Micelles formed by the self-assembly of block copolymers in selective solvents have attracted widespread attention and have uses in a wide variety of fields, whereas applications based on their ...electronic properties are virtually unexplored. Herein we describe studies of solution-processable, low-dispersity, electroactive fibre-like micelles of controlled length from π-conjugated diblock copolymers containing a crystalline regioregular poly(3-hexylthiophene) core and a solubilizing, amorphous regiosymmetric poly(3-hexylthiophene) or polystyrene corona. Tunnelling atomic force microscopy measurements demonstrate that the individual fibres exhibit appreciable conductivity. The fibres were subsequently incorporated as the active layer in field-effect transistors. The resulting charge carrier mobility strongly depends on both the degree of polymerization of the core-forming block and the fibre length, and is independent of corona composition. The use of uniform, colloidally stable electroactive fibre-like micelles based on common π-conjugated block copolymers highlights their significant potential to provide fundamental insight into charge carrier processes in devices, and to enable future electronic applications.
Square-planar platinum(II) complexes often stack cofacially to yield supramolecular fiber-like structures with interesting photophysical properties. However, control over fiber dimensions and the ...resulting colloidal stability is limited. We report the self-assembly of amphiphilic Pt(II) complexes with solubilizing ancillary ligands based on polyethylene glycol PEG n , where n = 16, 12, 7. The complex with the longest solubilizing PEG ligand, Pt-PEG 16 , self-assembled to form polydisperse one-dimensional (1D) nanofibers (diameters <5 nm). Sonication led to short seeds which, on addition of further molecularly dissolved Pt-PEG 16 complex, underwent elongation in a “living supramolecular polymerization” process to yield relatively uniform fibers of length up to ca. 400 nm. The fiber lengths were dependent on the Pt-PEG 16 complex to seed mass ratio in a manner analogous to a living covalent polymerization of molecular monomers. Moreover, the fiber lengths were unchanged in solution after 1 week and were therefore “static” with respect to interfiber exchange processes on this time scale. In contrast, similarly formed near-uniform fibers of Pt-PEG 12 exhibited dynamic behavior that led to broadening of the length distribution within 48 h. After aging for 4 weeks in solution, Pt-PEG 12 fibers partially evolved into 2D platelets. Furthermore, self-assembly of Pt-PEG 7 yielded only transient fibers which rapidly evolved into 2D platelets. On addition of further fiber-forming Pt complex (Pt-PEG 16 ), the platelets formed assemblies via the growth of fibers selectively from their short edges. Our studies demonstrate that when interfiber dynamic exchange is suppressed, dimensional control and hierarchical structure formation are possible for supramolecular polymers through the use of kinetically controlled seeded growth methods.
Poly(l-lactide) (PLLA)-based nanoparticles have attracted much attention with respect to applications in drug delivery and nanomedicine as a result of their biocompatibility and biodegradability. ...Nevertheless, the ability to prepare PLLA assemblies with well-defined shape and dimensions is limited and represents a key challenge. Herein we report access to a series of monodisperse complex and hierarchical colloidally stable 2D structures based on PLLA cores using the seeded growth, “living-crystallization-driven self-assembly” method. Specifically, we describe the formation of diamond-shaped platelet micelles and concentric “patchy” block co-micelles by using seeds of the charge-terminated homopolymer PLLA24PPh2MeI to initiate the sequential growth of either additional PLLA24PPh2MeI or a crystallizable blend of the latter with the block copolymer PLLA42-b-P2VP240, respectively. The epitaxial nature of the growth processes used for the creation of the 2D block co-micelles was confirmed by selected area electron diffraction analysis. Cross-linking of the P2VP corona of the peripheral block in the 2D block co-micelles using Pt nanoparticles followed by dissolution of the interior region in good solvent for PLLA led to the formation of novel, hollow diamond-shaped assemblies. We also demonstrate that, in contrast to the aforementioned results, seeded growth of the unsymmetrical PLLA BCPs PLLA42-b-P2VP240 or PLLA20-b-PAGE80 alone from 2D platelets leads to the formation of diamond-fiber hybrid structures.
The effect of electrospun cellulose nanocrystals (CNCs)-polyetherimide (PEI) hybrid nanofibrous mats on Mode I and Mode II interlaminar fracture toughness of unidirectional carbon/epoxy composite ...laminates is demonstrated. It is shown that the CNCs reinforced PEI nanofibrillar interleaves result in a ~28% increase in Mode I initial fracture toughness values compared to neat PEI nanofibrous interleaves. Specifically, the interrelated micro- and nano-scale toughening mechanisms including carbon fibre bridging, fibre necking, fibre rupture with CNCs aggregates, and nanofibre rupture contributed to the fracture toughness improvements under Mode-I loading. Nano-scale mechanisms of shear hackles, and crack pinning by CNCs aggregates increased the Mode II fracture toughness up to ~3 kJ/m2 as a result of a 6 wt% CNCs reinforced PEI nanofibrillar mat interleave. Interleaving laminated composites with electrospun CNCs-PEI hybrid nanofibrillar mats has been demonstrated as a novel and prospective strategy to strengthen and toughen interlaminar zones of carbon/epoxy composite laminates.
Although micelles derived from the solution self-assembly of amphiphilic molecules and polymers have been prepared with a wide variety of shapes, examples with well-defined branched structures have ...remained elusive. We describe a divergent, directed self-assembly approach to low dispersity dendritic micelles with a high degree of structural perfection and tailorable branch numbers and generations. We use block copolymer amphiphiles as precursors and a crystallization-driven seeded growth approach whereby the termini of fiber-like micelles function as branching sites. Different dendrimeric generations are accessible by adjusting the ratio of added unimers to pre-existing seed micelles where the branch positions are determined by the reduced coronal chain grafting density on the surface of the micelle crystalline core. We demonstrate the spatially defined decoration of the assemblies with emissive nanoparticles and utility of the resulting hybrids as fluorescent sensors for anions where the dendritic architecture enables ultrahigh sensitivity.
Toroidal nanostructures are of growing importance due to their unique geometry and potential utility in materials fabrication. Although a variety of amphiphilic block copolymers has been shown to ...self-assemble into toroidal micelles, the conventional methods used are often very slow with little control over the size of the resulting nanostructures. Here, we report a rapid and efficient synthetic route to prepare toroidal micelles of near uniform diameter through the cooperative coassembly of amorphous blends of polyferrocenylsilane block copolymer and homopolymer, where the degree of polymerization of the core-forming metalloblock in the former is greater than for the latter. The self-assembly process is accomplished within a few minutes, and the ring size of the toroids can be varied between 30 and 90 nm by adjusting the mass ratio of the block copolymer and homopolymer. The kinetic stability of the resulting toroidal micelles can be enhanced by frustrating core crystallization through solvent modulation and the toroids can also be readily used as templates to fabricate circular arrays of metal nanoparticles.
Seeded polymerisation of proteins forming amyloid fibres and their spread in tissues has been implicated in the pathogenesis of multiple neurodegenerative diseases: so called "prion-like" mechanisms. ...While ex vivo mammalian prions, composed of multichain assemblies of misfolded host-encoded prion protein (PrP), act as lethal infectious agents, PrP amyloid fibrils produced in vitro generally do not. The high-resolution structure of authentic infectious prions and the structural basis of prion strain diversity remain unknown. Here we use cryo-electron microscopy and atomic force microscopy to examine the structure of highly infectious PrP rods isolated from mouse brain in comparison to non-infectious recombinant PrP fibrils generated in vitro. Non-infectious recombinant PrP fibrils are 10 nm wide single fibres, with a double helical repeating substructure displaying small variations in adhesive force interactions across their width. In contrast, infectious PrP rods are 20 nm wide and contain two fibres, each with a double helical repeating substructure, separated by a central gap of 8-10 nm in width. This gap contains an irregularly structured material whose adhesive force properties are strikingly different to that of the fibres, suggestive of a distinct composition. The structure of the infectious PrP rods, which cause lethal neurodegeneration, readily differentiates them from all other protein assemblies so far characterised in other neurodegenerative diseases.
The increase in capabilities of Scanning Probe Microscopy (SPM) has resulted in a parallel increase in complexity that limits the use of this technique outside of specialised research laboratories. ...SPM automation could substantially expand its application domain, improve reproducibility and increase throughput. Here, we present a bottom-up design in which the combination of positioning stages, orientation, and detection of the probe produces an SPM design compatible with full automation. The resulting probe microscope achieves sub-femtonewton force sensitivity whilst preserving low mechanical drift (2.0±0.2 nm/min in-plane and 1.0±0.1 nm/min vertically). The additional integration of total internal reflection microscopy, and the straightforward operations in liquid, make this instrument configuration particularly attractive to future biomedical applications.
Rectangular platelets formed by the self-assembly of block copolymers in selective solvents are of interest for a range of applications. Recently, we showed that the seeded growth of crystallizable ...blends of a block copolymer and homopolymer yields well-defined, low area dispersity examples of these two-dimensional (2D) structures. The key feature was the use of the same crystallizable polymer segment in the seed and blend components to enable an efficient homoepitaxial growth process. Herein we demonstrate that this 2D crystallization-driven self-assembly approach can be extended to heteroepitaxial growth by the use of different crystallizable polymers with compatible crystal structures. This allows the formation of well-defined “patchy” rectangular platelets and platelet block comicelles with different core chemistries. The use of scanning transmission electron microscopy–energy-dispersive X-ray spectroscopy provided key information on the spatial location of the components in the resulting assemblies and thereby valuable insight into the 2D heteroepitaxial growth process.
Two-dimensional (2D) seeded growth of poly(ferrocenyldimethylsilane) (PFS) homopolymers that possess hydrophilic charged termini in solution has been investigated using the living ...crystallization-driven self-assembly method. The charge-terminated homopolymers, PFS n NMe3I, were synthesized through a combination of living anionic polymerization and post-polymerization thiol–ene “click” chemistry. Uniform and patchy high-aspect-ratio 2D structures were obtained by seeded growth in solution. We show that the aspect ratio of the resultant 2D platelets could be controlled over a wide range (ca. 2–20) by changing either the solvent polarity of the medium in which seeded growth was conducted, the substituents on the charged terminal group, or the characteristics of the seed micelle. The counteranion associated with the charge-terminated PFSNMe3+ homopolymers was found to have a substantial effect on the resulting morphology and colloidal stability of the resulting 2D platelets, which may be a consequence of relatively high charge density of the terminal quaternary ammonium cation.
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