Phase separation micelles

Solvents or homopolymers added to block copolymers bring about additional effects, especially, when the homopolymer is the same as one of the blocks [82-84]. Macroscopic phase separation, micelle formation and/or different mesophases can occur [65]. Disordered block copolymers, where the blocks are compatible, will not be considered here. 

In addition, polymer micelles have been demonstrated to be more stable and also have a significantly lower cmc than surfactant micelles. Further discussion of surfactant micelles is beyond the scope of this review, and, instead, the reader is directed to a recent review article by Armes. In fact, the polymer building blocks need not be amphiphilic and such phase-separated nanostructures can be formed from completely hydrophobic or lipophilic diblock copolymers that contain two segments with differing solubility (such as polystyrene- -polyisoprene) and hence can undergo phase separation in selective solvents. One example of such completely hydrophobic phase-separated micelles are those reported by Wooley and coworkers, which can be obtained from toluene and acetone solutions of a [polystyrene-a/f-poly(maleic anhydride)]-fc-polyisoprene Iriblock. Conversely, inverse structures are also accessible and are known as reverse micelles. These can be formed by adding a nonsolvent for the hydrophilic block to afford the opposite of a conventional micelle, for which the hydrophilic core is surrounded by a hydrophobic shell in a hydrophobic surrounding media. There have been a handful of reports on the application of these reverse micelles, for example, as nanoreactors and for the extraction of water-soluble molecules. ... 

Figure B3.6.4. Illustration of tliree structured phases in a mixture of amphiphile and water, (a) Lamellar phase the hydrophilic heads shield the hydrophobic tails from the water by fonning a bilayer. The amphiphilic heads of different bilayers face each other and are separated by a thin water layer, (b) Hexagonal phase tlie amphiphiles assemble into a rod-like structure where the tails are shielded in the interior from the water and the heads are on the outside. The rods arrange on a hexagonal lattice, (c) Cubic phase amphiphilic micelles with a hydrophobic centre order on a BCC lattice.

Aqueous-detergent solutions of appropriate concentration and temperature can phase separate to form two phases, one rich in detergents, possibly in the form of micelles, and the other depleted of the detergent (Piyde and Phillips, op. cit.). Proteins distribute between the two phases, hydrophobic (e.g., membrane) proteins reporting to the detergent-rich phase and hydrophilic proteins to the detergent-free phase. Indications are that the size-exclusion properties of these systems can also be exploited for viral separations. These systems would be handled in the same way as the aqueous two-phase systems. 

To complete this overview of chain models, we mention the dimer models, which represent the amphiphiles by just two units attached to each other [153-157]. They have been used to study curved bilayers [153], the kinetics of phase separation between oil and water in the presence of surfactants [155], and some aspects of self-assembled micelles [154,157] (see below). 

Aqueous-detergent solutions of appropriate concentration and temperature can phase-separate to form two phases, one rich in detergents, possibly in the form of micelles, and the other depleted of the detergent [Pryde and Phillips, Biochem. J., 233, 525-533 (1986)]. 

Fig. 67 Schematic of phase behaviour for blend of novolac epoxy resin with nearly symmetric poly(methyl acrylate-co-glycidylmelhacrylate)-0-polyisoprene. Ordered L can be swollen with up to about 30% of resin before macroscopic phase separation occurs, producing heterogeneous morphologies containing various amounts of L, C, worm-like micelles and pristine epoxy. At lower concentrations, disordered worm-like micelles transform into vesicles in dilute limit. According to [201]. Copyright 2003 Wiley...

Oheme and co-workers investigated335 in an aqueous micellar system the asymmetric hydrogenation of a-amino acid precursors using optically active rhodium-phosphine complexes. Surfactants of different types significantly enhance both activity and enantioselectivity provided that the concentration of the surfactants is above the critical micelle concentration. The application of amphiphilized polymers and polymerized micelles as surfactants facilitates the phase separation after the reaction. Table 2 shows selected hydrogenation results with and without amphiphiles and with amphiphilized polymers for the reaction in Scheme 61.335... 

A slight increase in the turbidity upon heating of aqueous solutions of the s-fractions of the NVCl/NVIAz-copolymers obtained from the feeds with initial comonomer molar ratios of 75 25 (Tcp 65 °C) and 80 20 (Tcp 66 °C) could be due to the micellization phenomena, although the absence of DSC peaks over the same temperature range testified to the non-cooperative character of the process. This could indicate that the chains of these s-type copolymers had, nevertheless, a certain amount of oligoNVCl blocks non-buried by the hydrophilic microenvironment sufficiently well and thus capable of participating in the hydrophobically-induced associative intermolecular processes at elevated temperatures. At the same time, the sequence of monomer units in the s-copolymers obtained from the feeds with the initial comonomer ratios of 85 15 and 90 10 (mole/mole) corresponded to the block-copolymers of another type. The basis for such a conclusion is the lack of macroscopic heat-induced phase separation at elevated temperatures (Fig. 3 a and b) and, simultaneously, the transi-... 

Block copolymers at high styrene contents behave similarly, with no break around the micellar region. Two of the block copolymers are shown separately in Figure 7c. The low M.W. BC 90 moves from an apparently adequate stabilization in CCI4 to a new level of modest protection at higher CyH g volume fractions. The block polymer of 42% styrene gives a hint of a discontinuity at the non-solvent content for micelle formation, but thereafter stabilizes the silica until the conditions approach those for phase separation. 

In the micellar region the trend to decreasing colloid stability is arrested and a partial improvement, in line with the enhanced level of polymer adsorption, is noted until the conditions for gross phase separation are reached. Only the intermediate block copolymer BC 42 shows indications of discontinuities in behavior at the solvent composition for micelle formation. The results presented here do not show the sharp transition from stability to instability found experimentally (4,8,17) by Napper and generally expected on theoretical grounds. However, there are important differences in experimental methodology that must be emphasised. 

A similar multiphase complication that should be kept in mind when discussing solutions at finite concentrations is possible micelle formation. It is well known that for many organic solutes in water, when the concentration exceeds a certain solute-dependent value, called the critical micelle concentration (cmc), the solute molecules are not distributed in a random uncorrelated way but rather aggregate into units (micelles) in which their distances of separation and orientations with respect to each other and to solvent molecules have strong correlations. Micelle formation, if it occurs, will clearly have a major effect on the apparent activity coefficient but the observation of the phenomenon requires more sophisticated analytical techniques than observation of, say, liquid-liquid phase separation. 

The interactions between SDS and water represent a compromise between the extremes of complete phase separation (as happens when benzene and water mix) and molecular dispersion (SDS in dilute aqueous solution). A micelle forms. To minimize the energetically unfavourable interactions with water, SDS molecules aggregate to form a variety of microscopic structures, such as the dandelion head in Figure 10.12. 

In a recent study, Jin and Kaplan (2003) demonstrate the formation of silk fibroin aggregates in the presence of polyethylene glycol, and present a step by step model for fiber formation based on the principle of micelle formation, and driven by dehydration as well as flow elongation. During this process, hydrophobic chains are exposed to the solvent, but because of the molecules high free energy, water solvation is unfavorable and phase separation followed by aggregation predominates. 

Phase separation model, of micellization, 24 128-129 Phase structure(s)... 

Addition of compounds such as long-chain alkyl compounds in re-versed-phase separations will alter the retention of ionic compounds but will have no effect on nonionic compounds unless the concentration is high enough to form micelles (for additional information, please refer to Chapter 8, reference 5). 

The mixed liposomal solutions were prepared by the ethanol-injection method(13) in order to obtain completely transparent solutions. It is interesting to note that miscibility of the photochromic amphiphiles with DPPC depend on the position of bulky azobenzene. If azobenzene is incorporated close to the end of long alkyl chain, a stable mixed bilayer state cannot be formed. On the other hand, when the azobenzene moiety is located near the head group or at the center of the hydrocarbon tail, the azobenzene amphiphiles are successfully incorporated into the bilayer membrane. No individual micelle formation nor phase separation in the bilayer was observed at 25 °C by absorption spectroscopy. However, the microstructure of the mixed liposomes depends on the type of azobenzene amphiphiles. 

Figure 6.5 Illustrations of nanoscale spherical assemblies resulting from block copolymer phase separation in solution are shown, along with the chemical compositions that have been employed to generate each of the nanostructures (a) core crosslinked polymer micelles (b) shell crosslinked polymer micelles (SCKs) with glassy cores (c) SCKs with fluid cores (d) SCKs with crystalline cores (e) nanocages, produced from removal of the core of SCKs (f) SCKs with the crosslinked shell shielded from solution by an additional layer of surface-attached linear polymer chains (g) crosslinked vesicles (h) shaved hollow nanospheres produced from cleavage of the internally and externally attached linear polymer chains from the structure of (g)...

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