Cellulose fibers modification through metal-free click chemistry for the elaboration of versatile functional surfaces

https://doi.org/10.1016/j.eurpolymj.2020.109866Get rights and content

Highlights

  • Heterogenous « click » reaction without metal on cellulose.

  • Activation of the surface of cellulose with bicyclononyne group.

  • XPS analysis highlight the substitution degree at the surface of cellulose.

Abstract

In the present work, a novel and versatile way was developed to functionalize cellulose fibers from wipes under heterogeneous conditions. The technic was based on metal-free click chemistry to avoid the persistence of any metal traces on cellulose. First, cellulose fibers were covalently pre-functionalized with bicyclononyne (BCN) to promoted azide-alkyne addition with molecules of interest, like coumarin and β-cyclodextrin derivatives. X-ray photoelectron microscopy (XPS) shows that one BCN group per cellulose unit was modified at the surface of the wipe. 3-azido-7-hydroxycoumarin that can be used as fluorophore for bio-sensoring applications was efficiently bound to the pre-functionalized cellulose with a yield of reaction estimated at 60%. The addition of 6-azido-per-6-deoxy-β-cyclodextrin (β-CD derivative) was investigated in order to target future organophosphorus decontamination properties to cellulose wipes. With the best reaction conditions, 60% of triazole groups corresponding to 4 reactive azido groups per β-CD derivative were detected by XPS proving the efficiency of the click reaction. The highest DS values were obtained after 96 h for β-CD 20 Eq (DS = 1.7% by elementary analysis and DS = 2.5% by weight measurements). Scanning electron microscopy observations highlighted a globally well distributed β-CD with some aggregates on the surface of the fibers. Thus, the pre-functionalized BCN-cellulose fibers could be used for many applications after an easy clicking of target compounds.

Introduction

Cellulose is the most abundant organic compound derived from biomass with a worldwide production in nature of many billions of tons per year [1] and so is of a great interest for the research of petroleum-based products replacement. It is used for various applications, especially for biomedical applications. For instance, cellulose is often used as support for biosensoring applications. Thus, cellulose-based biosensor was used as chromatographic absorbents for virus purification [2], for the detection of DNA hybridization [3], of the protease activity [4], of the elastase activity [5], [6], for the immobilization of enzymes [7]. Moreover, the immobilization of fluorescent molecules on cellulose enables to access to useful tools for the cellular uptake study on support [8]. In addition, cellulose was used to immobilize proteins. Especially, Mulchandani et al. have immobilized organophosphorus hydrolase (OPH) [9] on cellulose by genetically modifying Escherichia coli cell to express both cellulose binding domains and OPH before immobilization on the surface of textile hollow fibers [9], [10], [11]. Due to the large use of organophosphorus agents as pesticides and as chemical weapons and causing roughly 3 million cases of severe poisonings and 220 000 deaths worldwide annually [10], this strategy is of particular interest to access to efficient decontamination means.

Numerous articles described the chemical modifications of cellulose fibers to bring various properties such as, hydrophobicity [12], [13], thermoresponsivity [14], fluorescence [15], photo-responsivity [16], biological properties [17], [18], optical properties [19]. All those studies show the interest to have an easy and versatile way to functionalize cellulosic textile.

Anyway, cellulose shows lack of reactivity due to its specific structure, which is its main drawback faced with synthetic polymers. The main described modifications were carried out mostly in homogeneous phase, and in this case, the solubilization of the cellulose leads to a destruction of fibers and consecutively to the loss of its specific properties (mechanical, specific surface). Moreover, for industrial processes, the modification of cellulose in solid phase directly on the fibers is more suitable.

Different methods were described in order to easily functionalize cellulose such as Diels-Alder reactions [20] or thiol-ene “click” chemistry [13], [21], [22] Recently, “click” chemistry with functional molecules showed its efficiency for the rapid, easy and more environmentally friendly surface functionalization [23], [24]. Several groups developped a new cellulosic material thanks to copper azide-alkyne cycloaddition (CuAAC) reaction. To do so, different strategies are applied. The cellulose can be first tosylated before reaction with sodium azide to introduce the azido group. Finally, a “click” reaction is performed in presence of copper with a molecule containing an alkyne function [12], [25], [26], [27], [28]. An other way is also to adsorb on the cellulose surface carbomethoxycellulose bearing azido group [29].

Surprisingly, they are no report of cellulose modification through strain-promoted azide-alkyne cycloaddition (SPAAC). At the opposite of CuAAC, this reaction is metal free, which is huge asset for biological applications.

We report here the first study of the elaboration of a ready-to-use and biocompatible non-woven cellulose wipe. Our original and efficient strategy is based on the preparation of a pre-functionalized material by covalently attaching bicyclononyne (BCN) at the surface of cellulosic fibers. This modified cellulose wipe is then ready to engaged in a free-metal cycloaddition and it allows to tune on-demand the surface properties of the cellulose with various molecules of interest depending on the further application. Here, we chose to work on the one hand with a coumarin derivative as fluorophore model for bio-sensoring applications, and the other hand with β-cylodextrin (β-CD) to target OP decontamination systems. Indeed, Hatton et al. had proved the efficient degradation of chlorpyrifos by an iodosobenzoic acid (IBA) modified cellulose [30]. In another hand, various studies had shown the efficiency of enzyme mimics based on CDs substituted by a prevalent iodine or any α-nucleophile [31]. Consequently, immobilization of CD derivatives on cellulose could lead to an interesting solution in order to obtain a material having decontamination properties, i.e. sponges, protective clothes or even hemodialysis membranes for the treatment of poisoned people. To highlight the modified cellulose, we combined different analyses technics like X-ray photoelectron microscopy (XPS), scanning electron microscopy (SEM) and elementary analyses. To the best of our knowledge, this is the first study that describes the elaboration of highly modular cellulose via metal free click chemistry and with a full characterization of the performed modification.

Section snippets

Materials

4-dimethylaminopyridine (DMAP), anhydrous dimethylformamide (DMF) at 99.8%, anhydrous dichloromethane (DCM) at 99.8%, anhydrous methanol (MeOH) at 99.99% and White M2R (calcofluor) were purchased from Sigma-Aldrich. 3-azido-7-hydroxycoumarin was obtained from Carbosynth Limited. Non-woven cellulosic wipes were obtained from Kimberley-clark® (Kimwipes® Lite).

Synthesis of [(1R,8S,9S)-bicyclono-4-yn-9-yl] methyl 4-nitrophenyl carbonate (nitrophenylcarbonate-BCN)

(1R,8S,9s)-Bicyclo[6.1.0]non-4-yn-9-ylmethyl (4-nitrophenyl) carbonate was synthesized according to a known synthetic route [32].

Synthesis of per-6-azido-β-cyclodextrin

Per

Synthesis and characterization of the bicyclononyne cellulose (cellulose-BCN)

Cellulose-BCN was prepared by reacting nitrophenylcarbonate-BCN with a piece of dried wipe (Scheme 1). Due to the nitrophenyl group, the wipe turns yellowish after reaction and thoroughly rinsing. The influence of the reaction on the aspect of the cellulose fibers was checked by SEM. According to SEM pictures, no morphological change of the fibers was detected after the reaction with nitrophenylcarbonate-BCN (Fig. 1A and B). The fluorescent optical analysis proves the effective reaction of

Conclusion

In conclusion, we developed a new and versatile way to functionalize cellulose fibers. This innovative strategy is based on a strain-promoted azide-alkyne cycloaddition under heterogeneous conditions. The metal-free click chemistry is a very attractive approach to immobilize a large diversity of molecules on a textile support, and it avoids the persistence of any metal traces on cellulose after rinsing. Thus, we can extend the use of the functionalized textile to biological applications without

CRediT authorship contribution statement

Alex Myeye Biyogo: Investigation, Methodology, Writing - original draft. Louise Hespel: Conceptualization, Investigation, Methodology, Writing - original draft. Vincent Humblot: Resources, Investigation, Formal analysis, Writing - review & editing. Laurent Lebrun: Conceptualization, Methodology, Writing - review & editing. François Estour: Conceptualization, Methodology, Writing - review & editing.

Declaration of Competing Interest

We wish to confirm that there are no known conflicts of interest associated with this publication. The financial support of this work (the Normandy Region and the European Union) have not influenced its outcome.

Acknowledgment

The authors acknowledge IMPC (Institut des Matériaux de Paris Centre, FR CNRS 2482) and the C’Nano projects of the Region Ile-de-France, for Omicron XPS apparatus funding. The authors thank also the Normandy Region and the European Union for their financial support (FEDER E2M2-Poly-3D project). This work was partially supported by Normandie Universite (NU), the Région Normandie, the Centre National de la Recherche Scientifique (CNRS), Université de Rouen Normandie (URN), INSA Rouen Normandie,

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