch backbone by the CuAAC reaction (Tan, Li, Li, Dong, & Guo, 2016). Very recently, the synthesis of 1,2,3-triazolium groups by N-alkylating 1,2,3-triazole with alkyl halides begins to be paid close attention as they combine the interesting properties of ionic liquids and the versatile mechanical and broad-spectrum properties and applications of polymers and catalysis (Abdelhedi-Miladi et al., 2014; Mudraboyina et al., 2014; Ohmatsu, Hamajima, & Ooi, 2012). However, although the 1,2,3-triazole-linked starch derivatives have been reported and described, to date there are surprisingly very few reports describing the preparation of starch derivatives bearing 1,2,3-triazolium. Our group has recently pioneered the synthesis of starch derivative bearing 1,2,3-triazolium and pyridinium and this novel starch derivative showed strong antifungal activity because of the combined effect of 1,2,3-triazolium and pyridinium groups (Tan et al., 2017). However, the single influence of the alkylation of 1,2,3-triazole on the bioactivity of starch derivatives was still unknown. Although, many studies have reported that the length of alkyl groups had important influence on bioactivity of compounds (Tang et al., 2015), the effect of the length of alkyl groups in 1,2,3-triazolium moieties on the bioactivity of starch derivatives is still unknown.

The present study attempts to understand the structure-property relationships of 1,2,3-triazolium-functionalized starch derivatives with different alkyl chain length by quaternization of starch derivatives with 1,2,3-triazole issued from CuAAC. The impact of the length of alkyl groups in 1,2,3-triazolium moieties on the antifungal activity was investigated. The chemical structures of the starch derivatives were characterized using FTIR, UV-vis, 1H NMR, and 13C NMR spectra as well as elemental analysis. Three plant-threatening fungi, including Colletotrichum lagenarium (C. lagenarium), Fusarium oxysporum (F. oxysporum), and Watermelon fusarium (W. fusarium), were selected to evaluate the antifungal property of starch and starch derivatives by hypha measurement in vitro.

Section snippets

Material

Soluble starch from potato (granules) with weight-average molecular weight of 9.8 × 104 Da, was purchased from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China) and used without any further purification. N-bromosuccinimide (NBS), triphenylphosphine (TPP), 2-propyn-1-ol, 3-butyn-1-ol, 4-pentyn-1-ol, 5-hexyn-1-ol, and methyl iodide were purchased from the Sigma-Aldrich Chemical Corp (Shanghai, China). The other reagents were all analytical grade and used as received.

Fourier transform infrared (FTIR) spectroscopy

All spectra were recorded on

Chemical synthesis and characterization

The synthetic strategy for the preparation of 1,2,3-triazolium-functionalized starch derivatives is outlined in Scheme 1. There are three hydroxyl groups in anhydroglucose unit (AGU) of starch, a primary hydroxyl at C-6 and two secondary hydroxyls at C-2 and C-3. Thereinto, the primary hydroxyl at C-6 is the highest chemical reactive site because of minimal steric hindrance (Zhang & Edgar, 2014). Starch therefore can be brominated with regioselectivity at C-6, which should be benefit from the

Conclusion

In summary, we have proposed a straightforward synthetic route to novel 1,2,3-triazolium-functionalized starch derivatives with alkyl chains of various lengths by associating CuAAC step with efficient alkylation of 1,2,3-triazole with iodomethane. FTIR, UV-vis, 1H NMR, and 13C NMR spectra, and elemental analysis confirmed that 1,2,3-triazolium moieties had been successfully introduced to the starch backbone. The antifungal activity against three kinds of plant threatening fungal strains was

Acknowledgements

This work was supported by a grant from the National Natural Science Foundation of China (41576156), Shandong Province Science and Technology Development Plan (2015GSF121045), and Yantai Science and Technology Development Plan (2015ZH078), and the Public Science and Technology Research Funds Projects of Ocean (No. 201505022-3).

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