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Glycidyl methacrylate derivatized xylan-rich hemicelluloses: synthesis and characterizations

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Abstract

In this paper, a novel type of hemicellulosic derivative containing polymerizable double bonds (C=C) was synthesized by chemical reaction of xylan-rich hemicelluloses and glycidyl methacrylate (GMA) in dimethyl sulfoxide (DMSO) in presence of catalysts. The chemical structure, reaction mechanism, and rheological properties of the derivative were investigated by means of FT-IR, 1H and 13C-NMR, DEPT 135 NMR, GC–MS and rheometer. The influence of the reaction conditions including reaction time, temperature, catalysts, and the amount of reagents on the degree of substitution were investigated in detail. Results showed that the chemical reaction of xylan-rich hemicelluloses with GMA was transesterification, which resulted in direct attachment of methacrylate (MA) groups to xylan-rich hemicelluloses, instead of GMA. A maximum degree of substitution of 0.94 could be achieved under the optimum reaction condition (40 °C, 1.8 equiv of GMA to per xylose unit, 36 h, 20 % DMAP). Results from rheological analysis indicated that the aqueous solutions of the methacrylated xylan-rich hemicelluloses (MAXH; 0.5, 1.0 and 2.0 wt%) exhibited typical shear-thinning behavior in the range of shear rates tested. The viscoelasticity of MAXH solutions increased with the increasing concentration and DS.

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References

  • Chakraborty S, Sahoo B, Teraoka I, Miller LM, Gross RA (2005) Enzyme-catalyzed regioselective modification of starch nanoparticles. Macromolecules 38:61–68

    Article  CAS  Google Scholar 

  • Cunha AG, Gandini A (2010) Turning polysaccharides into hydrophobic materials: a critical review. Part 2. Hemicelluloses, chitin/chitosan, starch, pectin and alginates. Cellulose 17:1045–1065

    Article  CAS  Google Scholar 

  • Edlund U (2008) A microspheric system: hemicellulose-based hydrogels. J Bioact Compat Polym 23:171–186

    Article  CAS  Google Scholar 

  • Elizalde-Pena EA, Flores-Ramirez N, Luna-Barcenas G, Vasquez-García SR, Arámbula-Villa G, García-Gaitan B, Rutiaga-Quinones JG, Gonzalez-Hernandez J (2007) Synthesis and characterization of chitosan-g-glycidyl methacrylate with methyl methacrylate. Eur Polym J 43:3963–3969

    Article  CAS  Google Scholar 

  • Fang JM, Sun RC, Tomkinson J, Fowler P (2000) Acetylation of wheat straw hemicellulose B in a new non-aqueous swelling system. Carbohydr Polym 41:379–387

    Article  CAS  Google Scholar 

  • Ferreira L, Vidal MM, Geraldes CFGC, Gil MH (2000) Preparation and characterisation of gels based on sucrose modified with glycidyl methacrylate. Carbohydr Polym 41:15–24

    Article  CAS  Google Scholar 

  • Frechet JMJ, Henmi M, Gitsov I, Aoshima S, Leduc MR, Grubbs RB (1995) Self-condensing vinyl polymerization: an approach to dendritic materials. Science 269:1080–1083

    Article  CAS  Google Scholar 

  • Ge Y, Duan YF, Fang GZ, Zhang Y, Wang S (2009) Polysaccharides from fruit calyx of physalis alkekengi var. francheti: Isolation, purification, structural features and antioxidant activities. Carbohydr Polym 77:188–193

    Article  CAS  Google Scholar 

  • Geng ZC, Sun JX, Liang SF, Zhang FY, Zhang YY, Xu F, Sun RC (2006) Characterization of water-and alkali-soluble hemicellulosic polymers from sugarcane bagasse. Int J Polym Anal Charact 11:209–226

    Article  CAS  Google Scholar 

  • Goksu EI, Karamanlioglu M, Bakir U, Yilmaz L, Yilmazer U (2007) Production and characterization of films from cotton stalk xylan. J Agric Food Chem 55:10685–10691

    Article  CAS  Google Scholar 

  • Grondahl M, Eriksson L, Gatenholm P (2004) Material properties of plasticized hardwood xylans for potential application as oxygen barrier films. Biomacromolecules 5:1528–1535

    Article  Google Scholar 

  • Guilherme MR, Reis AV, Takahashi SH, Rubira AF, Feitosa JPA, Muniz EC (2005) Synthesis of a novel superabsorbent hydrogel by copolymerization of acrylamide and cashew gum modified with glycidyl methacrylate. Carbohydr Polym 61:464–471

    Article  CAS  Google Scholar 

  • Gupta S, Madan RN, Bansal MC (1987) Chemical composition of pinus caribaea hemicellulose. Tappi J 70:113–116

    CAS  Google Scholar 

  • Hansen NML, Plackett D (2008) Sustainable films and coatings from hemicelluloses: a review. Biomacromolecules 9:1493–1505

    Article  CAS  Google Scholar 

  • Hawker CJ, Bosman AW, Harth E (2001) New polymer synthesis by nitroxide mediated living radical polymerizations. Chem Rev 101:3661–3688

    Article  CAS  Google Scholar 

  • Hebeish A, Waly A, Abdel-Mohdy FA, Aly AS (1997) Synthesis and characterization of cellulose ion exchangers. I. Polymerization of glycidyl methacrylate, dimethylaminoethyl methacrylate, and acrylic acid with cotton cellulose using thiocarbonate-H2O2 redox system. J Appl Polym Sci 66:1029–1037

    Article  CAS  Google Scholar 

  • Hedin J, Ostlund A, Nyden M (2010) UV induced cross-linking of starch modified with glycidyl methacrylate. Carbohydr Polym 79:606–613

    Article  CAS  Google Scholar 

  • Heinze T, Koschella A (2008) Water-soluble 3-O-(2-methoxyethyl) cellulose: synthesis and characterization. Carbohydr Res 343:668–673

    Article  CAS  Google Scholar 

  • Hu XW, Du YM, Tang YF, Wang Q, Feng T, Yang JH, Kennedy JF (2007) Solubility and property of chitin in NaOH/urea aqueous solution. Carbohydr Polym 70:451–458

    Article  CAS  Google Scholar 

  • Ishizu K, Mori A (2000) Synthesis of hyperbranched polymers by self-addition free radical vinyl polymerization of photo functional styrene. Macromol Rapid Commun 21:665–668

    Article  CAS  Google Scholar 

  • Ishizu K, Shen XX, Tsubaki KI (2000) Radical copolymerization reactivity of methacryloyl-terminated poly (ethylene glycol methylether) with vinylbenzyl-terminated polystyrene macromonomers. Polymer 41:2053–2057

    Article  CAS  Google Scholar 

  • Koschella A, Fenn D, Illy N, Heinze T (2006) Regioselectively functionalized cellulose derivatives: a mini review. Macromol Symp 244:59–73

    Article  CAS  Google Scholar 

  • Li Y, Armes SP (2005) Synthesis and chemical degradation of branched vinyl polymers prepared via ATRP: use of a cleavable disulfide-based branching agent. Macromolecules 38:8155–8162

    Article  CAS  Google Scholar 

  • Lin D, Zhao YY (2007) Innovations in the development and application of edible coatings for fresh and minimally processed fruits and vegetables. Comp Re Food Sci Food Safety 6:60–75

    Article  CAS  Google Scholar 

  • Lindblad MS, Ranucci E, Albertsson AC (2001) Biodegradable polymers from renewable sources: new hemicellulose-based hydrogels. Macromol Rapid Commun 22:962–967

    Article  CAS  Google Scholar 

  • Lindblad MS, Albertsson AC, Ranucci E, Laus M, Giani E (2005) Biodegradable polymers from renewable sources: rheological characterization of hemicellulose-based hydrogels. Biomacromolecules 6:684–690

    Article  CAS  Google Scholar 

  • Lindblad MS, Sjoberg J, Albertsson AC, Hartman J (2007) Hydrogels from polysaccharides for biomedical applications. In: Argyropoulos DS (ed) Materials, chemicals, and energy from forest biomass. ACS, Washington, DC, pp 153–167

    Chapter  Google Scholar 

  • Mikkonen KS, Mathew AP, Pirkkalainen K, Serimaa R, Xu CL, Willför S, Oksman K, Tenkanen M (2010) Glucomannan composite films with cellulose nanowhiskers. Cellulose 17:69–81

    Article  CAS  Google Scholar 

  • Miyazaki S, Suzuki S, Kawasaki N, Endo K, Takahashi A, Attwood D (2001) In situ gelling xyloglucan formulations for sustained release ocular delivery of pilocarpine hydrochloride. Int J Pharm 229:29–36

    Article  CAS  Google Scholar 

  • Morimoto N, Endo T, Iwasaki Y, Akiyoshi K (2005) Design of hybrid hydrogels with self-assembled nanogels as xross-linkers: Interaction with proteins and chaperone-like activity. Biomacromolecules 6:1829–1834

    Article  CAS  Google Scholar 

  • Nagasaki Y, Ryutaro Ogawa R, Yamamoto S, Kato M, Kataoka K (1997) Synthesis of heterotelechelic poly (ethylene glycol) macromonomers. Preparation of poly (ethylene glycol) possessing a methacryloyl group at one end and a formyl group at the other end. Macromolecules 30:6489–6493

    Article  CAS  Google Scholar 

  • Ohsedo Y, Takashina R, Gong JP, Osada Y (2004) Surface friction of hydrogels with well-defined polyelectrolyte brushes. Langmuir 20:6549–6555

    Article  CAS  Google Scholar 

  • Peng F, Ren JL, Xu F, Bian J, Peng P, Sun RC (2010) Fractional study of alkali-soluble hemicelluloses obtained by graded ethanol precipitation from sugar cane bagasse. J Agric Food Chem 58:1768–1776

    Article  CAS  Google Scholar 

  • Peng XW, Ren JL, Sun RC (2011a) Homogeneous esterification of hemicelluloses with maleic anhydride in ionic liquid. Biomacromolecules 11:3519–3524

    Article  Google Scholar 

  • Peng XW, Ren JL, Zhong LX, Cao XF, Sun RC (2011b) Microwave-induced synthesis of carboxymethyl hemicelluloses and their rheological properties. J Agric Food Chem 59:570–576

    Article  CAS  Google Scholar 

  • Pohjanlehto H, Setälä H, Kammiovirta K, Harlin A (2011) The use of N, N’-diallylaldardiamides as cross-linkers in xylan derivatives-based hydrogels. Carbohyd Res 346:2736–2745

    CAS  Google Scholar 

  • Reis AV, Cavalcanti OA, Rubira AF, Muniz EC (2003) Synthesis and characterization of hydrogels formed from a glycidyl methacrylate derivative of galactomannan. Int J Pharm 267:13–25

    Article  CAS  Google Scholar 

  • Ren JL, Xu F, Sun RC, Peng P, Sun JX (2008) Studies of the lauroylation of wheat straw hemicelluloses under heating. J Agric Food Chem 56:1251–1258

    Article  CAS  Google Scholar 

  • Sasso C, Bruyant N, Beneventi D, Faure-Vincent J, Zeno E, Petit-Conil M, Didier Chaussy D, Belgacem MN (2011) Polypyrrole (PPy) chemical synthesis with xylan in aqueous medium and production of highly conducting PPy/nanofibrillated cellulose films and coatings. Cellulose. doi:10.1007/s10570-011-9583-2

  • Schwikal K, Heinze T, Ebringerova A, Petzold K (2006) Cationic xylan derivatives with high degree of functionalization. Macromol Symp 232:49–56

    Article  CAS  Google Scholar 

  • Sun RC, Wang XY, Sun XF, Sun JX (2002) Physicochemical and thermal characterisation of residual hemicelluloses isolated by TAED activated peroxide from ultrasonic irradiated and alkali organosolv pre-treated wheat straw. Polym Degrade Stabil 78:295–303

    Article  CAS  Google Scholar 

  • Torul H, Arslan N (2003) Production of carboxymethyl cellulose from sugar beet pulp cellulose and rheological behaviour of carboxymethyl cellulose. Carbohydr Polym 54:73–82

    Article  Google Scholar 

  • Tsukahara Y, Tsutsumi K, Yamashita Y, Shimada S (1990) Radical polymerization behavior of macromonomers. 2. comparison of styrene macromonomers having a methacryloyl end group and a vinylbenzyl end group. Macromolecules 23:5201–5208

    Article  CAS  Google Scholar 

  • Vaca-Garcia C, Borredon ME, Gaseta A (2001) Determination of the degree of substitution (DS) of mixed cellulose esters by elemental analysis. Cellulose 8:225–231

    Article  CAS  Google Scholar 

  • van Dijk-Wolthuis WNE, Franssen O, Talsma H, van Steenbergen MJ, Kettenes-van den Bosch JJ, Hennink WE (1995) Synthesis, characterization, and polymerization of glycidyl methacrylate derivatized dextran. Macromolecules 28:6317–6322

    Article  Google Scholar 

  • van Dijk-Wolthuis WNE, Kettenes-van den Bosch JJ, van der Kerk-van Hoof A, Hennink WE (1997) Reaction of dextran with glycidyl methacrylate: an unexpected transesterification. Macromolecules 30:3411–3413

  • Vervoort L, Busson R, Toppet S, Kinget R (1997) Inulin hydrogels as carriers for colonic drug targeting. I. Synthesis and characterization of methacrylated inulin and hydrogel formation. Pharm Res 14:1730–1737

    Article  CAS  Google Scholar 

  • Vervoort L, Van den Mooter G, Augustijns P, Kinget R (1999) Inulin hydrogels as carriers for colonic drug targeting. Rheological characterization of the hydrogel formation and the hydrogel network. J Pharm Sci 2:209–214

    Article  Google Scholar 

  • Weber N, Weitkamp P, Mukherjee KD (2001) Fatty acid steryl, stanyl, and steroid esters by esterification and transesterification in vacuo using candida rugosa lipase as catalyst. J Agric Food Chem 49:67–71

    Article  CAS  Google Scholar 

  • Xu C, Willfor S, Holmlund P, Holmboma B (2009) Rheological properties of water-soluble spruce O-acetyl galactoglucomannans. Carbohydr Polym 75:498–504

    Article  CAS  Google Scholar 

  • Yadav GD, Devi KM (2004) Immobilized lipase-catalysed esteri’cation and transesteri’cation reactions in non-aqueous media for the synthesis of tetrahydrofurfuryl butyrate: comparison and kinetic modeling. Chem Eng Sci 59:373–383

    Article  CAS  Google Scholar 

  • Yang JY, Zhou XS, Fang J (2011) Synthesis and characterization of temperature sensitive hemicellulose-based hydrogels. Carbohyr Polym 86:1113–1117

    Article  CAS  Google Scholar 

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Acknowledgments

This work was supported by the grants from National Natural Science Foundation of China (No. 31070530 and 30930073), Foundation for the Author of National Excellent Doctoral Dissertation of China (No. 201169), Project of Guangzhou Science and Technology Plan (No. 11C52080723/2011J4100065), Science and Technology project of Guangdong Province (No. 2011B050400015), and the Fundamental Research Funds for the Central Universities (No. 2012ZZ0081), SCUT.

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Authors and Affiliations

  1. State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou, China

    Xinwen Peng, Junli Ren, Wenbin Shi & Bojie Hu

  2. Institute of Biomass Chemistry and Technology, Beijing Forestry University, Beijing, China

    Linxin Zhong & Runcang Sun

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  1. Xinwen Peng
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  2. Junli Ren
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  3. Linxin Zhong
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Correspondence to Junli Ren.

Appendix: Abbreviations

Appendix: Abbreviations

 

Full name

Abbreviations

Xylan-rich hemicelluloses

XH

Glycidyl methacrylate

GMA

Methacrylate

MA

Methacrylated xylan-rich hemicelluloses

MAXH

Dendrocalamus membranaceus Munro

DmM

4-O-methyl-d-glucuronic acid

MeGlcA

Dimethyl sulfoxide

DMSO

4-Dimethyl-amino-pyridine

DMAP

N-bromosuccinimide

NBS

Triethylamine

TEA

Potassiumtert-butoxide

PB

Xylose units in xylan-rich hemicelluloses

Nx

Degree of substitution

DS

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Peng, X., Ren, J., Zhong, L. et al. Glycidyl methacrylate derivatized xylan-rich hemicelluloses: synthesis and characterizations. Cellulose 19, 1361–1372 (2012). https://doi.org/10.1007/s10570-012-9718-0

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