Supramolecular Polymerization of Polymeric Nanorods Mediated by Block Copolymers

Abstract

Introducing a second component is an effective way to manipulate polymerization behavior. However, this phenomenon has rarely been observed in colloidal systems, such as polymeric nanoparticles. Here, we report the supramolecular polymerization of polymeric nanorods mediated by block copolymers. Experimental observations and simulation results illustrate that block copolymers surround the polymeric nanorods and mainly concentrate around the two ends, leaving the hydrophobic side regions exposed. These polymeric nanorods connect in a side‐by‐side manner through hydrophobic interactions to form bundles. As polymerization progresses, the block copolymers gradually deposit onto the bundles and finally assemble into helical nanopatterns on the outermost surface, which terminates the polymerization. It is anticipated that this work could offer inspiration for a general strategy of controllable supramolecular polymerization.

Controllable Copolymerization of Polymeric Micelles for the Construction of Supramolecular Chains

“…In the second step, the micelle solutions were incubated at a low temperature of 5 °C to induce supramolecular polymerization. As revealed by previous work, , the two ends of the micelles usually possess relatively higher energy due to both the imperfect coverage of the hydrophilic component and the higher curvature of the end region. The solvophobicity of PBLG increases with a decrease in temperature, making micelle ends act as reactive points.…”

Modulating living crystallization-driven self-assembly behaviors of oligo(p-phenylene ethynylene)-containing block copolymers and micellar stability by solvent and corona-forming chain length

“…Li, Lin, Xu, Manners and co-workers also reported the formation of hierarchical fibril superstructures via the end-to-end coupling of fiber-and oval-like micelles containing a liquid crystalline or crystalline segment, including a poly(cholesteryl methacryloyloxy ethyl carbonate), poly(γ-benzyl-L-glutamate), PFS or poly(ε-caprolactone) core-forming block. [61][62][63][64][65] In these systems, the end-to-end coupling process is usually driven by reducing the overall core/corona interfacial energy from a thermo-dynamic point of view. Most of the connections between the subunits of diamond-and platelet-like micelles appeared to be in the regions of acute angles of diamond-and platelet-like micelles as indicated by red arrows in Fig.…”

Aqueous Circularly Polarized Luminescence Induced by Homopolypeptide Self-Assembly

“…Aqueous dispersed aggregates with well-defined tunable nanostructures, formed through self-assembly of polypeptides, have drawn significant attention due to their intrinsic biodegradability, environmental compatibility, and applicability in the biomedical field. − The versatility of polypeptides, in conjunction with their chirality and ability to form conformationally stable and regular secondary structures (helices, sheets, turns), provides a unique platform for designing nanomaterials with controllable structural features. ,− Recently, Du and co-workers discovered that selective solvents can impose a huge impact on the morphology of the homopolypeptide-based self-assembly from the nanotoroid to the nanorod. , Through the co-assembly of polypeptide mixtures, Lin and co-workers constructed superhelices with adjustable chirality regulated by the chiral homopolypeptides and copolypeptides. , Given the chiral structure of most polypeptides, it is of great significance to endow unique optical properties beyond their novel assembly structures, which can endow the biodegradable nanomaterials with certain photophysical activities to enable them to be applied in environmentally friendly optoelectronic devices and in biomedical fields. Despite the increasing enthusiasm for designing novel nanomaterials by polypeptide self-assembly, research on their optical properties as well as nanostructure–property relationships has been rarely reported.…”

“…11,12 Through the co-assembly of polypeptide mixtures, Lin and co-workers constructed superhelices with adjustable chirality regulated by the chiral homopolypeptides and copolypeptides. 13,14 Given the chiral structure of most polypeptides, it is of great significance to endow unique optical properties beyond their novel assembly structures, which can endow the biodegradable nanomaterials with certain photophysical activities to enable them to be applied in environmentally friendly optoelectronic devices and in biomedical fields. Despite the increasing enthusiasm for designing novel nanomaterials by polypeptide self-assembly, research on their optical properties as well as nanostructure−property relationships has been rarely reported.…”