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Facile strategy for preparation of alkyne-functionalized cellulose fibers with click reactivity

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Abstract

A facile strategy for preparation of alkyne-functionalized cellulose fibers with click reactivity is reported herein. Poly(3-ethynylaniline) [poly(3-EA)] with pendant alkynyl groups was obtained by chemical oxidation polymerization of 3-ethynylaniline with ammonium persulfate in low-concentration hydrochloric acid solution at ice-bath temperature and used to generate alkyne-functionalized cellulose fibers in situ from pulp fibres. Successful preparation of alkyne-functionalized cellulose fibers was confirmed by attenuated total reflectance Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. The effects of process variables on poly(3-EA) deposition and fiber loss were investigated, and suitable preparation conditions identified. Deposition of poly(3-EA) did not change the crystallinity or hydrophilicity of the cellulose fibers. Poly(3-EA) and alkyne-functionalized cellulose fibers reacted with azides by Cu(I)-catalyzed alkyne–azide 1,3-dipolar cycloaddition. Thus, this in situ chemical polymerization technology provides a new platform for click functionalization of cellulose fibers. Applications of cellulose fibers produced in this way are limited to those without demanding requirements in terms of product strength or color.

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References

  • Agag T, Vietmeier K, Chernykh A, Ishida H (2012) Side-chain type benzoxazine-functional cellulose via click chemistry. J Appl Polym Sci 125:1346–1351

    Article  CAS  Google Scholar 

  • Agard NJ, Prescher JA, Bertozzi CR (2004) A strain-promoted [3 + 2] azide-alkyne cycloaddition for covalent modification of biomolecules in living systems. J Am Chem Soc 126:15046–15047

    Article  CAS  Google Scholar 

  • Alila S, Ferraria AM, do Rego AMB, Boufi S (2009) Controlled surface modification of cellulose fibers by amino derivatives using N,N′-carbonyldiimidazole as activator. Carbohydr Polym 77:553–562

    Article  CAS  Google Scholar 

  • Belgacem MN, Gandini A (eds) (2008) Surface modification of cellulose fibres. In: Monomers, polymers and composites from renewable resources. Elsevier, Amsterdam, pp 385–400

  • Bock VD, Hiemstra H, Van Maarseveen JH (2006) Cu(I)-catalyzed alkyne–azide “click” cycloadditions from a mechanistic and synthetic perspective. Eur J Org Chem 3:51–68

    Article  Google Scholar 

  • Bodin A, Ahrenstedt L, Fink H, Brumer H, Risberg B, Gatenholm P (2007) Modification of nanocellulose with a xyloglucan-RGD conjugate enhances adhesion and proliferation of endothelial cells: implications for tissue engineering. Biomacromolecules 8:3697–3704

    Article  CAS  Google Scholar 

  • Chen GJ, Tao L, Mantovani G, Ladmiral V, Burt DP, Macpherson JV, Haddleton DM (2007) Synthesis of azide/alkyne-terminal polymers and application for surface functionalisation through a [2 + 3] Huisgen cycloaddition process, “click chemistry”. Soft Matter 3:732–739

    Article  CAS  Google Scholar 

  • Chen ZX, Zhu JT, Xie HB, Li S, Wu YM, Gong YF (2010) Copper(I)-catalyzed synthesis of novel 4-(trifluoromethyl)-[1,2,3]triazolo[1,5-a]quinoxalines via cascade reactions of N-(o-haloaryl)alkynylimine with sodium azide. Adv Synth Catal 352:1296–1300

    Article  CAS  Google Scholar 

  • Chen Y, Qian XR, An XH (2011) Preparation and characterization of conductive paper via in situ polymerization of 3,4-ethylenedioxythiophene. BioResources 6:3410–3423

    CAS  Google Scholar 

  • Derikvand F, Yin DT, Barrett R, Brumer H (2016) Cellulose-based biosensors for esterase detection. Anal Chem 88:2989–2993

    Article  CAS  Google Scholar 

  • Ding CY, Qian XR, Shen J, An XH (2010) Preparation and characterization of conductive paper via in situ polymerization of pyrrole. BioResources 5:303–315

    CAS  Google Scholar 

  • Elchinger PH, Faugeras PA, Boëns B, Brouillette F, Montplaisir D, Zerrouki R, Lucas R (2011) Polysaccharides: the “click” chemistry impact. Polymers 3:1607–1651

    Article  CAS  Google Scholar 

  • Filpponen I, Kontturi E, Nummelin S, Rosilo H, Kolehmainen E, Ikkala O, Laine J (2012) Generic method for modular surface modification of cellulosic materials in aqueous medium by sequential “click” reaction and adsorption. Biomacromolecules 13:736–742

    Article  CAS  Google Scholar 

  • Finn MG, Kolb HC, Fokin VV, Sharpless KB (2008) Click chemistry: definition and aims. Prog Chem 20:1–4

    Google Scholar 

  • Gandini A, Pasquini D (2012) The impact of cellulose fibre surface modification on some physico-chemical properties of the ensuing papers. Ind Crop Prod 35:15–21

    Article  CAS  Google Scholar 

  • Grigoray O, Wondraczek H, Heikkila E, Fardim P, Heinze T (2014) Photoresponsive cellulose fibers by surface modification with multifunctional cellulose derivatives. Carbohydr Polym 111:280–287

    Article  CAS  Google Scholar 

  • Hafren J, Zou WB, Cordova A (2006) Heterogeneous ‘organoclick’ derivatization of polysaccharides. Macromol Rapid Commun 27:1362–1366

    Article  CAS  Google Scholar 

  • Huang W, Huang JJ, Xu CH, Gu SJ, Xu WL (2014) Surface functionalization of cellulose membrane via heterogeneous “click” grafting of zwitterionic sulfobetaine. Polym Bull 71:2559–2569

    Article  CAS  Google Scholar 

  • Junka K, Filpponen I, Johansson L-S, Kontturi E, Rojas OJ, Laine J (2014) A method for the heterogeneous modification of nanofibrillar cellulose in aqueous media. Carbohydr Polym 100:107–115

    Article  CAS  Google Scholar 

  • Kolb HC, Finn MG, Sharpless KB (2001) Click chemistry: diverse chemical function from a few good reactions. Angew Chem 40:2004–2021

    Article  CAS  Google Scholar 

  • Krouit M, Bras J, Belgacem MN (2008) Cellulose surface grafting with polycaprolactone by heterogeneous click-chemistry. Eur Polym J 44:4074–4081

    Article  CAS  Google Scholar 

  • Lee DG, Chang VS (1979) Oxidation of hydrocarbons. 9. The oxidation of alkynes by potassium permanganate. J Org Chem 44:2726–2730

    Article  CAS  Google Scholar 

  • Lei Y, Qian XR, Shen J, An XH (2012) Integrated reductive/adsorptive detoxification of Cr(VI)-contaminated water by polypyrrole/cellulose fiber composite. Ind Eng Chem Res 51:10408–10415

    Article  CAS  Google Scholar 

  • Li J, Qian XR, Wang LJ, An XH (2010) XPS characterization and percolation behavior of polyaniline-coated conductive paper. BioResources 5:712–726

    CAS  Google Scholar 

  • Liebert T, Hansch C, Heinze T (2006) Click chemistry with polysaccharides. Macromol Rapid Commun 27:208–213

    Article  CAS  Google Scholar 

  • Liu XY, Qian XR, Shen J, Zhou WP, An XH (2012) An integrated approach for Cr(VI)-detoxification with polyaniline/cellulose fiber composite prepared using hydrogen peroxide as oxidant. Bioresour Technol 124:516–519

    Article  CAS  Google Scholar 

  • Ly EB, Bras J, Sadocco P, Belgacem MN, Dufresne A, Thielemans W (2010) Surface functionalization of cellulose by grafting oligoether chains. Mater Chem Phys 120:438–445

    Article  CAS  Google Scholar 

  • Mangiante G, Alcouffe P, Burdin B, Gaborieau M, Zeno E, Petit-Conil M, Bernard J, Charlot A, Fleury E (2013) Green nondegrading approach to alkyne-functionalized cellulose fibers and biohybrids thereof: synthesis and mapping of the derivatization. Biomacromolecules 14:254–263

    Article  CAS  Google Scholar 

  • Mao H, Wu XN, Qian XR, An XH (2014) Conductivity and flame retardancy of polyaniline-deposited functional cellulosic paper doped with organic sulfonic acids. Cellulose 21:697–704

    Article  CAS  Google Scholar 

  • Meng X, Edgar KJ (2016) “Click” reactions in polysaccharide modification. Prog Polym Sci 53:52–85

    Article  CAS  Google Scholar 

  • Ogata Y, Sawaki Y, Ohno T (1982) Mechanism for oxidation of phenylacetylenes with peroxymonophosphoric acid. Oxirene as an intermediate inconvertible to ketocarbene. J Am Chem Soc 104:216–219

    Article  CAS  Google Scholar 

  • Paquet O, Krouit M, Bras J, Thielemans W, Belgacem MN (2010) Surface modification of cellulose by PCL grafts. Acta Mater 58:792–801

    Article  CAS  Google Scholar 

  • Pohl M, Morris GA, Harding SE, Heinze T (2009) Studies on the molecular flexibility of novel dendronized carboxymethyl cellulose derivatives. Eur Polym J 45:1098–1110

    Article  CAS  Google Scholar 

  • Roy D, Semsarilar M, Guthrie JT, Perrier S (2009) Cellulose modification by polymer grafting: a review. Chem Soc Rev 38:2046–2064

    Article  CAS  Google Scholar 

  • Stejskal J, Gilbert RG (2002) Polyaniline. Preparation of a conducting polymer. Pure Appl Chem 74:857–867

    Article  CAS  Google Scholar 

  • Tang JS, Wang LX, Jing XB, Wang FS (1989) The effect of acid concentration on the aniline polymerization and the characterization of polymers obtained. Acta Polym Sin 2:188–191

    Google Scholar 

  • van Berkel SS, Dirks ATJ, Debets MF, van Delft FL, Cornelissen JJLM, Nolte RJM, Rutjes FPJT (2007) Metal-free triazole formation as a tool for bioconjugation. ChemBioChem 8:1504–1508

    Article  Google Scholar 

  • Xiong FQ, Han YM, Li GY, Qin TF, Wang SQ, Chu FX (2016) Research status of click chemistry used for chemical modification of lignocellulose. Sci Silvae Sin 52:90–96

    Google Scholar 

  • Xu C, Spadiut O, Silva ACA, Brumer H (2012) Chemo-enzymatic assembly of clickable cellulose surfaces via multivalent polysaccharides. ChemSusChem 5:661–665

    Article  CAS  Google Scholar 

  • Yilmaz F, Kucukyavuz Z (2013) The influence of polymerization temperature on structure and properties of polyaniline. E-Polymers 9:48–57

    Google Scholar 

  • Zampano G, Bertoldo M, Bronco S (2009) Poly(ethyl acrylate) surface-initiated ATRP grafting from wood pulp cellulose fibers. Carbohydr Polym 75:22–31

    Article  CAS  Google Scholar 

  • Zhao GL, Hafren J, Deiana L, Cordova A (2010) Heterogeneous “organoclick” derivatization of polysaccharides: photochemical thiol-ene click modification of solid cellulose. Macromol Rapid Commun 31:740–744

    Article  CAS  Google Scholar 

  • Zhou Q, Baumann MJ, Brumer H, Teeri TT (2006) The influence of surface chemical composition on the adsorption of xyloglucan to chemical and mechanical pulps. Carbohydr Polym 63:449–458

    Article  CAS  Google Scholar 

  • Zhou Q, Rutland MW, Teeri TT, Brumer H (2007) Xyloglucan in cellulose modification. Cellulose 14:625–641

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors gratefully acknowledge the National Natural Science Foundation of China (grant no. 31370579) for financial support of this work.

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Authors and Affiliations

  1. Key Laboratory of Bio-based Materials Science and Technology of Ministry of Education, Northeast Forestry University, Harbin, 150040, People’s Republic of China

    Guifa Xiao, Chunyue Ding, Feiyu Song, Xueren Qian & Xianhui An

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  1. Guifa Xiao
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  2. Chunyue Ding
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  3. Feiyu Song
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  4. Xueren Qian
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  5. Xianhui An
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Correspondence to Xueren Qian.

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Xiao, G., Ding, C., Song, F. et al. Facile strategy for preparation of alkyne-functionalized cellulose fibers with click reactivity. Cellulose 24, 591–607 (2017). https://doi.org/10.1007/s10570-016-1153-1

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