Multicompartment micelles

Li, Z. B. Hillmyer, M. A. Lodge, T. P., Control of structure in multicompartment micelles by blending mu-ABC star terpolymers with AB diblock copolymers. Macromolecules 2006, 39, 765-771. 

S. Kubowicz, J.F. Baussard, J.F. Lutz, A.F. Thunemann, H. von Berlepsch, A. Laschewsky, Multicompartment micelles formed by self-assembly of linear ABC triblock copolymers in aqueous medium, Angew. Chem. Int. Ed. 44 (2005) 5262-5265. 

Z. Li, E. Kesselman, Y. Talmon, M.A. Hillmeyer, T.P. Lodge, Multicompartment micelles from ABC miktoarm stars in water. Science 306 (2004) 98-101. 

Fig. 8 Multicompartment micelle formation from p-EOF star terpolymers and binary blends of p-EOF/EO. (a) Hamburger micelle from p-EOF with a very long PEO block, (b) Segmented wormlike micelle from p-EOF with a short PEO block, (c) Hamburger micelle from blends of p-EOF/EO. Reprinted with permission from Hillmyer et al. [79]. Copyright 2006 American...

Figures 9-11 show that the IG SCF predictions can only qualitatively be used to analyse binary spherical brushes. By the same token, we might expect that a 3G SCF analysis may give a binary spherical brush even more degrees of freedom to form structures with even lower symmetries, for example by splitting up the compact B regions over several subregions. So-called raspberry-like multicompartment micelles have indeed been reported recently [14, 18, 78,79].

Miiller et al. [18] demonstrated that by carefully choosing the composition of triblock copolymers and adjusting the preparation techniques, precise hierarchical self-assembly of multicompartment micelles can be achieved, which can polymerize into micrometer structures (Fig. 5.10). 

Figure 17 Schematic illustration of a multicompartment micelle from (PE0)(PEE)(PFP0) miktoarm stars and binary blends of (PE0)(PEE) (PFPO) with PEO (a) hamburger micelle from the miktoarm star with a very long PEO block (0), (b) segmented wormlike micelle from the star with a short PEO block (0), and (c) hamburger micelle from blends (PEO) (PEE)(PFPO)/PEO. Reprinted from Li, Z. Hillmyer, M. A. Lodge, T. P. Macromolecules 2006, 39, 765. " °...

VBFP pentafluorophenyl 4-vinylbenzyl ether) was synthesized by a three-step sequential monomer addition, using benzyl dithio benzoate as CTA (Scheme 23). By postpolymerization reaction, the PVBCl block was quaternized by N-methylmorpholine yielding the cationic amphiphilic PVBM-PSt-PVBFP terpolymer comprising two highly incompatible hydrophobic blocks. The interest in this terpolymer stems from its ability to form multicompartment micelles of a novel nanostructure in aqueous media. 

Schacher E, Betthausen E, Walther A, Schmalz A, Pergushov D, Muller A (2009) Interpolyelectrolyte complexes of dynamic multicompartment micells. ACS Nano 3 2095... 

Figure 9 Top cartoon representations of a spherical micelle, a wormlike micelle, and a vesicle. The red blocks represent the solvophilic blocks, and the blue blocks represent the solvophobic blocks. Bottom example TEM images showing diffa-ent micelle morphologies adopted by block copolymers in solution, (a) Spherical micelles formed from polyfethylene oxide)-f>-polycaprolactone (PEO-f>-PCL) copolymers.(b) Wormlike micelles, vesicles, and octupi formed by mixing PEO-fc-polybutadiene (PEO-fc-PB) block copolymers. (Reproduced from Ref. 32. American Chemical Society, 2004.) (c) Vesicles formed from PEO-f>-PCL copolymers. (Reproduced from Ref. 33. Royal Society of Chemistry, 2011.) (d) Multicompartment micelles formed from a triblock copolyma-. (Reproduced from Ref. 34. American Chemical Society, 2010.) (e) Stomatocytes formed using PEO-f>-polystyrene (PEO-f>-PS) copolyma-s. (Reproduced from Ref. 35. American Chemical Society, 2010.) (f) Toroidal micelles coexisting with cylindrical micelles and sphaical micelles formed from poly(acrylic acid)-f>-poly(methacrylic acid)-fc-PS (PAA-f>-PMA-f>-PS) triblock copolymers. (Reproduced from Ref. 36. Royal Society of Chemistry, 2009.)...

Figure 18 Cryo-TEM micrographs of micellar aggregates in 0.5 wt% aqueous solutions of amphiphilic Iriblock copol3raiCTs (a) core-shell micelles formed from (OEGA)7o-(EHA)i4o-(FA)i3. Scale bar = 50 mn. (b) Patched multicompartment micelles formed from (EHA)i2o-(OEGA)io9-(FA)23. Scale bar = 50 nm. (c) Monomers used for the synthesis of triphiUc ABC block copol3raiCTs. (Adapted from Ref. 34. American Chemical Society, 2010.)...

Figure 20 A triblock copolymer (a) with two outer hydrophilic blocks that can self-assemble into mixed micelles (b), partly demixed or multicompartment micelles (c), or completely demixed, biphasic Janus micelles (d). The amphiphilicity on triggering the hydrophilic to hydrophobic transition may result in superstructure formation. (Reproduced from Ref. 49. American Chemical Society, 2010.)...

C.V. Synatschke, T. Nomoto, H. Cabral, M. Fortsch, K. Toh, Y. Matsumoto, K. Miyazaki, A. Hanisch, F.H. Schacher, A. Kishimura, N. Nishiyama, A.H. Muller, and K. Kataoka, Multicompartment micelles with adjustable poly(ethylene glycol) shell for efficient in vivo photodynamic therapy, ACS Nano, 8 (2), 1161-72,2014. 

The term multicompartment micelles is used to describe micelles with water-soluble shells and internally segmented cores, where two (or more) separate types... 

Saito N, Liu C, Lodge TP, Hillmyer MA (2008) Multicompartment micelles from polyester-containing ABC miktoarm star terpolymers. Macromolecules 41 8815-8822... 

Liu, C., Hillmyer, M.A., and Lodge, T.P. (2009a) Multicompartment micelles from pH-responsive miktoarm star block... 

Lodge, T.P. et al. (2005) Simultaneous, segregated storage of two agents in a multicompartment micelle. Journal of die American Chemical Society, 127,17608-17609. 

Li, Z.B., HiUmyer, M.A., and Lodge, TP. (2006b) Morphologies of multicompartment micelles formed by ABC miktoarm star terpolymers. Langmuir, 22,9409-9417. 

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