Self-assembling polymer with structured surface

One assembly example is polyethylenamine (PEI)-mediated self-assembly of FePt nanoparticles [56]. PEI is an all -NH-based polymer that can replace oleate/oleylamine molecules around FePt nanoparticles and attach to hydrophilic glass or silicon oxide surface through ionic interactions [52], A PEI/FePt assembly is readily fabricated by dipping the substrate alternately into PEI solution and FePt nanoparticle dispersion. Figure 10 shows the assembly process and TEM images of the 4 nm Fes8Pt42 nanoparticle self-assemblies on silicon oxide surfaces. Characterizations of the layered structures with X-ray reflectivity and AFM indicate that PEI-mediated FePt assemblies have controlled thickness and the surfaces of the assemblies are smooth with root mean square roughness less than 2 nm. 

Cationic polymers are defined as polyelectrolytes cariying positive charges, and they are either derived from natural sources such as chitosan, or chemically synthesized where the charges have been incorporated on their backbone and/or side chains. They may also exist as block copolymers, where one of the blocks is decorated with positive charges. When these block copolymers consist of a hydrophobic block, they readily undergo self-assembly in aqueous solutions and form micellar structures with a positively charged surface. Similarly, if the block copolymer consists of two hydrophobic blocks, one at each end, the system may self-assemble into network structures called hydrogels, which are water-rich 3D interconnected networks. 

Tethering may be a reversible or an irreversible process. Irreversible grafting is typically accomplished by chemical bonding. The number of grafted chains is controlled by the number of grafting sites and their functionality, and then ultimately by the extent of the chemical reaction. The reaction kinetics may reflect the potential barrier confronting reactive chains which try to penetrate the tethered layer. Reversible grafting is accomplished via the self-assembly of polymeric surfactants and end-functionalized polymers [59]. In this case, the surface density and all other characteristic dimensions of the structure are controlled by thermodynamic equilibrium, albeit with possible kinetic effects. In this instance, the equilibrium condition involves the penalties due to the deformation of tethered chains. 

The most versatile method to prepare such hollow capsules is self-assembly [203-205, 214, 215]. Owing to their amphiphilic nature and molecular geometry, lipid-based amphiphiles can aggregate into spherical closed bilayer structures in water so-called liposomes. It is quite reasonable that the hollow sphere structure of liposomes makes them suitable as precursors for the preparation of more functional capsules via modification of the surfaces with polymers and ligand molecules [205, 216, 217]. Indeed, numerous studies based on liposomes in this context have been performed [205, 209, 213]. 

Recently, a new class of inhibitors (nonionic polymer surfactants) was identified as promising agents for drug formulations. These compounds are two- or three-block copolymers arranged in a linear ABA or AB structure. The A block is a hydrophilic polyethylene oxide) chain. The B block can be a hydrophobic lipid (in copolymers BRIJs, MYRJs, Tritons, Tweens, and Chremophor) or a poly(propylene oxide) chain (in copolymers Pluronics [BASF Corp., N.J., USA] and CRL-1606). Pluronic block copolymers with various numbers of hydrophilic EO (,n) and hydrophobic PO (in) units are characterized by distinct hydrophilic-lipophilic balance (HLB). Due to their amphiphilic character these copolymers display surfactant properties including ability to interact with hydrophobic surfaces and biological membranes. In aqueous solutions with concentrations above the CMC, these copolymers self-assemble into micelles. 

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