, Volume 22, Issue 4, pp 2365–2374 | Cite as

Synthesis, characterization, and micellar behaviors of hydroxyethyl cellulose-graft-poly(lactide/ε-caprolactone/p-dioxanone)

  • Wenjiao Ge
  • Yanzhu Guo
  • Haoquan Zhong
  • Xiaohui Wang
  • Runcang Sun
Original Paper


In response to the shortage of petroleum resources and the growing need for sustainable development, cellulose-based amphiphilic copolymers have emerged as a new generation of value-added functional nanostructures from biomass resources. In this article, 17 amphiphilic hydroxyethyl cellulose-based graft copolymers with different side chains, including poly(lactide), poly(ε-caprolactone) and poly(p-dioxanone), were synthesized via homogeneous ring opening polymerization in ionic liquid 1-butyl-3-methylimidazolium chloride and characterized by FT-IR, 1H NMR, thermogravimetric analysis and gel permeation chromatography. The resultant copolymers can self-assemble into micelles with a low critical micelle concentration that varies in the range of 0.03–0.24 mg/ml. TEM observations revealed the obtained micelles had a spherical and well-distributed morphology, and DLS analysis showed the nanoscaled sizes were between 40 and 150 nm. These HEC-based micelles can be used as nano-sized vesicles and have great latent forces in drug delivery systems.


Amphiphilic Hydroxyethyl cellulose Self-assemble Nanomicelles 



This work was financially supported by the Program for New Century Excellent Talents in University (grant no. NCET-13-0215), the Science and Technology Program of Guangzhou, China (grant no. 2014J4100039) and Open Foundation of State Key Laboratory of Pulp and Paper Engineering, South China University of Technology (grant no. 201312).


  1. Chang C, Wei H, Quan CY, Li YY, Liu J, Wang ZC, Cheng SX, Zhang XZ, Zhuo RX (2008) Fabrication of thermosensitive PCL-PNIPAAm-PCL triblock copolymeric micelles for drug delivery. J Polym Sci Polym Chem 46:3048–3057CrossRefGoogle Scholar
  2. Chen C-H, Hsieh M-F, Ho Y-N, Huang C-M, Lee J-S, Yang C-Y, Chang Y (2011a) Enhancement of catechin skin permeation via a newly fabricated mPEG-PCL-graft-2-hydroxycellulose membrane. J Membr Sci 371:134–140CrossRefGoogle Scholar
  3. Chen CH, Cuong NV, Chen YT, So RC, Liau I, Hsieh MF (2011b) Overcoming multidrug resistance of breast cancer cells by the micellar doxorubicin nanoparticles of mPEG-PCL-graft-cellulose. J Nanosci Nanotechnol 11:53–60CrossRefGoogle Scholar
  4. Coulembier O, Degee P, Hedrick JL, Dubois P (2006) From controlled ring-opening polymerization to biodegradable aliphatic polyester: especially poly(beta-malic acid) derivatives. Prog Polym Sci 31:723–747CrossRefGoogle Scholar
  5. Gong P, Yang Y, Yi H, Fang S, Zhang P, Sheng Z, Gao G, Gao D, Cai L (2014) Polypeptide micelles with dual pH activatable dyes for sensing cells and cancer imaging. Nanoscale 6:5416–5424CrossRefGoogle Scholar
  6. Guo YZ, Wang XH, Shu XC, Shen ZG, Sun RC (2012) Self-assembly and paclitaxel loading capacity of cellulose-graft-poly(lactide) nanomicelles. J Agric Food Chem 60:3900–3908CrossRefGoogle Scholar
  7. Guo YZ, Liu Q, Chen H, Wang XH, Shen ZG, Shu XC, Sun RC (2013a) Direct grafting modification of pulp in ionic liquids and self-assembly behavior of the graft copolymers. Cellulose 20:873–884CrossRefGoogle Scholar
  8. Guo YZ, Wang XZ, Shen ZG, Shu XC, Sun RC (2013b) Preparation of cellulose-graft-poly(ε-caprolactone) nanomicelles by homogeneous ROP in ionic liquid. Carbohydr Polym 92:77–83CrossRefGoogle Scholar
  9. Hao Y, Peng J, Li J, Zhai M, Wei G (2009) An ionic liquid as reaction media for radiation-induced grafting of thermosensitive poly (N-isopropylacrylamide) onto microcrystalline cellulose. Carbohydr Polym 77:779–784CrossRefGoogle Scholar
  10. Hassani LN, Hendra F, Bouchemal K (2012) Auto-associative amphiphilic polysaccharides as drug delivery systems. Drug Discov Today 17:608–614CrossRefGoogle Scholar
  11. Jacobsen S, Degee PH, Fritz HG, Dubois PH, Jerome R (1999) Polylactide (PLA)—a new way of production. Polym Eng Sci 39:1311–1319CrossRefGoogle Scholar
  12. Jiang C, Wang X, Sun P, Yang C (2011) Synthesis and solution behavior of poly(ε-caprolactone) grafted hydroxyethyl cellulose copolymers. Int J Biol Macromol 48:210–214CrossRefGoogle Scholar
  13. Jones MC, Leroux JC (2010) Reverse micelles from amphiphilic branched polymers. Soft Matter 6:5850–5859CrossRefGoogle Scholar
  14. Kang H, Liu R, Huang Y (2013) Cellulose derivatives and graft copolymers as blocks for functional materials. Polym Int 62:338–344CrossRefGoogle Scholar
  15. Klemm D, Heublein B, Fink HP, Bohn A (2005) Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Int Edit 44:3358–3393CrossRefGoogle Scholar
  16. Labet M, Thielemans W (2011) Improving the reproducibility of chemical reactions on the surface of cellulose nanocrystals: ROP of ε-caprolactone as a case study. Cellulose 18:607–617CrossRefGoogle Scholar
  17. Labet M, Thielemans W (2012) Citric acid as a benign alternative to metal catalysts for the production of cellulose-grafted-polycaprolactone copolymers. Polym Chem 3:679–684CrossRefGoogle Scholar
  18. Li Y, Liu R, Liu W, Kang H, Wu M, Huang Y (2008) Synthesis, self-assembly, and thermosensitive properties of ethyl cellulose-g-P(PEGMA) amphiphilic copolymers. J Polym Sci Polym Chem 46:6907–6915CrossRefGoogle Scholar
  19. Lin C, Zhan H, Liu M, Habibi Y, Fu S, Lucia LA (2013) RAFT synthesis of cellulose-g-polymethylmethacrylate copolymer in an ionic liquid. J Appl Polym Sci 127:4840–4849CrossRefGoogle Scholar
  20. Liu Y, Cao X, Luo M, Le Z, Xu W (2009) Self-assembled micellar nanoparticles of a novel star copolymer for thermo and pH dual-responsive drug release. J Colloid Interface Sci 329:244–252CrossRefGoogle Scholar
  21. Liu XY, Chen J, Sun P, Liu ZW, Liu ZT (2010) Grafting modification of ramie fibers with poly(2,2,2-trifluoroethyl methacrylate) via reversible addition-fragmentation chain transfer (RAFT) polymerization in supercritical carbon dioxide. React Funct Polym 70:972–979CrossRefGoogle Scholar
  22. Lu H, Su F, Mei Q, Zhou X, Tian Y, Tian W, Johnson RH, Meldrum DR (2012) A series of poly N-(2-hydroxypropyl)methacrylamide copolymers with anthracene-derived fluorophores showing aggregation-induced emission properties for bioimaging. J Polym Sci Polym Chem 50:890–899CrossRefGoogle Scholar
  23. Miller T, Breyer S, van Colen G, Mier W, Haberkorn U, Geissler S, Voss S, Weigandt M, Goepferich A (2013) Premature drug release of polymeric micelles and its effects on tumor targeting. Int J Pharm 445:117–124CrossRefGoogle Scholar
  24. Moghaddam PN, Avval ME, Fareghi AR (2014) Modification of cellulose by graft polymerization for use in drug delivery systems. Colloid Polym Sci 292:77–84CrossRefGoogle Scholar
  25. Pinkert A, Marsh KN, Pang S, Staiger MP (2009) Ionic liquids and their interaction with cellulose. Chem Rev 109:6712–6728CrossRefGoogle Scholar
  26. Quan SL, Kang SG, Chin IJ (2010) Characterization of cellulose fibers electrospun using ionic liquid. Cellulose 17:223–230CrossRefGoogle Scholar
  27. Sun N, Rodriguez H, Rahman M, Rogers RD (2011) Where are ionic liquid strategies most suited in the pursuit of chemicals and energy from lignocellulosic biomass? Chem Commun 47:1405–1421CrossRefGoogle Scholar
  28. Wang XH, Guo YZ, Li D, Chen H, Sun RC (2012a) Fluorescent amphiphilic cellulose nanoaggregates for sensing trace explosives in aqueous solution. Chem Commun 48:5569–5571CrossRefGoogle Scholar
  29. Wang XL, Zhai YL, Tang DL, Liu GY, Wang YZ (2012b) Self-assembly, drug-delivery behavior, and cytotoxicity evaluation of amphiphilic chitosan-graft-poly (1,4-dioxan-2-one) copolymers. J Polym Res 19:1221–1227Google Scholar
  30. Wang C, Yan D, Li Q, Sun W, Xing J (2014a) Ionic liquid pretreatment to increase succinic acid production from lignocellulosic biomass. Bioresour Technol 172:283–289CrossRefGoogle Scholar
  31. Wang X, Chen Y, Dahmani FZ, Yin L, Zhou J, Yao J (2014b) Amphiphilic carboxymethyl chitosan-quercetin conjugate with P-gp inhibitory properties for oral delivery of paclitaxel. Biomaterials 35:7654–7665CrossRefGoogle Scholar
  32. Weerachanchai P, Kwak SK, Lee J-M (2014) Effects of solubility properties of solvents and biomass on biomass pretreatment. Bioresour Technol 170:160–166CrossRefGoogle Scholar
  33. Zhang Y, Wang M, Zheng Y, Tan H, Hsu BY, Yang ZC, Wong SY, Chang AY, Choolani M, Li X, Wang J (2013) PEOlated micelle/silica as dual-layer protection of quantum dots for stable and targeted bioimaging. Chem Mater 25:2976–2985CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2015

Authors and Affiliations

  1. 1.State Key Laboratory of Pulp and Paper EngineeringSouth China University of TechnologyGuangzhouChina
  2. 2.Institute of Light Industry and Chemical EngineeringDalian Polytechnic UniversityDalianChina
  3. 3.Institute of Biomass Chemistry and TechnologyBeijing Forestry UniversityBeijingChina

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