Synthesis and pH-dependent micellization of 2-(diisopropylamino)ethyl methacrylate based amphiphilic diblock copolymers via RAFT polymerization

被引:52
作者
Hu, Ying Qian
Kim, Min Sang
Kim, Bong Sup
Lee, Doo Sung [1 ]
机构
[1] Sungkyunkwan Univ, Dept Polymer Sci & Engn, Suwon 440746, Gyeonggi, South Korea
[2] Sungkyunkwan Univ, Polymer Technol Inst, Suwon 440746, Gyeonggi, South Korea
基金
新加坡国家研究基金会;
关键词
amphiphilic diblock copolymer; pH-sensitive micelles; reversible addition-fragmentation chain transfer (RAFT) polymerization;
D O I
10.1016/j.polymer.2007.04.011
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
The polymerization of 2-(diisopropylamino)ethylmethacrylate (DPA) by RAFT mechanism in the presence of 4-cyanopentanoic acid dithio-benzoate in 1,4-dioxane was studied. The DPA homopolymer was employed as a macro chain transfer agent to synthesize pH-sensitive amphiphilic block copolymers using poly(ethylene glycol) methyl ether methacrylate (PEGMA) as the hydrophilic block. H-1 NMR and GPC measurements confirmed the successful synthesis of these copolymers. Potentiometric titrations and fluorescence experiments proved that the copolymers underwent a sharp transition from unimers to micelles at a pH of similar to 6.7 in phosphate buffered saline solutions. It was found that the hydrophilic/hydrophobic balance of these block copolymers had no apparent effect on their pH-induced micellization behaviors. The DLS investigation revealed that the micelles have a mean hydrodynamic diameter below 60 rim with a narrow size distribution. (C) 2007 Elsevier Ltd. All rights reserved.
引用
收藏
页码:3437 / 3443
页数:7
相关论文
共 26 条
[1]   Synthesis and aqueous solution properties of near-monodisperse tertiary amine methacrylate homopolymers and diblock copolymers [J].
Bütün, V ;
Armes, SP ;
Billingham, NC .
POLYMER, 2001, 42 (14) :5993-6008
[2]   Experimental requirements for an efficient control of free-radical polymerizations via the reversible addition-fragmentation chain transfer (RAFT) process [J].
Favier, Arnaud ;
Charreyre, Marie-Therese .
MACROMOLECULAR RAPID COMMUNICATIONS, 2006, 27 (09) :653-692
[3]   Tunable pH- and temperature-sensitive copolymer libraries by reversible addition-fragmentation chain transfer copolymerizations of methacrylates [J].
Fournier, David ;
Hoogenboom, Richard ;
Thijs, Hanneke M. L. ;
Paulus, Renzo M. ;
Schubert, Ulrich S. .
MACROMOLECULES, 2007, 40 (04) :915-920
[4]   Synthesis of new amphiphilic diblock copolymers and their self-assembly in aqueous solution [J].
Garnier, S ;
Laschewsky, A .
MACROMOLECULES, 2005, 38 (18) :7580-7592
[5]   Phosphorylcholine-based pH-responsive diblock copolymer micelles as drug delivery vehicles: Light scattering, electron microscopy, and fluorescence experiments [J].
Giacomelli, C ;
Le Men, L ;
Borsali, R ;
Lai-Kee-Him, J ;
Brisson, A ;
Armes, SP ;
Lewis, AL .
BIOMACROMOLECULES, 2006, 7 (03) :817-828
[6]   Stimuli-reponsive polymers and their bioconjugates [J].
Gil, ES ;
Hudson, SM .
PROGRESS IN POLYMER SCIENCE, 2004, 29 (12) :1173-1222
[7]   Supramolecular drug-delivery systems based on polymeric core-shell architectures [J].
Haag, R .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (03) :278-282
[8]   Block copolymer micelles for drug delivery: design, characterization and biological significance [J].
Kataoka, K ;
Harada, A ;
Nagasaki, Y .
ADVANCED DRUG DELIVERY REVIEWS, 2001, 47 (01) :113-131
[9]   pH-responsive PEG-poly(β-amino ester) block copolymer micelles with a sharp transition [J].
Kim, MS ;
Hwang, SJ ;
Han, JK ;
Choi, EK ;
Park, HJ ;
Kim, JS ;
Lee, DS .
MACROMOLECULAR RAPID COMMUNICATIONS, 2006, 27 (06) :447-451
[10]   Characterizing the structure of pH dependent polyelectrolyte block copolymer micelles [J].
Lee, AS ;
Gast, AP ;
Bütün, V ;
Armes, SP .
MACROMOLECULES, 1999, 32 (13) :4302-4310