Polyion complex vesicles

Schrage S, Sigel R, Schlaad H (2003) Formation of amphiphilic polyion complex vesicles from mixtures of oppositely charged block ionomers. Macromolecules 36(5) 1417-1420... 

Anraku Y, Kishimura A, Oba M et al (2010) Spontaneous formation of nanosized unilamellar polyion complex vesicles with tunable size and properties. J Am Chem Soc 132 1631-1636... 

Kishimura A, Koide A, Osada K, Yamasaki Y, Kataoka K. Encapsulation of myoglobin in PEGylated polyion complex vesicles made from a pair of oppositely charged block iono-mers a physiologically available oxygen carrier. Angew Chem Int Ed 2007 46(32) 6085-8. 

Chuanoi S, Anraku Y, Hori M, Kishimura A, Kataoka K. Fabrication of polyion complex vesicles with enhanced salt and tempo ature resistance and their potential applications as enzymatic nanoreactors. Biomacromolecules 2014 15(7) 2389-97. 

Kishimura A. Development of polyion complex vesicles (PlCsomes) from block copoly mers for biomedical applications. Polym J 2013 45(9) 892-7. 

Anraku Y, Kishimura A, Yamasaki Y, Kataoka K. Living unimodal growth of polyion complex vesicles via two-dimensional supramolecular polymerization. J Am Chem Soc 2013 135(4) 1423-9. 

The problem with using surfactant-modified stationary phases in LC is that the surfactant will usually slowly elute (bleed) from the support thus resulting in different retention behavior of solutes with time. This is why most applications are in the area of GC or GLC. An exciting recent advance has been reported by Okahata, et al (181). Namely, a procedure has been developed for immobilizing a stable surfactant vesicle bilayer as the stationary phase in GC. A bilayer polyion complex composed of DODAB vesicles and sodium poly(styrene sulfonate) was deposited on Uniport HP and its properties as a GC stationary phase evaluated. Unlike previous lipid bilayers which exhibited poor physical stability, the DODAB polyion phase was stable. Additionally, the temperature-retention behavior of test solutes exhibited a phase transition inflection point. The work demonstrates that immobilized surfactant vesicle bilayer stationary phases can be employed in GC separations (181). Further work in this direction will likely lead to many such unique gas chromatographic supports and novel separations. 

Synthesis macrosurfactants, polysoaps, polyelectrolytes as building blocks preparation of spherical, cylindrical, multicompartment, and schizophrenic micelles, polymer vesicles, polyion complexes bottom-up self-assembly stimuli-sensitive colloids... 

Figure 5.30 Schematic illustration of a polyion complex (PIC) vesicle generated by blending a poly(l,2-butadiene-Z)-cesium methacrylate) block ionomer with an oppositely charged poly(styrene-Z)-l-methyl-4-vinylpyridinium iodide) block ionomer. Note that the internal and external polymer brushes are chemically dissimilar, demonstrating the fine tunability and enhanced versatility of this class of materials. (Adapted from Schrage, S., Sigel, R. and Schlaad, H. Macromolecules 36, 1417, 2003, and reprinted with permission. Copyright (2003) American Chemical Society.)...

The study of membrane and nucleic acid systems presents greater complexities. The study of lipids and insoluble membrane proteins in association with them can be achieved in solution scattering [75,76] by the use of lipid vesicles to solubilize the system of interest. Membrane proteins can alternatively be studied by solubilization using detergent micelles. The exception to this generalization is the group of plasma hpoproteins which are readily soluble in aqueous buffers. Systems with nucleic acids (i.e. protein-nucleic acid complexes, viruses, ribosomes and chromatin) [24-27,77,78] are not affected by these solubihty problems. However, lipid and nucleic acid systems are both further complicated in their analyses by the polyionic character of these macromolecules. Particular care is required concerning the partial specific volumes of the individual components to be used within the system of interest. 

Fig. 24. 32 Left Structure of guanidinium calix[6]arene 7. Right. Vesicle experiments (i) Addition of polyions (e.g., ctDNA) and counterion activators (e.g., DG, guanidiniocalixarenes) to vesicles with internal reporter ions (e.g., DPX, HPTS) and counterion inactivators (e.g., pK) triggers (ii) the formation of membrane-active polyion-counterion complexes (e.g., ctDNA-DG), (ill) DPX export, (iv) the formation of internal polyion-counterion complexes (e.g., ctDNA-DG-pK), etc M = Na [100]. (Reprinted from Ref. [100])...

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