Self-Organization in Solutions of Stiff-Chain Amphiphilic Macromolecules

Abstract

Conformational properties of amphiphilic stiff-chain macromolecules in concentrated solutions in poor solvent have been studied via computer modeling. We have found that the conformational state of macromolecules in such systems depends on the macromolecular stiffness and on the way the solution has been prepared. Thus, if the concentration of globules increased from a very diluted solution, the globules remain stable, independent of the macromolecular stiffness, and do not aggregate even in concentrated solutions. On the other hand, if the solvent quality is gradually decreased in a solution with a concentration much larger than that of a semidilute solution, then relatively flexible chains form separate globules, whereas semirigid macromolecules tend to aggregate and form braid-like conformations. The results obtained agree with the published experimental data and can be used for directed synthesis of macromolecules modeling the behavior of biopolymers.

Dissipative particle dynamics study on the mesostructures of n-octadecane/water emulsion with alternating styrene–maleic acidcopolymers as emulsifier

“…Mesomolecular stiffness affects the conformational properties of macromolecules and properties of their concentrated solutions 49 as well as the phase separation dynamics of a semidilute polymer solution. 30 Therefore, the chain stiffness should also play a role in the emulsion formation.…”

Solute-Triggered Morphological Transitions of an Amphiphilic Heterografted Brush Copolymer as a Single-Molecule Drug Carrier

“…Similarly, when referring to the formation of unimolecular micelles from the self-assembly of polymers exhibiting an amphiphilic character, it is the type of hydrophobes, hydrophobe sequence distribution and grafting density, polymer concentration, chain stiffness, and hydrophilic-to-hydrophobic ratio that will determine the intra- vs intermolecular balance. − For their structural similarity to proteins, the formation of unimolecular micelles has largely been examined for random copolymers of monomers bearing short hydrophilic and hydrophobic moieties. − ,, The advancement of polymerization methods enabling the synthesis of complex macromolecular architectures has also allowed for the study of intrachain association of polymers with more complex architectures including those with long or multicomponent branches. − …”

New strategy to create ultra-thin surface layer of grafted amphiphilic macromolecules

“…[30][31][32][33][34][35] The globules of such macromolecules have a complex core-shell structure: the interiors consist of hydrophobic units, while the outer shell is composed of hydrophilic units. In semidilute solution, the amphiphilic flexible macromolecules condense into individual soluble globules 31 while the rigid macromolecules tend to aggregate with formation of braid fibril-like complexes 36 or bundle aggregates of a few chains. 37 In both cases, the hydrophobic backbones of the chains intertwine and form a core, whereas hydrophilic groups are located on the surface.…”