One-step synthesis and self-assembly behavior of thermo-responsive star-shaped β-cyclodextrin--(P(MEO 2MA-co-PEGMA))21 copolymers

doi:10.1007/s11706-017-0388-6

Frontiers of Materials Science

2017, Vol. 11

Issue (3): 223-232 https://doi.org/10.1007/s11706-017-0388-6

本期目录

One-step synthesis and self-assembly behavior of thermo-responsive star-shaped β-cyclodextrin--(P(MEO ₂MA-co-PEGMA))₂₁ copolymers

Lulu WEI¹, Beibei LU¹, Lei LI¹, Jianning WU¹, Zhiyong LIU¹(

), Xuhong GUO^1,²

¹. School of Chemistry and Chemical Engineering, Shihezi University/Key Laboratory of Materials-Oriented Chemical Engineering of Xinjiang Uygur Autonomous Region/Engineering Research Center of Materials-Oriented Chemical Engineering of Xinjiang Bingtuan, Shihezi 832003, China
². State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

全文: PDF(381 KB) HTML

Abstract：

A novel β-cyclodextrin–poly(2-(2-methoxyethoxy)ethyl methacrylate)-co-poly(ethylene glycol) methacrylate (abbreviated as: β-CD–(P(MEO₂MA-co-PEGMA))₂₁) was prepared by using the one-step strategy, and then the star-shaped copolymers were used in the atom transfer radical polymerization (ATRP). The structure of star-shaped β-CD–(P(MEO₂MA-co-PEGMA))₂₁ copolymers were studied by FTIR, ¹H NMR and gel permeation chromatography (GPC). The star-shaped copolymers could self-assembled into micelles in aqueous solution owing to the outer amphiphilic β-CD as a core and the hydrophilic P(MEO₂MA-co-PEGMA) segments as a shell. These thermo-responsive star-shaped copolymers micelles exhibited lower critical solution temperature (LCST) in water, which could be finely tuned by changing the feed ratio of MEO₂MA to PEGMA. The LCST of star-shaped β-CD–(P(MEO₂MA-co-PEGMA))₂₁ copolymer micelles were increased from 35°C to 58°C with the increasing content of PEGMA. The results were investigated by DLS and TEM. When the temperature was higher than corresponding LCSTs, the micelles started to associate and form spherical nanoparticles. Therefore, β-CD–(P(MEO₂MA-co-PEGMA))₂₁ star-shaped copolymer micelles could be potentially applied in nano-carrier, nano-reactor, smart materials and biomedical fields.

Key words： star-shaped copolymers thermo-responsive β-cyclodextrin (β-CD) self-assembly atom transfer radical polymerization (ATRP)

收稿日期: 2017-04-11 出版日期: 2017-08-24

Corresponding Author(s): Zhiyong LIU

引用本文:

. [J]. Frontiers of Materials Science, 2017, 11(3): 223-232.
Lulu WEI, Beibei LU, Lei LI, Jianning WU, Zhiyong LIU, Xuhong GUO. One-step synthesis and self-assembly behavior of thermo-responsive star-shaped β-cyclodextrin--(P(MEO ₂MA-co-PEGMA))₂₁ copolymers. Front. Mater. Sci., 2017, 11(3): 223-232.

链接本文:

https://academic.hep.com.cn/foms/CN/10.1007/s11706-017-0388-6
https://academic.hep.com.cn/foms/CN/Y2017/V11/I3/223

Fig.1

Fig.2

Fig.3

Fig.4

Fig.5

Fig.6

Tab.1

Fig.7

Fig.8

Fig.9

Fig.10

Fig.11

1	Lapienis G. Star-shaped polymers having PEO arms. Progress in Polymer Science, 2009, 34(9): 852–892 https://doi.org/10.1016/j.progpolymsci.2009.04.006
2	Aloorkar N H, Kulkarni A S, Patil R A, et al.. Star polymers: an overview. International Journal of Pharmaceutical Sciences and Nanotechnology, 2012, 5(2): 1675–1684
3	Ramkissoon-Ganorkar C , Baudyš M , Kim S W . Effect of ionic strength on the loading efficiency of model polypeptide/protein drugs in pH-/temperature-sensitive polymers. Journal of Biomaterials Science: Polymer Edition, 2000, 11(1): 45–54 https://doi.org/10.1163/156856200743481 pmid: 10680607
4	Zhao S P, Zhou F, Li L Y . pH- and temperature-responsive behaviors of hydrogels resulting from the photopolymerization of allylated chitosan and N-isopropylacrylamide, and their drug release profiles. Journal of Polymer Research, 2012, 19(9): 9944 https://doi.org/10.1007/s10965-012-9944-z
5	Miladinovic Z R , Micic M , Suljovrujic E . Temperature/pH dual responsive OPGMA based copolymeric hydrogels prepared by gamma radiation: an optimisation study. Journal of Polymer Research, 2016, 23(4): 77
6	Wang H, Yan H, Zhu Y J , et al.. Synthesis and characterization of thermo-responsive supramolecular diblock copolymers. Journal of Polymer Research, 2016, 23(4): 73–81 https://doi.org/10.1007/s10965-016-0949-x
7	Ward M A, Georgiou T K. Thermoresponsive polymers for biomedical applications. Polymers, 2011, 3(4): 1215–1242 https://doi.org/10.3390/polym3031215
8	Wang M, Gao Y F, Cao C X, et al.. Binary solvent colloids of thermosensitive poly(N-isopropylacrylamide) microgel for smart windows. Industrial & Engineering Chemistry Research, 2014, 53(48): 18462–18472 https://doi.org/10.1021/ie502828b
9	Mu C G, Fan X D, Tian W, et al.. Miktoarm star polymers with poly(N-isopropylacrylamide) or poly(oligo(ethylene glycol) methacrylate) as building blocks: synthesis and comparison of thermally-responsive behaviors. Polymer Chemistry, 2012, 3(5): 1137–1149 https://doi.org/10.1039/c2py20029e
10	Li Y W, Guo H L, Zhang Y F, et al.. Pseudo-graft polymer based on adamantyl-terminated poly(oligo(ethylene glycol) methacrylate) and homopolymer with cyclodextrin as pendant: its thermoresponsivity through polymeric self-assembly and host-guest inclusion complexation. RSC Advances, 2014, 4(34): 17768–17779 https://doi.org/10.1039/C3RA47861K
11	Zhang Z X, Liu K L, Li J. Self-assembly and micellization of a dual thermoresponsive supramolecular pseudo-block copolymer. Macromolecules, 2011, 44(5): 1182–1193 https://doi.org/10.1021/ma102196q
12	Mao J, Ji X L, Bo S Q. Synthesis and pH/temperature-responsive behavior of PLLA-b-PDMAEMA block polyelectrolytes prepared via ROP and ATRP. Macromolecular Chemistry and Physics, 2011, 212(7): 744–752 https://doi.org/10.1002/macp.201000672
13	Ma Z Y, Jia X, Zhang G X , et al.. pH-responsive controlled-release fertilizer with water retention via atom transfer radical polymerization of acrylic acid on mussel-inspired initiator. Journal of Agricultural and Food Chemistry, 2013, 61(23): 5474–5482 https://doi.org/10.1021/jf401102a pmid: 23692274
14	Matyjaszewski K, Tsarevsky N V. Macromolecular engineering by atom transfer radical polymerization. Journal of the American Chemical Society, 2014, 136(18): 6513–6533 https://doi.org/10.1021/ja408069v pmid: 24758377
15	Matyjaszewski K, Miller P J, Pyun J, et al.. Synthesis and characterization of star polymers with varying arm number, length, and composition from organic and hybrid inorganic–organic multifunctional initiators. Macromolecules, 1999, 32(20): 6526–6535 https://doi.org/10.1021/ma9904823
16	Szejtli J. Introduction and general overview of cyclodextrin chemistry. Chemical Reviews, 1998, 98(5): 1743–1754 https://doi.org/10.1021/cr970022c pmid: 11848947
17	Tian Z C, Chen C, Allcock H R . Injectable and biodegradable supramolecular hydrogels by inclusion complexation between poly(organophosphazenes) and α-cyclodextrin. Macromolecules, 2013, 46(7): 2715–2724 https://doi.org/10.1021/ma4004314
18	Dong H, Li Y, Yu J , et al.. A versatile multicomponent assembly via β-cyclodextrin host-guest chemistry on graphene for biomedical applications. Small, 2013, 9(3): 446–456 https://doi.org/10.1002/smll.201201003 pmid: 23047287
19	Davis M E, Brewster M E. Cyclodextrin-based pharmaceutics: past, present and future. Nature Reviews Drug Discovery, 2004, 3(12): 1023–1035 https://doi.org/10.1038/nrd1576 pmid: 15573101
20	Machín R, Isasi J R, Vélaz I. β-Cyclodextrin hydrogels as potential drug delivery systems. Carbohydrate Polymers, 2012, 87(3): 2024–2030 https://doi.org/10.1016/j.carbpol.2011.10.024
21	Chen G, Jiang M. Cyclodextrin-based inclusion complexation bridging supramolecular chemistry and macromolecular self-assembly. Chemical Society Reviews, 2011, 40(5): 2254–2266 https://doi.org/10.1039/c0cs00153h pmid: 21344115
22	Chen B Y, Pang X H, Dong C M. Dual stimuli-responsive supramolecular polypeptide-based hydrogel and reverse micellar hydrogel mediated by host-guest chemistry. Advanced Functional Materials, 2010, 20(4): 579–586 https://doi.org/10.1002/adfm.200901400
23	Shao S Q, Si J X, Tang J B, et al.. Jellyfish-shaped amphiphilic dendrimers: synthesis and formation of extremely uniform aggregates. Macromolecules, 2014, 47(3): 916–921 https://doi.org/10.1021/ma4025619
24	Pang X C, Zhao L, Akinc M , et al.. Novel amphiphilic multi-arm, star-like block copolymers as unimolecular micelles. Macromolecules, 2011, 44(10): 3746–3752 https://doi.org/10.1021/ma200594j
25	Pang X C, Zhao L, Feng C W , et al.. Novel amphiphilic multiarm, starlike coil-rod diblock copolymers via a combination of click chemistry with living polymerization. Macromolecules, 2011, 44(18): 7176–7183 https://doi.org/10.1021/ma201564t
26	Zhang Q, Su L, Collins J , et al.. Dendritic cell lectin-targeting sentinel-like unimolecular glycoconjugates to release an anti-HIV drug. Journal of the American Chemical Society, 2014, 136(11): 4325–4332 https://doi.org/10.1021/ja4131565 pmid: 24568546
27	Lutz J F, Hoth A. Preparation of ideal PEG analogues with a tunable thermosensitivity by controlled radical copolymerization of 2-(2-methoxyethoxy) ethyl methacrylate and oligo (ethylene glycol) methacrylate. Macromolecules, 2006, 39(2): 893–896 https://doi.org/10.1021/ma0517042
28	Yuan W Z, Li X F, Gu S Y, et al.. Amphiphilic chitosan graft copolymer via combination of ROP, ATRP and click chemistry: synthesis, self-assembly, thermosensitivity, fluorescence, and controlled drug release. Polymer, 2011, 52(3): 658–666 https://doi.org/10.1016/j.polymer.2010.12.052
29	Kotsuchibashi Y, Ebara M, Hoffman A S , et al.. Temperature-responsive mixed core nanoparticle properties determined by the composition of statistical and block copolymers in the core. Polymer Chemistry, 2015, 6(10): 1693–1697 https://doi.org/10.1039/C4PY01794C
30	Das S, Samanta S, Chatterjee D P , et al.. Thermosensitive water-soluble poly(ethylene glycol)-based polythiophene graft copolymers. Journal of Polymer Science Part A: Polymer Chemistry, 2013, 51(6): 1417–1427 https://doi.org/10.1002/pola.26514
31	Elias P Z, Liu G W, Wei H, et al.. A functionalized, injectable hydrogel for localized drug delivery with tunable thermosensitivity: synthesis and characterization of physical and toxicological properties. Journal of Controlled Release, 2015, 208: 76–84 https://doi.org/10.1016/j.jconrel.2015.03.003 pmid: 25747144
32	Zhang Z X, Liu X, Xu F J , et al.. Pseudo-block copolymer based on star-shaped poly(N-isopropylacrylamide) with a β-cyclodextrin core and guest-bearing PEG: Controlling thermoresponsivity through supramolecular self-assembly. Macromolecules, 2008, 41(16): 5967–5970 https://doi.org/10.1021/ma8009646
33	Medel S, Manuel García J, Garrido L , et al.. Thermo- and pH-responsive gradient and block copolymers based on 2-(2-methoxyethoxy)ethyl methacrylate synthesized via atom transfer radical polymerization and the formation of thermoresponsive surfaces. Journal of Polymer Science Part A: Polymer Chemistry, 2011, 49(3): 690–700 https://doi.org/10.1002/pola.24480
34	Rieger J, Grazon C, Charleux B , et al.. Pegylated thermally responsive block copolymer micelles and nanogels via in situ RAFT aqueous dispersion polymerization. Journal of Polymer Science Part A: Polymer Chemistry, 2009, 47(9): 2373–2390 https://doi.org/10.1002/pola.23329
35	Gil E S, Hudson S M. Stimuli-responsive polymers and their bioconjugates. Progress in Polymer Science, 2004, 29(12): 1173–1222 https://doi.org/10.1016/j.progpolymsci.2004.08.003
36	Hoffman A S, Stayton P S. Bioconjugates of smart polymers and proteins: synthesis and applications. Macromolecular Symposia, 2004, 207(1): 139–152 https://doi.org/10.1002/masy.200450314
37	Badi N, Lutz J F. PEG-based thermogels: applicability in physiological media. Journal of Controlled Release, 2009, 140(3): 224–229 https://doi.org/10.1016/j.jconrel.2009.04.012 pmid: 19376170

Viewed

Full text

Abstract

Cited

Shared

Discussed