Fibril Assembly and Gelation of Macromolecules with Amphiphilic Repeating Units

Abstract

This paper reports the self-assembly of the fibrillar network in a concentrated solution of macromolecules with an amphiphilic structure of repeating units. The investigation of amphiphilic homopolymers and alternating copolymers with the linear and cyclic topologies, the solution with different polymer concentrations and solvent qualities, allows us to conclude that the ability to form a fibrillar gel with branched fibrils and regular subchain thickness is inherent for macromolecules with the solvophobic backbone and solvophilic pendants. The elements of the gel structure, such as the mesh size and fibrillar thickness, the number of cross-links, and their functionality, can be tuned and customized according to the requirements of their application. The results could be helpful for the directed design of the synthetic analogue of the relevant extracellular matrix, in tissue engineering, for fibrotic disease treatment and cell encapsulation.

Self-Assembled Graft Copolymer Nanofibers with an Adjustable Internal and External Structure

“…Description of this procedure can be found in our previous papers. 44,45 With homogeneous distribution of macromolecules, in all subcells, the local polymer content p (%) is p = c• 100%. When macromolecules aggregate, the part of subcells loses the macromolecules and even becomes completely free of polymer (p = 0), while in the others, the numerical polymer density increases.…”

“…Characteristic distribution of amphiphilic macromolecules in the solution was measured through the calculation of local polymer content p expressed as % of the total number of monomer units in the system in cubic subcells with edge L s . Description of this procedure can be found in our previous papers. , With homogeneous distribution of macromolecules, in all subcells, the local polymer content p (%) is p = c· 100%. When macromolecules aggregate, the part of subcells loses the macromolecules and even becomes completely free of polymer ( p = 0), while in the others, the numerical polymer density increases.…”

“…Another promising, yet still poorly studied, candidate for the nanofiber formation is graft copolymers with amphiphilicity at the level of a repeating unit. − Recently, our group showed via generic mesoscale simulation the universal ability of such macromolecules to easily self-assemble into fibrillar networks in the selective solvent or solvent mixtures. , Further, amphiphilic homopolymer and comb-like macromolecules due to the effective surface activity of monomer units and their connectivity with each other can be affected by specific interactions, unique for these types of macromolecules . This is the so-called orientation-induced attraction, which allows us to reduce the entropy losses of side pendants and leads to the formation of clusters from few core–shell aggregates.…”