Defect-Induced Secondary Crystals Drive Two-Dimensional to Three-Dimensional Morphological Evolution in the Co-Self-Assembly of Polyferrocenylsilane Block Copolymer and Homopolymer.

Bottom-up fabrication protocols for uniform 3D hierarchical structures in solution are rare. We report two different approaches to fabricate uniform 3D spherulites and their precursors using mixtures of poly(ferrocenyldimethylsilane) (PFS) block copolymer (BCP) and PFS homopolymer (HP). Both protocols are designed to promote defects in 2D assemblies that serve as intermediate structures. In a multistep seeded growth protocol, we add the BCP/HP mixture to (1D) rod-like PFS micelles in a selective solvent as first-generation seeds. This leads to 2D platelet structures. If this step is conducted at a high supersaturation, secondary crystals form on the basal surface of these platelets. Co-crystallization and rapid crystallization of BCP/HP promote the formation of defects that act as nucleation sites for secondary crystals, resulting in multilayer platelets. This is the key step. The multilayer platelets serve as second-generation seeds upon subsequent addition of BCP/HP blends and, with increasing supersaturation, lead to the sequential formation of uniform (3D) hedrites, sheaves, and spherulites. Similar structures can also be obtained by a simple one-pot direct self-assembly (heating-cooling-aging) protocol of PFS BCP/HP blends. In this case, for a carefully chosen but narrow temperature range, PFS HPs nucleate formation of uniform structures, and the annealing temperature regulates the supersaturation level. In both protocols, the competitive crystallization kinetics of HP/BCP affects the morphology. Both protocols exhibit broad generality. We believe the morphological transformation from 2D to 3D structures, regulated by defect formation, co-crystallization, and supersaturation levels, could apply to various semicrystalline polymers. Moreover, the 3D structures are sufficiently robust to serve as recoverable carriers for nanoparticle catalysts, exhibiting valuable catalytic activity and opening new possibilities for applications requiring exquisite 3D structures.

Tuning the Functionality of Self-Assembled 2D Platelets in the Third Dimension.

The decoration of 2D nanostructures using heteroepitaxial growth is of great importance to achieve functional assemblies employed in biomedical, electrical, and mechanical applications. Although the functionalization of polymers before self-assembly has been investigated, the exploration of direct surface modification in the third dimension from 2D nanostructures has, to date, been unexplored. Here, we used living crystallization-driven self-assembly to fabricate poly(ε-caprolactone)-based 2D platelets with controlled size. Importantly, surface modification of the platelets in the third dimension was achieved by using functional monomers and light-induced polymerization. This method allows us to selectively regulate the height and fluorescence properties of the nanostructures. Using this approach, we gained unprecedented spatial control over the surface functionality in the specific region of complex 2D platelets.

Tailored Energy Funneling in Photocatalytic π-Conjugated Polymer Nanofibers for High-Performance Hydrogen Production.

The creation of artificial high-performance photosynthetic assemblies with a tailorable antenna system to deliver absorbed solar energy to a photosynthetic reaction center, thereby mimicking biological photosynthesis, remains a major challenge. We report the construction of recyclable, high-performance photosynthetic nanofibers with a crystalline π-conjugated polyfluorene core as an antenna system that funnels absorbed solar energy to spatially defined sensitized Co(II) porphyrin photocatalysts for the hydrogen evolution reaction. Highly effective energy funneling was achieved by tuning the dimensions of the nanofibers to exploit the very long exciton diffusion lengths (>200 nm) associated with the highly crystalline polyfluorene core formed using the living crystallization-driven self-assembly seeded growth method. This enabled efficient solar light-driven hydrogen production from water with a turnover number of over 450 for 8 h of irradiation, an H2 production rate of ca. 65 mmol h-1 g-1, and an overall quantum yield of 0.4% in the wavelength region (<405 nm) beyond the absorption of the molecular photocatalyst. The strategy of using a tailored antenna system based on π-conjugated polymers and maximizing exciton transport to a reaction center reported in this work opens up future opportunities for potential applications in other fields such as solar overall water splitting, CO2 reduction, and photocatalytic small molecule synthesis.

High-resolution cryo-electron microscopy structure of block copolymer nanofibres with a crystalline core.

Seeded growth of crystallizable block copolymers and π-stacking molecular amphiphiles in solution using living crystallization-driven self-assembly is an emerging route to fabricate uniform one-dimensional and two-dimensional core-shell micellar nanoparticles of controlled size with a range of potential applications. Although experimental evidence indicates that the crystalline core of these nanomaterials is highly ordered, a direct observation of their crystal lattice has not been successful. Here we report the high-resolution cryo-transmission electron microscopy studies of vitrified solutions of nanofibres made from a crystalline core of poly(ferrocenyldimethylsilane) (PFS) and a corona of polysiloxane grafted with 4-vinylpyridine groups. These studies show that poly(ferrocenyldimethylsilane) chains pack in an 8-nm-diameter core lattice with two-dimensional pseudo-hexagonal symmetry that is coated by a 27 nm 4-vinylpyridine corona with a 3.5 nm distance between each 4-vinylpyridine strand. We combine this structural information with a molecular modelling analysis to propose a detailed molecular model for solvated poly(ferrocenyldimethylsilane)-b-4-vinylpyridine nanofibres.

Polyphosphinoborane Block Copolymer Synthesis Using Catalytic Reversible Chain-Transfer Dehydropolymerization.

An amphiphilic block copolymer of polyphosphinoborane has been prepared by a mechanism-led strategy of the sequential catalytic dehydropolymerization of precursor monomers, H3 B ⋅ PRH2 (R=Ph, n-hexyl), using the simple pre-catalyst [Rh(Ph2 PCH2 CH2 PPh2 )2 ]Cl. Speciation, mechanism and polymer chain growth studies support a step-growth process where reversible chain transfer occurs, i.e. H3 B ⋅ PRH2 /oligomer/polymer can all coordinate with, and be activated by, the catalyst. Block copolymer [H2 BPPhH]110 -b-[H2 BP(n-hexyl)H]11 can be synthesized and self-assembles in solution to form either rod-like micelles or vesicles depending on solvent polarity.

AIE-Active, Stimuli-Responsive Fluorescent 2D Block Copolymer Nanoplatelets Based on Corona Chain Compression.

Aggregation-induced emission (AIE) represents a powerful tool in nanoscience as a result of enhanced luminescence in the condensed state. Although AIEgenic materials have been utilized in a wide range of applications, well-defined self-assembled nanoparticles with tailorable and uniform dimensions and morphology remain challenging to access. Herein, we use the seeded growth, living crystallization-driven self-assembly (CDSA) method to prepare size-tunable and uniform AIE-active 2D nanoplatelets from amphiphilic block copolymer (BCP) precursors with a crystallizable core-forming block and a corona-forming block to which tetraphenylethene (TPE) groups were covalently grafted as AIE-active pendants. The nanoplatelets were formed as a result of a solvophobicity-induced 1D to 2D morphology preference change, which accompanied the seeded growth of a BCP with a quaternized corona-forming block bearing the TPE luminogen. The 2D nanoplatelets exhibited a solvent-responsive fluorescent emission, and examples with coronas containing homogeneously distributed AIE-active TPE groups and Hg(II)-capturing thymine units exhibited excellent performance as proof-of-concept "turn-on" sensors for Hg(II) detection with a rapid response, high selectivity, and a low detection limit (5-125 × 10-9 M, i.e., 1-25 ppb). The fluorescence intensity was found to be nonlinear with respect to analyte concentration and to increase with the area of the nanoplatelet. This behavior is consistent with a cooperative mechanism based on changes in the steric compression of the corona chains, which gives rise to a restriction of the intramolecular motion (RIM) effect.

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.

Solution structure and oligomeric state of the E. coliglycerol facilitator.

Protein dynamics at atomic resolution can provide deep insights into the biological activities of proteins and enzymes but they can also make structure and dynamics studies challenging. Despite their well-known biological and pharmaceutical importance, integral membrane protein structure and dynamics studies lag behind those of water-soluble proteins mainly owing to solubility problems that result upon their removal from the membrane. Escherichia coli glycerol facilitator (GF) is a member of the aquaglyceroporin family that allows for the highly selective passive diffusion of its substrate glycerol across the inner membrane of the bacterium. Previous molecular dynamics simulations and hydrogen-deuterium exchange studies suggested that protein dynamics play an important role in the passage of glycerol through the protein pore. With the aim of studying GF dynamics by solution and solid-state nuclear magnetic resonance (NMR) spectroscopy we optimized the expression of isotope-labelled GF and explored various solubilizing agents including detergents, osmolytes, amphipols, random heteropolymers, lipid nanodiscs, bicelles and other buffer additives to optimize the solubility and polydispersity of the protein. The GF protein is most stable and soluble in lauryl maltose neopentyl glycol (LMNG), where it exists in a tetramer-octamer equilibrium. The solution structures of the GF tetramer and octamer were determined by negative-stain transmission electron microscopy (TEM), size-exclusion chromatography small-angle X-ray scattering (SEC-SAXS) and solid-state magic-angle spinning NMR spectroscopy. Although NMR sample preparation still needs optimization for full structure and dynamics studies, negative stain TEM and SEC-SAXS revealed low-resolution structures of the detergent-solubilized tetramer and octamer particles. The non-native octamer appears to form from the association of the cytoplasmic faces of two tetramers, the interaction apparently mediated by their disordered N- and C-termini. This information may be useful in future studies directed at reducing the heterogeneity and self-association of the protein.