Zhifeng Bai

Polymersomes with ionic liquid interiors dispersed in water.

We describe polymersomes with ionic liquid interiors dispersed in water. The vesicles are prepared via a simple and spontaneous migration of poly(butadiene-b-ethylene oxide) (PB-PEO) block copolymer vesicles from a hydrophobic ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]), to water at room temperature. As PB is insoluble in both water and [EMIM][TFSI] and PEO is well solvated in both media, the vesicles feature a PB membrane with PEO brushes forming both interior and exterior coronas. The robust and stable PB-PEO vesicles migrate across the liquid-liquid interface with their ionic liquid interiors intact and form a stabilized aqueous dispersion of vesicles enclosing microscopic ionic liquid pools. The nanostructure of the vesicles with ionic liquid interiors dispersed in water is characterized by direct visualization using cryogenic transmission electron microscopy. Upon heating, the vesicles can be quantitatively transferred back to [EMIM][TFSI], thus enabling facile recovery. The reversible transport capability of the shuttle system is demonstrated by the use of distinct hydrophobic dyes, which are selectively and simultaneously loaded in the vesicle membrane and interior. Furthermore, the fluorescence of the loaded dyes in the vesicles enables probing of the microenvironment of the vesicular ionic liquid interior through solvatochromism and direct imaging of the vesicles using laser scanning confocal microscopy. This vesicle system is of particular interest as a nanocarrier or nanoreactor for reactions, catalysis, and separations using ionic liquids.

Thermodynamics and mechanism of the block copolymer micelle shuttle between water and an ionic liquid.

The micelle shuttle utilizing block copolymer micelles as nanocarriers for transportation between water and a hydrophobic ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]), is examined in detail. Rhodamine B, a dye with a high molar absorptivity and fluorescence quantum yield, is conjugated to a short poly(1,2-butadiene) homopolymer and then loaded in amphiphilic poly((1,2-butadiene)-block-ethylene oxide) (PB-PEO) block copolymer micelles. The round-trip transportation of the micelles between water and the ionic liquid is simply triggered by temperature; it is fully reversible, quantitative, and without leakage. Quantitative fluorescence analysis reveals that the micelle distribution in the biphasic system has a very strong temperature dependence, which is favorable for control of the transportation. The standard Gibbs free energy change (DeltaG(o)), standard enthalpy change (DeltaH(o)), and standard entropy change (DeltaS(o)) of the micelle shuttle are extracted from the temperature dependence of the micelle distribution. Both DeltaH(o) and DeltaS(o) are positive, indicating an entropy-driven process. The slow yet spontaneous micelle shuttle is explored under quiescent conditions to understand the transfer kinetics. Both of the two-way transfers involve three steps, formation of micelle-concentrated [EMIM][TFSI]/water droplets in the initial phase, sedimentation/creaming of the droplets to the interface, and diffusion of the micelles to the destination phase. A detailed mechanism for the transfer is therefore proposed.

Pluronic micelle shuttle between water and an ionic liquid.

We demonstrate an effective micelle shuttle between water and a hydrophobic ionic liquid and its application in transportation in the biphasic system, using a commercially available and inexpensive Pluronic block copolymer. The poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (P123) block copolymer self-assembles into micelles in both water and the ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate, as characterized by dynamic light scattering. The poly(ethylene oxide) blocks provide the well-solvated corona, whereas the poly(propylene oxide) blocks form the solvophobic core. The micelles can spontaneously transfer between the two phases upon a simple temperature stimulus; the transfer is reversible and repeatable, and (1)H NMR analysis indicates quantitative transfer. The micelle nanocarriers are used to transport various cargoes in the biphasic system: fully reversible transport of hydrophobic small organic dyes into and out of water and facile extraction of an ionic liquid-phobic polymer from the ionic liquid. This simple round-trip delivery system may be used in delivery, separations, and extraction in synthesis and biphasic catalysis involving ionic liquids.

Spontaneous phase transfer of thermosensitive hairy particles between water and an ionic liquid.

This article describes the temperature-induced phase transfer behavior of a series of thermosensitive polymer brush-grafted particles between water and a hydrophobic ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]). Six samples were made by surface-initiated atom transfer radical polymerization: silica particles grafted with poly(methoxypoly(ethylene glycol) methacrylate) (PPEGMMA) with two different molecular weights, poly(methoxytri(ethylene glycol) methacrylate) (PTEGMMA), poly(methoxydi(ethylene glycol) methacrylate) (PDEGMMA), and two copolymers of PEGMMA and TEGMMA with different compositions (P(PEGMMA-co-TEGMMA)-82 and P(PEGMMA-co-TEGMMA)-74). The cloud points of free PPEGMMA with M(n,SEC) of 23 and 40 kDa, P(PEGMMA-co-TEGMMA)-82, P(PEGMMA-co-TEGMMA)-74, and PTEGMMA in [EMIM][TFSI]-saturated water were 95, 94, 80, 72, and 43 °C, respectively. PDEGMMA was not soluble in the ionic liquid-saturated water. PPEGMMA brush-grafted particles moved spontaneously and completely from water to the [EMIM][TFSI] phase upon heating at 80 °C. When cooled to 22 °C, all particles returned to the water layer. From UV-vis absorbance measurements, the transfer temperature (T(tr)) of PPEGMMA-grafted particles from water to the ionic liquid was 42 °C. Thermodynamic analysis showed that the particle transfer was an entropically driven process. P(PEGMMA-co-TEGMMA)-82, P(PEGMMA-co-TEGMMA)-74, and PTEGMMA brush-grafted particles also underwent reversible and quantitative transfer between the two phases upon heating at 70 °C and cooling at 0 °C; their transfer temperatures from water to [EMIM][TFSI] were 36, 30, and 16 °C, respectively. T(tr) was a linear function of the cloud point of the corresponding free polymer in ionic liquid-saturated water. In contrast, PDEGMMA-grafted particles moved spontaneously to the ionic liquid layer upon heating but did not return to water even after prolonged stirring at 0 °C.