Nikos Petzetakis

Cylindrical micelles from the living crystallization-driven self-assembly of Poly(lactide)-containing block copolymers

The synthesis and self-assembly of poly(lactide)-b-poly(acrylic acid) and poly(lactide)-b-poly(dimethylaminoethylacrylate) block copolymers by a combination of ring-opening polymerization and reverse-addition fragmentation chain transfer (RAFT) polymerization is reported. Self-assembly of block copolymers containing enantiopure homochiral poly(lactide), PLA, by a simple direct dissolution methodology results in core-crystallization to afford micelles with a cylindrical morphology. Amorphous atactic PLA cores and conditions that did not promote crystallization resulted in spherical micelles. Cylindrical micelles were characterized by transmission electron microscopy (TEM) with cryo-TEM, small angle neutron scattering (SANS) and angular dependent dynamic light scattering (DLS) proving that the cylindrical morphology was persistent in solution. Manipulation of the assembly conditions enabled the length and dispersity of the resultant cylindrical micelles to be controlled.

Crystallization-driven sphere-to-rod transition of poly(lactide)-b-poly(acrylic acid) diblock copolymers: mechanism and kinetics

The aqueous crystallization-driven sphere-to-rod transition of poly(lactide)-b-poly(acrylic acid), PLA-b-PAA block copolymers, with a short homochiral PLA core forming block and a 10 times longer (in terms of degree of polymerization) PAA corona forming block is presented. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) is utilized to follow the kinetics of the transition and wide angle X-ray diffraction (WAXD) to confirm the correlation between degree of crystallinity and morphology. Studies at different concentrations and solvent mixtures provide valuable information regarding the nucleation and growth mechanism of the system, showing that the micelle dynamics are a key aspect of the assembly process. Furthermore, the in situ crystallization-driven cylinder formation during the acrylate ester hydrolysis reaction is demonstrated. Finally, we report that the micelle morphology can be switched between cylinders and spheres by facilitating or blocking the crystallization of the core block, demonstrating a simple method to control the morphology of the resultant assembly.

A simple approach to characterizing block copolymer assemblies: graphene oxide supports for high contrast multi-technique imaging.

Block copolymers are well-known to self-assemble into a range of 3-dimensional morphologies. However, due to their nanoscale dimensions, resolving their exact structure can be a challenge. Transmission electron microscopy (TEM) is a powerful technique for achieving this, but for polymeric assemblies chemical fixing/staining techniques are usually required to increase image contrast and protect specimens from electron beam damage. Graphene oxide (GO) is a robust, water-dispersable, and nearly electron transparent membrane: an ideal support for TEM. We show that when using GO supports no stains are required to acquire high contrast TEM images and that the specimens remain stable under the electron beam for long periods, allowing sample analysis by a range of electron microscopy techniques. GO supports are also used for further characterization of assemblies by atomic force microscopy. The simplicity of sample preparation and analysis, as well as the potential for significantly increased contrast background, make GO supports an attractive alternative for the analysis of block copolymer assemblies.

Hollow block copolymer nanoparticles through a spontaneous one-step structural reorganization.

The spontaneous one-step synthesis of hollow nanocages and nanotubes from spherical and cylindrical micelles based on poly(acrylic acid)-b-polylactide (P(AA)-b-P(LA)) block copolymers (BCPs) has been achieved. This structural reorganization, which occurs simply upon drying of the samples, was elucidated by transmission electron microscopy (TEM) and atomic force microscopy (AFM). We show that it was necessary to use stain-free imaging to examine these nanoscale assemblies, as the hollow nature of the particles was obscured by application of a heavy metal stain. Additionally, the internal topology of the P(AA)-b-P(LA) particles could be tuned by manipulating the drying conditions to give solid or compartmentalized structures. Upon resuspension, these reorganized nanoparticles retain their hollow structure and display significantly enhanced loading of a hydrophobic dye compared to the original solid cylinders.