Block copolymer assemblies with cross-link stabilization: From single-component monolayers to bilayer blends with PEO-PLA

被引:63
作者
Ahmed, F
Hategan, A
Discher, DE [1 ]
Discher, BM
机构
[1] Univ Penn, Dept Bioengn, Chem & Biomol Engn Dept, Philadelphia, PA 19104 USA
[2] Univ Penn, Dept Biochem & Biophys, Philadelphia, PA 19104 USA
关键词
D O I
10.1021/la034178l
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Amphiphilic diblock copolymers containing poly(ethylene oxide) (PEO) and saturated polybutadiene (PBD) hydrophobic chains have been cross-linked in both monolayer and bilayer assemblies. For monolayers, the Langmuir isotherm proves consistent with prior measures of density and compressibility for bilayer vesicles, and the monolayers can be macroscopically transferred as Langmuir-Blodgett films. Since the films are inverted (PBD oriented away from the slide) at the air-water interface, they spontaneously reorganize when immersed in water into wormlike micelles. However, this transition is quenched when the film is stabilized by free radical polymerization. Atomic force microscopy shows a stabilized but pitted film, which allows height measurements that prove consistent with a monolayer. With bilayer vesicles, we investigate several additional aspects of cross-linking. Spatial control of membrane cross-linking on the micrometer-scale is demonstrated by dynamic inflation-deflation of a membrane fixed to the end of a micropipet. Complete polymerization of the bilayer renders vesicles resilient to chloroform solubilization, whereas preblending with a non-cross-linkable diblock copolymer of PEO-polylactic acid, undermines vesicle stability in chloroform-water solutions. The results prove miscibility and stable integration of two disparate block copolymers in a membrane, as well as a first-order scheme for controlled release of encapsulants.
引用
收藏
页码:6505 / 6511
页数:7
相关论文
共 48 条
[1]  
AHMED F, UNPUB
[2]  
Bangham A D, 1968, Prog Biophys Mol Biol, V18, P29, DOI 10.1016/0079-6107(68)90019-9
[3]  
BANGHAM AD, 1974, METHODS MEMBRANE BIO, V11, P38
[4]   Chemisorbed poly(propylene sulphide)-based copolymers resist biomolecular interactions [J].
Bearinger, JP ;
Terrettaz, S ;
Michel, R ;
Tirelli, N ;
Vogel, H ;
Textor, M ;
Hubbell, JA .
NATURE MATERIALS, 2003, 2 (04) :259-264
[5]   Molecular weight dependence of polymersome membrane structure, elasticity, and stability [J].
Bermudez, H ;
Brannan, AK ;
Hammer, DA ;
Bates, FS ;
Discher, DE .
MACROMOLECULES, 2002, 35 (21) :8203-8208
[6]   Polymersomes: Tough vesicles made from diblock copolymers [J].
Discher, BM ;
Won, YY ;
Ege, DS ;
Lee, JCM ;
Bates, FS ;
Discher, DE ;
Hammer, DA .
SCIENCE, 1999, 284 (5417) :1143-1146
[7]   Cross-linked polymersome membranes: Vesicles with broadly adjustable properties [J].
Discher, BM ;
Bermudez, H ;
Hammer, DA ;
Discher, DE ;
Won, YY ;
Bates, FS .
JOURNAL OF PHYSICAL CHEMISTRY B, 2002, 106 (11) :2848-2854
[8]   Polymer vesicles [J].
Discher, DE ;
Eisenberg, A .
SCIENCE, 2002, 297 (5583) :967-973
[9]   PERMEABILITY CHARACTERISTICS OF POLYMERIC BILAYER-MEMBRANES FROM METHACRYLOYL AND BUTADIENE LIPIDS [J].
DORN, K ;
KLINGBIEL, RT ;
SPECHT, DP ;
TYMINSKI, PN ;
RINGSDORF, H ;
OBRIEN, DF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (06) :1627-1633
[10]   Elastomeric suspended membranes generated via Langmuir-Blodgett transfer [J].
Goedel, WA ;
Heger, R .
LANGMUIR, 1998, 14 (13) :3470-3474