Scalable and uniform 1D nanoparticles by synchronous polymerization, crystallization and self-assembly

Abstract

The preparation of well-defined nanoparticles based on soft matter, using solution-processing techniques on a commercially viable scale, is a major challenge of widespread importance. Self-assembly of block copolymers in solvents that selectively solvate one of the segments provides a promising route to core-corona nanoparticles (micelles) with a wide range of potential uses. Nevertheless, significant limitations to this approach also exist. For example, the solution processing of block copolymers generally follows a separate synthesis step and is normally performed at high dilution. Moreover, non-spherical micelles-which are promising for many applications-are generally difficult to access, samples are polydisperse and precise dimensional control is not possible. Here we demonstrate the formation of platelet and cylindrical micelles at concentrations up to 25% solids via a one-pot approach-starting from monomers-that combines polymerization-induced and crystallization-driven self-assembly. We also show that performing the procedure in the presence of small seed micelles allows the scalable formation of low dispersity samples of cylindrical micelles of controlled length up to three micrometres.

Semi‐Fluorinated Methacrylates: A Class of Versatile Monomers for Polymerization‐Induced Self‐Assembly

“…Despite its robustness and versatility for potential applications, PISA still has many restraints, one of which is the limited choice of monomers and solvents . For example, only a few monomers, such as styrene, benzyl methacrylate, 2‐hydroxypropyl methacrylate, and diacetone acrylamide, were applied to reversible addition‐fragmentation chain‐transfer (RAFT) dispersion polymerization, and the most used solvents were ethanol and H 2 O. Whereas aqueous emulsion polymerization tolerates a variety of hydrophobic monomers, the structure and composition of the hydrophilic stabilizing blocks need to be delicately tuned to prepare polymer assemblies with high order structure .…”

Reactive and Functional Nanoobjects by Polymerization‐Induced Self‐Assembly

“…Particularly, there are many functionalities that have been introduced in RDRP‐made polymers that have not been yet included in PISA nanoobjects. Since other polymerization mechanisms are slowly making an appearance in the PISA realm, some functional groups that are incompatible with radical polymerization might soon appear. Besides, multivalent initiators/CTAs and monomers are also of interest to simplify the PISA process and to access high‐performance materials.…”

“…When they are insoluble (i.e., when PISA starts from two immiscible phases), the mechanism is based on surfactant‐free emulsion polymerization. The underpinning polymerization mechanism is typically based on an RDRP technique—mostly reversible addition–fragmentation chain‐transfer (RAFT) polymerization but also nitroxide‐mediated polymerization (NMP) and to a lower extent copper‐mediated RDRP—but a few examples based on further living polymerization mechanisms such as ring‐opening metathesis polymerization (ROMP) and anionic polymerization, or even on non‐living radical polymerization, have appeared.…”

Saccharide‐based nanocarriers for targeted therapeutic and diagnostic applications

“…Recently, along with the introduction of facile polymerization‐induced self‐assembly techniques for the synthesis of self‐assembled nanovectors, techniques such as reversible addition–fragmentation chain transfer or anionic polymerizations have made reasonable strides in the synthesis of nanostructures by combining the insolubility‐driven self‐assembly of the growing second block from a soluble block. However, these methods still have certain limitations as they have not been employed for the synthesis of biomedical nanocarriers from natural macromolecules.…”