A Thermoreversible Micellization−Transfer−Demicellization Shuttle between Water and an Ionic Liquid

Bai, Zhongxiang; He, Yiyong; Young, Nicholas P.; Lodge, Timothy P.

doi:10.1021/ma8011152

Cited by 54 publications

(84 citation statements)

References 38 publications

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“…It has been demonstrated that the driving force for the phase transfer of self-assembled PB−PEO and PS−PEO micelles in the biphasic system is the higher affinity of PEO to water than [EMIM]-[TFSI] at room temperature. 17,18 However, we have found that the phase transfer of PS−PEO assemblies is also strongly dependent on the volume fraction of solvophilic PEO block (f PEO ) in the block copolymers, as illustrated in Figure 2. Based on the phase transfer diagram (Figure 2), a minimum f PEO [TFSI] to water regardless of molecular weight from 200 g/mol to 1000 kg/mol.…”

Section: ■ Introductionmentioning

confidence: 98%

Interfacial Tension-Hindered Phase Transfer of Polystyrene-b-poly(ethylene oxide) Polymersomes from a Hydrophobic Ionic Liquid to Water

Lodge

2015

Langmuir

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We examine the phase transfer of polystyrene-b-poly(ethylene oxide) (PS-PEO) polymersomes from a hydrophobic ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]), into water. The dependence of the phase transfer on the molecular weight and PEO volume fraction (fPEO) of the PS-PEO polymersomes was systematically studied by varying the molecular weight of PS (10,000-27,000 g/mol) as well as by varying the volume fraction of PEO (fPEO) between 0.1 and 0.3. We demonstrate a general boundary for the phase transfer in terms of a reduced tethering density for PEO (σPEO), which is independent of the molecular weight of the hydrophobic PS. The reduced PEO tethering density was controlled by changing the polymersome size (i.e., increased polymersome sizes increase σPEO), confirming that it is the driving force in the transfer of PS-PEO polymersomes at room temperature. The phase transfer dependence on σPEO was also analyzed in terms of the free energy of polymersomes in the biphasic system. The quality of the aqueous phase, which affects the interfacial tension of the PS membrane, influenced the phase transfer. We systematically reduced the interfacial tension by adding a water-selective solvent, THF, which has a similar effect to increasing σPEO. The results indicate that the interfacial tension between the membrane and water plays an important role in the phase transfer with the corona and that the phase transfer can be controlled either by the dimensions of the polymersomes or by the suitability of the solvent for the membrane. The interfacial tension-hindered phase transfer of polymersomes in the biphasic water-[EMIM][TFSI] system will inform the design of temperature-sensitive and reversible nanoreactors and the separation of polydisperse particles according to size by tuning the quality of the solvent.

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Section: ■ Introductionmentioning

confidence: 98%

Interfacial Tension-Hindered Phase Transfer of Polystyrene-b-poly(ethylene oxide) Polymersomes from a Hydrophobic Ionic Liquid to Water

Lodge

2015

Langmuir

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“…Similar to the conventional Winsor I microemulsion extraction, hydrophobic ILs provide the chance for transferring organic product from nonionic surfactant micelle aqueous solution to excess IL phase by the novel Winsor I microemulsion extraction. Furthermore, the peculiar characters of hydrophobic ILs also lead to the novel Winsor I microemulsion extraction have some potential advantages, such as relatively high phase transfer temperature (81°C) [24] for operation at room temperature, very limited solubility of [Bmim]PF 6 in water at room temperature for removal of the contaminated nonionic surfactant in the excess IL phase by washing with water [25], and extraction of organic compounds with broad polar spectrum [21].…”

Section: Introductionmentioning

confidence: 99%

Transferring of red Monascus pigments from nonionic surfactant to hydrophobic ionic liquid by novel microemulsion extraction

Shen

Zhang

Liu

et al. 2014

Separation and Purification Technology

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“…This route has been investigated for both small molecule surfactants 3–7 and amphiphilic polymers. 8–11 Advantages of these self-assembled structures over non-supported systems include the segregation of reactive components in order to perform cascade reactions, 12, 13 the ability to react hydrophobic substrates in water, 8 increased local concentration of substrates 14–18 and simple catalyst recovery. 10 Recently, Uozumi and co-workers have shown that a nitrogen-carbon-nitrogen (NCN) pincer Pd-amphiphile was capable of self-assembling into vesicles and sequestering hydrophobic substrates into the catalytically active membrane.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Y-tailed amphiphilic homopolymers – aqueous nanoreactors for high activity, low loading SCS pincer catalysts

et al. 2013

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A new amphiphilic homopolymer bearing an SCS pincer palladium complex has been synthesized by reversible addition fragmentation chain transfer polymerization. The amphiphile has been shown to form spherical and worm-like micelles in water by cryogenic transmission electron microscopy and small angle neutron scattering. Segregation of reactive components within the palladium containing core results in increased catalytic activity of the pincer compound compared to small molecule analogues. This allows carbon-carbon bond forming reactions to be performed in water with reduced catalyst loadings and enhanced activity.

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A Thermoreversible Micellization−Transfer−Demicellization Shuttle between Water and an Ionic Liquid

Cited by 54 publications

References 38 publications

Interfacial Tension-Hindered Phase Transfer of Polystyrene-b-poly(ethylene oxide) Polymersomes from a Hydrophobic Ionic Liquid to Water

Interfacial Tension-Hindered Phase Transfer of Polystyrene-b-poly(ethylene oxide) Polymersomes from a Hydrophobic Ionic Liquid to Water

Transferring of red Monascus pigments from nonionic surfactant to hydrophobic ionic liquid by novel microemulsion extraction

Catalytic Y-tailed amphiphilic homopolymers – aqueous nanoreactors for high activity, low loading SCS pincer catalysts

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