Functional Noncentrosymmetric Nanoparticle-Nanofiber Hybrids via Selective Fragmentation.

Noncentrosymmetric nanostructures are an attractive synthetic target as they can exhibit complex interparticle interactions useful for numerous applications. However, generating uniform, colloidally stable, noncentrosymmetric nanoparticles with low aspect ratios is a significant challenge using solution self-assembly approaches. Herein, we outline the synthesis of noncentrosymmetric multiblock co-nanofibers by subsequent living crystallization-driven self-assembly of block co-polymers, spatially confined attachment of nanoparticles, and localized nanofiber fragmentation. Using this strategy, we have fabricated uniform diblock and triblock noncentrosymmetric π-conjugated nanofiber-nanoparticle hybrid structures. Additionally, in contrast to Brownian motion typical of centrosymmetric nanoparticles, we demonstrated that these noncentrosymmetric nanofibers undergo ballistic motion in the presence of H2O2 and thus could be employed as nanomotors in various applications, including drug delivery and environmental remediation.

Efficient energy transport in an organic semiconductor mediated by transient exciton delocalization.

Efficient energy transport is desirable in organic semiconductor (OSC) devices. However, photogenerated excitons in OSC films mostly occupy highly localized states, limiting exciton diffusion coefficients to below ~10-2 cm2/s and diffusion lengths below ~50 nm. We use ultrafast optical microscopy and nonadiabatic molecular dynamics simulations to study well-ordered poly(3-hexylthiophene) nanofiber films prepared using living crystallization-driven self-assembly, and reveal a highly efficient energy transport regime: transient exciton delocalization, where energy exchange with vibrational modes allows excitons to temporarily re-access spatially extended states under equilibrium conditions. We show that this enables exciton diffusion constants up to 1.1 ± 0.1 cm2/s and diffusion lengths of 300 ± 50 nm. Our results reveal the dynamic interplay between localized and delocalized exciton configurations at equilibrium conditions, calling for a re-evaluation of exciton dynamics and suggesting design rules to engineer efficient energy transport in OSC device architectures not based on restrictive bulk heterojunctions.

Seeded Self-Assembly of Charge-Terminated Poly(3-hexylthiophene) Amphiphiles Based on the Energy Landscape.

The creation of 1D π-conjugated nanofibers with precise control and optimized optoelectronic properties is of widespread interest for applications as nanowires. "Living" crystallization-driven self-assembly (CDSA) is a seeded growth method of growing importance for the preparation of uniform 1D fiber-like micelles from a range of crystallizable polymeric amphiphiles. However, in the case of polythiophenes, one of the most important classes of conjugated polymer, only limited success has been achieved to date using block copolymers as precursors. Herein, we describe studies of the living CDSA of phosphonium-terminated amphiphilic poly(3-hexylthiophene)s to prepare colloidally stable nanofibers. In depth studies of the relationship between the degree of polymerization and the self-assembly behavior permitted the unveiling of the energy landscape of the living CDSA process. On the basis of the kinetic and thermodynamic insight provided, we have been able to achieve an unprecedented level of control over the length of low dispersity fiber-like micelles from 40 nm to 2.8 µm.

Surface Patterning of Uniform 2D Platelet Block Comicelles via Coronal Chain Collapse.

The formation of colloids with anisotropically patterned surfaces is of growing interest for the creation of hierarchical structures and the templating of nanoparticles. We have recently shown that well-defined two-dimensional platelets with low areal dispersities can be formed by the seeded growth of a blend of homopolymers and block copolymers. Herein we form rectangular platelets containing two block copolymers with different coronal chemistries. On addition of a solvent that is only able to solvate the corona of one block, we were able to form colloidally stable micelles with patterned surfaces via coronal collapse. Scanning transmission electron microscopy-energy-dispersive X-ray spectroscopy and atomic force microscopy were employed to provide information on the structure and size of the patches decorating the micelle surfaces.

1D Self-Assembly and Ice Recrystallization Inhibition Activity of Antifreeze Glycopeptide-Functionalized Perylene Bisimides.

Antifreeze glycoproteins (AFGPs) are polymeric natural products that have drawn considerable interest in diverse research fields owing to their potent ice recrystallization inhibition (IRI) activity. Self-assembled materials have emerged as a promising class of biomimetic ice growth inhibitor, yet the development of AFGP-based supramolecular materials that emulate the aggregative behavior of AFGPs have not yet been reported. This work reports the first example of the 1D self-assembly and IRI activity of AFGP-functionalized perylene bisimides (AFGP-PBIs). Glycopeptide-functionalized PBIs underwent 1D self-assembly in water and showed modest IRI activity, which could be tuned through substitution of the PBI core. This work presents essential proof-of-principle for the development of novel IRIs as potential supramolecular cryoprotectants and glycoprotein mimics.

Erratum: Uniform electroactive fibre-like micelle nanowires for organic electronics.

This corrects the article DOI: 10.1038/ncomms15909.

Uniform electroactive fibre-like micelle nanowires for organic electronics.

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.

Uniform "Patchy" Platelets by Seeded Heteroepitaxial Growth of Crystallizable Polymer Blends in Two Dimensions.

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.