|
|
|
| Crystallization induced micellization of poly(p-dioxanone)-block-polyethylene glycol diblock copolymer functionalized with pyrene moiety |
| Chang-Lei Liu, Gang Wu, Si-Chong Chen, Jiao You, Yu-Zhong Wang |
| Center for Degradable and Flame-Retardant Polymeric Materials, State Key Laboratory of Polymer Materials Engineering, College of Chemistry, National Engineering Laboratory of Eco-Friendly Polymeric Materials (Sichuan), Sichuan University, Chengdu 610064, China |
|
|
|
|
Abstract Poly(p-dioxanone)-block-polyethylene glycol diblock copolymers functionalized with pyrene moieties (Py-PPDO-b-PEG) at the chain ends of PPDO blocks were synthesized for preparing anisotropic micelles with improved stability. The micellization and crystallization of the copolymers were investigated by nano differential scanning calorimetry (Nano DSC), transmission electron microscopy (TEM), UV-vis spectrophotometery, fluorophotometer, and dynamic light scattering (DLS), respectively. The results indicated that the aggregation of pyrene induced by intermolecular interaction lead to micellization of Py-PPDO-b-PEG at much lower concentrations than those of PPDO-b-PEG copolymers without pyrene moieties. The aggregation of pyrene moieties may also serve as nucleation agent and therefore enhance the crystallization rate of PPDO blocks. Fluorescence measurements by using Nile Red as the fluorescent agent indicated that the micelles of Py-PPDO-b-PEG have high stability and load capacity for hydrophobic molecules.
|
|
Received: 20 May 2014
Published: 22 July 2014
|
| Fund: This work was financially supported by the National Natural Science Foundation of China (Nos. 21274093 and 51121001), Program for Changjiang Scholars and Innovative Research Team in University of Ministry of Education of China (No. IRT1026), and National High-Tech Research and Development Program (863 Program) of China (No. 2012AA062904). |
|
Corresponding Authors:
Si-Chong Chen, Yu-Zhong Wang
E-mail: chensichong@scu.edu.cn;yzwang@scu.edu.cn
|
|
|
|
| [1] |
W.N. He, J.T. Xu, Crystallization assisted self-assembly of semicrystalline block copolymers, Prog. Polym. Sci. 37 (2012) 1350-1400.
|
| [12] |
L.G. Yin, M.A. Hillmyer, Disklike micelles in water from polyethylene-containing diblock copolymers, Macromolecules 44 (2011) 3021-3028.
|
| [22] |
M. Harada, I. Bobe, H. Saito, et al., Improved anti-tumor activity of stabilized anthracy-cline polymeric micelle formulation, NC-6300, Cancer Sci. 102 (2011) 192-199.
|
| [19] |
G. Riess, Micellization of block copolymers, Prog. Polym. Sci. 28 (2003) 1107-1170.
|
| [4] |
N. Petzetakis, A.P. Dove, R.K. O'Reilly, Cylindrical micelles from the living crystallization-driven self-assembly of poly(lactide)-containing block copolymers, Chem. Sci. 2 (2011) 955-960.
|
| [15] |
G. Wu, S.C. Chen, X.L. Wang, et al., Dynamic origin and thermally induced evolution of new self-assembled aggregates from an amphiphilic comb-like graft copolymer: a multiscale and multimorphological procedure, Chem. Eur. J. 18 (2012) 12237-12241.
|
| [16] |
F. Song, W.T. Shi, X.T. Dong, et al., Fennel-like nanoaggregates based on polysaccharide derivatives and their application in drug delivery, Colloids Surf. B 113 (2014) 501-504.
|
| [17] |
S.C. Chen, L.L. Li, H. Wang, et al., Synthesis and micellization of amphiphilic multibranched poly(p-dioxanone)-block-poly(ethylene glycol), Polym. Chem. 3 (2012) 1231-1238.
|
| [18] |
F.Y. Zhai, W. Huang, G. Wu, et al., Nanofibers with very fine core-shell morphology from anisotropic micelle of amphiphilic crystalline-coil block copolymer, ACS nano 7 (2013) 4892-4901.
|
| [21] |
J. RiosDoria, A. Carie, T. Costich, et al., A versatile polymer micelle drug delivery system for encapsulation and in vivo stabilization of hydrophobic anticancer drugs, J. Drug Deliv. 2012 (2012) (Article ID 951741).
|
| [24] |
X.L. Wang, Y.R. Mou, S.C. Chen, et al., A water-soluble PPDO/PEG alternating multiblock copolymer: synthesis, characterization, and its gel-sol transition behavior, Eur. Polym. J. 45 (2009) 1190-1197.
|
| [11] |
W.N. He, B. Zhou, J.T. Xu, B.Y. Du, Z.Q. Fan, Two growth modes of semicrystalline cylindrical poly(e-caprolactone)-b-poly(ethylene oxide) micelles, Macromolecules 45 (2012) 9768-9778.
|
| [7] |
Y. Zhao, X. Shi, H. Gao, et al., Thermo-and pH-sensitive polyethylene-based diblock and triblock copolymers: synthesis and self-assembly in aqueous solution, J. Mater. Chem. 22 (2012) 5737-5745.
|
| [23] |
P. Opanasopit, M. Yokoyama, M. Watanabe, et al., Block copolymer design for camptothecin incorporation into polymeric micelles for passive tumor targeting, Pharm. Res. 21 (2004) 2001-2008.
|
| [8] |
Z.Y. Li, R. Liu, B.Y. Mai, et al., Temperature-induced and crystallization-driven selfassembly of polyethylene-b-poly(ethylene oxide) in solution, Polymer 54 (2013) 1663-1670.
|
| [9] |
D.D. Yao, Y.J. Guo, S.G. Chen, J.N. Tang, Y.M. Chen, Shaped core/shell polymer nanoobjects with high antibacterial activities via block copolymer microphase separation, Polymer 54 (2013) 3485-3491.
|
| [13] |
S.C. Chen, G. Wu, J. Shi, Y.Z. Wang, Novel "star anise"-like nano aggregate prepared by self-assembling of preformed microcrystals from branched crys-talline-coil alternating multi-block copolymer, Chem. Commun. 47 (2011) 4198-4200.
|
| [14] |
H. Wang, C.L. Liu, G. Wu, et al., Temperature dependent morphological evolution and formation mechanism of anisotropic nano aggregates from crystalline-coil block copolymer of poly(p-dioxanone) and poly (ethylene glycol), Soft Matter 9 (2013) 8712-8722.
|
| [20] |
T.C. Lai, H. Cho, G.S. Kwon, Reversibly core cross-linked polymeric micelles with pH-and reduction-sensitivities: effects of cross-linking degree on particle stability, drug release kinetics, and anti-tumor efficacy, Polym. Chem. 5 (2014) 1650-1661.
|
| [5] |
N. Petzetakis, D. Walker, A.P. Dove, R.K. O'Reilly, Crystallization-driven sphere-to-rod transition of poly(lactide)-b-poly(acrylic acid) diblock copolymers: mechanism and kinetics, Soft Matter 8 (2012) 7408-7414.
|
| [10] |
A.M. Mihut, J.J. Crassous, J.F. Dechézelles, et al., Towards smart self-assembly of colloidal silica particles through diblock copolymer crystallization, Polymer 54 (2013) 3874-3881.
|
| [25] |
L. Yan, W. Wu, W. Zhao, et al., Reduction-sensitive core-cross-linked mPEG-poly (ester-carbonate) micelles for glutathione-triggered intracellular drug release, Polym. Chem. 3 (2012) 2403-2412.
|
| [2] |
P.A. Rupar, L. Chabanne, M.A. Winnik, I. Manners, Non-centrosymmetric cylindrical micelles by unidirectional growth, Science 337 (2012) 559-562.
|
| [3] |
H. Qiu, G. Cambridge, M.A. Winnik, I. Manners, Multi-armed micelles and block co-micelles via crystallization-driven self-assembly with homopolymer nanocrystals as initiators, J. Am. Chem. Soc. 135 (2013) 12180-12183.
|
| [6] |
J. Schmelz, M. Karg, T. Hellweg, H. Schmalz, General pathway toward crystallinecore micelles with tunable morphology and corona segregation, ACS Nano 5 (2011) 9523-9534.
|
| [27] |
M. Krishna, Excited-state kinetics of the hydrophobic probe Nile Red in membranes and micelles, J. Phys. Chem. A 103 (1999) 3589-3595.
|
| [26] |
C.J. Chen, Q. Jin, G.Y. Liu, et al., Reversibly light-responsive micelles constructed via a simple modification of hyperbranched polymers with chromophores, Polymer 53 (2012) 3695-3703.
|
|
|
|
