Flexible Block Copolymer Metamaterials Featuring Hollow Ordered Nanonetworks with Ultra-High Porosity and Surface-To-Volume Ratio.

By utilizing bicontinuous and nanoporous ordered nanonetworks, such as double gyroid (DG) and double diamond (DD), metamaterials with exceptional optical and mechanical properties can be fabricated through the templating synthesis of functional materials. However, the volume fraction range of DG in block copolymers is significantly narrow, making it unable to vary its porosity and surface-to-volume ratio. Here, the theoretically limited structural volume of the DG phase in coil-coil copolymers is overcome by enlarging the conformational asymmetry through the association of mesogens, providing fast access to achieving flexible structured materials of ultra-high porosities. The new materials design, dual-extractable nanocomposite, is created by incorporating a photodegradable block with a solvent-extractable mesogen (m) into an accepting block, resulting in a new hollow gyroid (HG) with the largely increased surface-to-volume ratio and porosity of 77 vol%. The lightweight HG exhibits a low refractive index of 1.11 and a very high specific reduced modulus, almost two times that of the typical negative gyroid (porosity≈53%) and three times that of the positive gyroid (porosity≈24%). This novel concept can significantly extend the DG phase window of block copolymers and the corresponding surface-to-volume ratio, being applicable for nanotemplate-synthesized nanomaterials with a great gain of mechanical, catalytic, and optoelectronic properties.

Photonic Crystal Reflectors with Ultrahigh Sensitivity and Discriminability for Detecting Extremely Low-Concentration Surfactants.

Developing a facile, intuitive, ultrahigh-sensitive sensor to detect harmful substances in water is critical. Here, an ultrahigh-sensitive sensor is fabricated using a quaternized lamellae-structured polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) block copolymer (BCP), capable of detecting the heavily used surfactants including sodium dodecyl sulfate (SDS) and sodium methyl sulfate (SMS) through direct visualization of the structural color change. Two distinct detecting mechanisms, including unexpected blue-shifting and red-shifting reflectance wavelengths, are found for low and high concentrations of the SDS surfactant, respectively, due to concentration-dependent compatibility between the quaternized P2VP (QP2VP) block chains and SDS molecules. As the SDS concentration is low (0-1 mM), the QP2VP chains undergo the counter anionic exchange with the hydrophobic alkyl chains of the SDS, resulting in a blue shift toward colorlessness. In contrast, as the SDS concentration is high (>1 mM), the nanoaggregation of the SDS molecules in the layered QP2VP microdomain leads to enhanced hydration nature and increased lamellar periodicity with the red-shifting reflectance wavelength. In contrast, SMS with weaker hydrophobicity results in unchanged and red-shifting reflectance wavelengths at low and high concentrations. Inspired by this, detecting the extremely low-concentration SDS surfactant (0.01 mM) by direct visualization is achieved. The structural color change for surfactant detection also exhibits excellent reversibility and discriminability, providing a straightforward method of detecting anionic surfactants.

High-resolution three-dimensional structural determination of unstained double-gyroid block copolymers through scanning transmission electron microscopy.

Block copolymer-based multicomponent materials have garnered considerable attention because of tunable properties due to their various constituents. The use of electron tomography through transmission electron microscopy (TEM) for the three-dimensional (3D) imaging of stained block copolymers is an established approach for investigating structure-property relationships. Recently, scanning transmission electron microscopy (STEM) with an annular dark-field (ADF) detector has emerged as a method for the 3D structural analysis of unstained block copolymers. However, because of a lack of electron contrast, only a few low-resolution 3D reconstructions were reported for light elements. Herein, we report the first 3D structural analysis of a 200-nm-thick film composed of unstained double-gyroid block copolymers-polystyrene-b-poly(2-vinylpyridine) (PS-P2VP)-at a resolution of 8.6 nm through spherical aberration Cs-corrected STEM. At this resolution, P2VP molecules can be distinguished from PS molecules in z-contrast 3D reconstructions obtained both experimentally and theoretically. The 3D reconstructions revealed structural differences between stained and unstained specimens.

Chiral Silica with Preferred-Handed Helical Structure via Chiral Transfer.

A strategy to obtain chiral silica using an achiral stereoregular polymer with polyhedral oligomeric silsesquioxane (POSS) side chains is described herein. The preferred helical conformation of the POSS-containing polymer could be achieved by mixing isotactic polymethacrylate-functionalized POSS (it-PMAPOSS) and a chiral dopant. The array structure of POSS molecules, which are placed along the helical conformation, is memorized even after removing the chiral dopant at high temperatures, leading to a chiral silica compound with exclusive optical activity after calcination.

Live Templates of a Supramolecular Block Copolymer for the Synthesis of Ordered Nanostructured TiO2 Films via Guest Exchange.

In this work, we introduce a facile method based on host-guest chemistry to synthesize a range of nanostructured TiO2 materials using supramolecular templates of a dendron-jacketed block copolymer (DJBCP). The DJBCP is composed of amphiphilic dendrons (4'-(3,4,5-tridodecyloxybenzoyloxy)benzoic acid, TDB) selectively incorporated into a P4VP block of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) via hydrogen bonding. The PS-b-P4VP host acts as a structure-directing template, while the guest molecules (TDB) assist the self-assembly nanostructures and zone-axis alignment, resulting in the nanostructured template of vertically oriented cylinders formed via successive phase transformations from Im3̅m to R3̅m to P6mm upon thermal annealing in the doctor-blade-cast film. The guest molecules subsequently direct the titania precursors into the P4VP domains of the templates via supramolecular guest exchange during immersion of the film in a designated precursor solution containing a P4VP-selective solvent. The subsequent UV irradiation step leads to the formation of PS-b-P4VP/TiO2 hybrids. Finally, removal of the host template by calcination leaves behind mesoporous channels and makes sacrifices to be a carbon source for carbon-doping TiO2 materials. Various TiO2 nanoarchitectures, namely, vertical and wiggly micrometer-length channels, inverse opals, fingerprint-like channels, heterogeneous multilayers, and nanotubes, have been fabricated by highly tunable DJBCP nanostructures.