Mapping Coexistence Phase Diagrams of Block Copolymer Micelles and Free Unimer Chains

被引:13
作者
Li, Xiuli [1 ,2 ]
Cooksey, Tyler J. [3 ]
Kidd, Bryce E. [1 ,2 ]
Robertson, Megan L. [3 ]
Madsen, Louis A. [1 ,2 ]
机构
[1] Virginia Tech, Dept Chem, Blacksburg, VA 24061 USA
[2] Virginia Tech, Macromol Innovat Inst, Blacksburg, VA 24061 USA
[3] Univ Houston, Dept Chem & Biomol Engn, Houston, TX 77004 USA
基金
美国国家科学基金会;
关键词
NUCLEAR-MAGNETIC-RESONANCE; POLYMERIC MICELLES; FIELD GRADIENT; TRIBLOCK COPOLYMERS; LENGTH DEPENDENCE; SELF-DIFFUSION; DELIVERY; WATER; NMR; TEMPERATURE;
D O I
10.1021/acs.macromol.8b01220
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Block copolymer micelles can carry molecular cargo in a nanoscopic package that is tunable via polymer structure in combination with cargo and/or solution properties. We use NMR spectroscopy and diffusometry to investigate spherical micelles that self-assemble from diblock poly(ethylene oxide)-b-(epsilon-caprolactone) (PEO-PCL) at 1% w/v in D2O-THF-d(8) mixed solvents. For two series of micelles with block masses of 2 and 3 kg/mol (PEO and PCL, respectively) and 5 and 8 kg/ mol, we quantify diffusion coefficients and relative populations of micelles and free unimers over a range of temperatures (21-50 degrees C) and solvent compositions (10-100 vol % THF-d(8)). Micelles and free unimers coexist over surprisingly large areas of these micelle-unimer phase diagrams and with a large variation of relative populations. This study provides a new avenue for understanding how inter- and intramolecular interactions fundamentally affect unimer exchange, cargo release, the thermodynamics of chain partitioning, and the tuning of micelle structure and dynamics.
引用
收藏
页码:8127 / 8135
页数:9
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