Diblock micelles

Micellar structure has been a subject of much discussion [104]. Early proposals for spherical [159] and lamellar [160] micelles may both have merit. A schematic of a spherical micelle and a unilamellar vesicle is shown in Fig. Xni-11. In addition to the most common spherical micelles, scattering and microscopy experiments have shown the existence of rodlike [161, 162], disklike [163], threadlike [132] and even quadmple-helix [164] structures. Lattice models (see Fig. XIII-12) by Leermakers and Scheutjens have confirmed and characterized the properties of spherical and membrane like micelles [165]. Similar analyses exist for micelles formed by diblock copolymers in a selective solvent [166]. Other shapes proposed include ellipsoidal [167] and a sphere-to-cylinder transition [168]. Fluorescence depolarization and NMR studies both point to a rather fluid micellar core consistent with the disorder implied by Fig. Xm-12. 

AB diblock copolymers in the presence of a selective surface can form an adsorbed layer, which is a planar form of aggregation or self-assembly. This is very useful in the manipulation of the surface properties of solid surfaces, especially those that are employed in liquid media. Several situations have been studied both theoretically and experimentally, among them the case of a selective surface but a nonselective solvent [75] which results in swelling of both the anchor and the buoy layers. However, we concentrate on the situation most closely related to the micelle conditions just discussed, namely, adsorption from a selective solvent. Our theoretical discussion is adapted and abbreviated from that of Marques et al. [76], who considered many features not discussed here. They began their analysis from the grand canonical free energy of a block copolymer layer in equilibrium with a reservoir containing soluble block copolymer at chemical potential peK. They also considered the possible effects of micellization in solution on the adsorption process [61]. We assume in this presentation that the anchor layer is in a solvent-free, melt state above Tg. The anchor layer is assumed to be thin and smooth, with a sharp interface between it and the solvent swollen buoy layer. 

Several studies have been performed to investigate the compatibalizing effect of blockcopolymers [67,158, 188,196-200], It is generally shown that the diblock copolymer concentration is enhanced at the interface between incompatible components when suitable materials are chosen. Micell formation and extremely slow kinetics make these studies difficult and specific non-equilibrium starting situations are sometimes used. Diblock copolymers are tethered to the interface and this aspect is reviewed in another article in this book [14]. 

Tamil S.S., Spatz, J.P., Klok H.A., and Martin M. Gold-polypyrrole core-shell particles in diblock copolymer micells, Aiiv. Mater., 10, 132, 1998. 

In 2000, the first example of ELP diblock copolymers for reversible stimulus-responsive self-assembly of nanoparticles was reported and their potential use in controlled delivery and release was suggested [87]. Later, these type of diblock copolypeptides were also covalently crossUnked through disulfide bond formation after self-assembly into micellar nanoparticles. In addition, the encapsulation of l-anilinonaphthalene-8-sulfonic acid, a hydrophobic fluorescent dye that fluoresces in hydrophobic enviromnent, was used to investigate the capacity of the micelle for hydrophobic drugs [88]. Fujita et al. replaced the hydrophilic ELP block by a polyaspartic acid chain (D ). They created a set of block copolymers with varying... 

Further modification of the above nanostructures is useful for obtaining new functional materials. Thirdly, we apply the dopant-induced laser ablation technique to site-selectively doped thin diblock copolymer films with spheres (sea-island), cylinders (hole-network), and wormlike structures on the nanoscale [19, 20]. When the dye-doped component parts are ablated away by laser light, the films are modified selectively. Concerning the laser ablation of diblock copolymer films, Lengl et al. carried out the excimer laser ablation of diblock copolymer monolayer films, forming spherical micelles loaded with an Au salt to obtain metallic Au nanodots [21]. They used the laser ablation to remove the polymer matrix. In our experiment, however, the laser ablation is used to remove one component of block copolymers. Thereby, we can expect to obtain new functional materials with novel nanostmctures. 

Figure 23. Polymer A and polymer B form the diblock copolymer micelles where metal nanoparticles can be grown.

Figure 24. TEM images of different gold nanoparticles grown in the micelles of diblock copolymers, a 6nm, b 4nm, c 2.5 nm.

Diblock copolymers consist of contiguous sequences of two different covalently bound monomer units, arranged in an -A-A-A-B-B-B-B- structure. In an appropriate solvent, the diblock copolymers spontaneously self-assemble into micelles with cores which are essentially pure in one component and a diameter... 

Figure 11.8 Formation of ordered nanoparticles of metal from diblock copolymer micelles, (a) Diblock copolymer (b) metal salt partition to centres of the polymer micelles (c) deposition of micelles at a surface (d) micelle removal and reduction of oxide to metal, (e) AFM image of carbon nanotubes and cobalt catalyst nanoparticles after growth (height scale, 5 nm scan size, lxl pm). [Part (e) reproduced from Ref. 47].

Fig. 51 Phase diagram for PS-PI diblock copolymer (Mn = 33 kg/mol, 31vol% PS) as function of temperature, T, and polymer volume fraction, cp, for solutions in dioctyl ph-thalate (DOP), di-n-butyl phthalate (DBP), diethyl phthalate (DEP) and M-tetradecane (C14). ( ) ODT (o) OOT ( ) dilute solution critical micelle temperature, cmt. Subscript 1 identifies phase as normal (PS chains reside in minor domains) subscript 2 indicates inverted phases (PS chains located in major domains). Phase boundaries are drawn as guide to eye, except for DOP in which OOT and ODT phase boundaries (solid lines) show previously determined scaling of PS-PI interaction parameter (xodt

Finally, we have designed and synthesized a series of block copolymer surfactants for C02 applications. It was anticipated that these materials would self-assemble in a C02 continuous phase to form micelles with a C02-phobic core and a C02-philic corona. For example, fluorocarbon-hydrocarbon block copolymers of PFOA and PS were synthesized utilizing controlled free radical methods [104]. Small angle neutron scattering studies have demonstrated that block copolymers of this type do indeed self-assemble in solution to form multimolecular micelles [117]. Figure 5 depicts a schematic representation of the micelles formed by these amphiphilic diblock copolymers in C02. Another block copolymer which has proven useful in the stabilization of colloidal particles is the siloxane based stabilizer PS-fr-PDMS [118,119]. Chemical... 

Arimura H, Ohya Y, Ouchi T (2005) Formation of core-shell type biodegradable polymeric micelles from amphiphilic poly(aspartic acid)-Wock-polylactide diblock copolymer. Biomacromolecules 6 720-725... 

A number of diblock copolymers of NIPAM and hydrophobic comonomers have been prepared by various groups and assessed in terms of micellar structure, thermosensitivity, and applications. For example, PS-fo-PNIPAM was shown to form either micelles consisting of a PS core and a PNIPAM corona, or vesicles. The assemblies were colloidally stable at elevated temperature [262-266]. 

Information about the process associated with the CMC has been provided by Tsunashima et al. [ 17], who investigated the micellization of a PS-PB diblock in various solvents. In these studies, DLS was used to measure R. Measurements were performed in solvents having the same refractive index of either the PS or PB chains, allowing the determination of the characteristic... 

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