Construction of the single-diamond-structured titania scaffold-Recreation of the holy grail photonic structure.

As one of the most stunning biological nanostructures, the single-diamond (SD) surface discovered in beetles and weevils exoskeletons possesses the widest complete photonic bandgap known to date and is renowned as the "holy grail" of photonic materials. However, the synthesis of SD is difficult due to its thermodynamical instability compared to the energetically favoured bicontinuous double diamond and other easily formed lattices; thus, the artificial fabrication of SD has long been a formidable challenge. Herein, we report a bottom-up approach to fabricate SD titania networks via a one-pot cooperative assembly scenario employing the diblock copolymer poly(ethylene oxide)-block-polystyrene as a soft template and titanium diisopropoxide bis(acetylacetonate) as an inorganic precursor in a mixed solvent, in which the SD scaffold was obtained by kinetically controlled nucleation and growth in the skeletal channels of the diamond minimal surface formed by the polymer matrix. Electron crystallography investigations revealed the formation of tetrahedrally connected SD frameworks with the space group Fd [Formula: see text] m in a polycrystalline anatase form. A photonic bandgap calculation showed that the resulting SD structure has a wide and complete bandgap. This work solves the complex synthetic enigmas and offers a frontier in hyperbolic surfaces, biorelevant materials, next-generation optical devices, etc.

Synthesis of a zeolite@mesoporous silica composite to improve the low-frequency acoustic performance of a miniature loudspeaker system.

Herein, a zeolite@mesoporous silica composite (Z@MS) with a hierarchical porous structure was synthesized and employed as the filling material in miniature loudspeakers. The material was synthesized via a simple surfactant-directed sol-gel process in which MFI zeolites with a high silica-alumina ratio (>1000) were encapsulated in mesoporous silica with worm-like pores templated by Brij 72 under acidic conditions. Pressure spray drying technology was adopted to reassemble the intermediate slurry into hierarchical porous microspheres with large particle sizes (∼200 µm). The resonance frequency of the miniature loudspeaker system decreased by 339.77 Hz upon loading Z@MS as the filling material. The excellent acoustic performance can be considered as the result of a synergy of respective energy transmission effects among hierarchical porous structures.

Chiral Mesostructured Inorganic Materials with Optical Chiral Response.

Fabricating chiral inorganic materials and revealing their unique quantum confinement-determined optical chiral responses are crucial tasks in the multidisciplinary fields of chemistry, physics, and biology. The field of chiral mesostructured inorganic materials started from the synthesis of individual nanocrystals and evolved to include their assembly from metals, semiconductors, ceramics, and inorganic salts endowed with various chiral structures ranging from atomic to micron scales. This tutorial review highlights the recent research on chiral mesostructured inorganic materials, especially the novel expression of mesostructured chirality and endowed optical chiral response, and it may inspire us with new strategies for the design of chiral inorganic materials and new opportunities beyond the traditional applications of chirality. Fabrication methods for chiral mesostructured inorganic materials are classified according to chirality type, scale, and symmetry-breaking mechanism. Special attention is given to highlight systems with original discoveries, exceptional phenomena, or unique mechanisms of optical chiral response for left- and right-handedness.

Synchronous quantitative analysis of chiral mesostructured inorganic crystals by 3D electron diffraction tomography.

Chiral mesostructures exhibit distinctive twisting and helical hierarchical stacking ranging from atomic to micrometre scales with fascinating structural-chiral anisotropy properties. However, the detailed determination of their multilevel chirality remains challenging due to the limited information from spectroscopy, diffraction techniques, scanning electron microscopy and the two-dimensional projections in transmission electron microscopy. Herein, we report a general approach to determine chiral hierarchical mesostructures based on three-dimensional electron diffraction tomography (3D EDT), by which the structure can be solved synchronously according to the quantitative measurement of diffraction spot deformations and their arrangement in reciprocal space. This method was verified on two samples-chiral mesostructured nickel molybdate and chiral mesostructured tin dioxide-revealing hierarchical chiral structures that cannot be determined by conventional techniques. This approach provides more precise and comprehensive identification of the hierarchical mesostructures, which is expected to advance our understanding of structural-chiral anisotropy at the fundamental level.

Mechanism of diastereoisomer-induced chirality of BiOBr.

Chiral molecule-driven asymmetric structures are known to be elusive because of the intriguing chirality transfer from chiral molecules to achiral species. Here, we found that the chiral assembly of BiOBr is independent of the chirality of the organic molecular inducer but dependent on geometric structural matching between the inducer and inorganic species. Diastereoisomeric sugar alcohols (DSAs) with identical numbers of carbon chiral centers and functional groups but with different R/S configurations and optical activities (OAs) were chosen as symmetry-breaking agents for inducing chiral mesostructured BiOBr films (CMBFs) under hydrothermal conditions. Multiple levels of chirality with different handedness were identified in the CMBFs. Density functional theory (DFT) calculations and molecular dynamics (MD) simulations suggest that asymmetric defects in the Br-Bi tetragonal cone caused by physically adsorbed DSAs on the surfaces of the BiOBr crystals are the geometric basis for triggering the chiral twist in the BiOBr monolayer. Our findings provide new insights for understanding the origin of chirality and the chiral transfer mechanism underlying the assembly of achiral species.

Chiral mesostructured hydroxide zinc carbonate for enantioseparation in high performance liquid chromatography.

Chiral mesostructured hydroxide zinc carbonate coated silica gel (CMHZC@S) was prepared by a hydrothermal route using amino acids as symmetry-breaking agents. CMHZC@S with three levels of hierarchical chiralities, as a chiral stationary phase (CSP), showed enantiomeric separation ability for high performance liquid chromatography (HPLC).

DNA-Assisted Creation of a Library of Ultrasmall Multimetal/Metal Oxide Nanoparticles Confined in Silica.

Supported ultrasmall metal/metal oxide nanoparticles (UMNPs) with sizes in the range of 1-5 nm exhibit unique properties in sensing, catalysis, biomedicine, etc. However, the metal-support and metal-metal precursor interactions were not as well controlled to stabilize the metal nanoparticles on/in the supports. Herein, DNA is chosen as a template and a ligand for the silica-supported UMNPs, taking full use of its binding ability to metal ions via either electrostatic or coordination interactions. UMNPs thus are highly dispersed in silica via self-assembly of DNA and DNA-metal ion interactions with the assistance of a co-structural directing agent (CSDA). A large number of metal ions are easily retained in the mesostructured DNA-silica materials, and their growth is controlled by the channels after calcination. Based on this directing concept, a material library, consisting of 50 mono- and 54 bicomponent UMNPs confined within silica and with narrow size distribution, is created. Theoretical calculation proves the indispensability of DNA with combination of several organics in the synthesis of ultrasmall metal nanoparticles. The Pt-silica and Pt/Ni-silica chosen from the library exhibit good catalytic performance for toluene combustion. This generalizable and straightforward synthesis strategy is expected to widen the corresponding applications of supported UMNPs.

Spin Selectivity of Chiral Mesostructured Iron Oxides with Different Magnetisms.

Spin selectivity physically depends on either magnetic materials with strong internal magnetic fields or symmetry-breaking materials with large spin-orbit coupling (SOC). However, the spin selectivity of symmetry-breaking magnetic materials is not understood. Herein, the spin selectivity of iron oxides with different magnetisms arising from varying spin alignment is investigated. Chiral mesostructured films of Fe3 O4 (CMFFs), γ-Fe2 O3 (CMγFs), and α-Fe2 O3 (CMαFs), which share the same mesostructure, are prepared by a controllable calcination process of chiral mesostructured FeOOH films (CMOFs) grown on the substrate via an amino acid-induced hydrothermal route. CMFFs and CMγFs with ferrimagnetism exhibit magnetic field-dependent and simultaneously chirality-independent magnetic circular dichroism (MCD) signals, while CMαFs with antiferromagnetism exhibit chirality-dependent, magnetic field-independent MCD signals. It is speculated that the competitive effect between the spin alignment-induced and chirality-induced effective magnetic fields determines the energy splitting of opposite spins in the materials with different magnetisms.

Chiral Mesostructured BiOBr Films with Circularly Polarized Colour Response.

Achieving strong and broadband circularly polarized colour responses in chiral inorganic materials is challenging. Here, we fabricated chiral mesostructured bismuth oxybromide (BiOBr) films (CMBFs) via hydrothermal growth using chiral sugar alcohols as symmetry-breaking agents. The layered slabs of BiOBr crystals with weak van-der-Waals interactions are prone to mismatching due to the chiral driving force, resulting in hierarchically chiral arrangements of fine size. Three levels of chirality exist in the CMBFs: primary, helical distortion crystal lattices of a nanoflake, secondary, helical stacking of nanoflakes to form nanoplates, and tertiary, chiral vortexes arranged by nanoplates. The CMBFs displayed optical activities (OAs) over a wide wavelength range of 350-2500 nm with an anisotropic factor of up to 0.99, which led to a significant chirality-dependent colour response to circularly polarized light. The high selectivity can be considered as the result of enhanced resonance due to structural-handedness matching and the synergistic effect of multiple OAs.

Resistance-Chiral Anisotropy of Chiral Mesostructured Half-metallic Fe3 O4 Films.

Half-metallic materials are theoretically predicted to be metallic and insulating, which have not been confirmed experimentally, and the predictions are still in doubt. We report the resistance-chiral anisotropy (R-ChA), i.e., chirality-dependent electrical conductivity, in chiral mesostructured Fe3 O4 films (CMFFs) grown on the substrates via a hydrothermal method using amino acids as symmetry-breaking agents. Two levels of chirality exist in the CMFFs: primary distortion of the crystal lattice forms twisted nanoflakes, and secondary helical stacking of nanoflakes forms fan-shaped nanoplates. At temperatures below 30 K, the CMFFs exhibited metallic conductivity and insulation for one handedness and the other, respectively. The chirality-dependent effective magnetic fields were speculated to stabilize the opposite spin in the antipodal chiral frame, which led to the free transport of electrons in one handedness of the chiral structure and immobility for the other handedness.

Self-Assembly of Single-Diamond-Surface Networks.

Biological scaffolds with hyperbolic surfaces, especially single gyroid and single-diamond structures, have sparked immense interest for creating novel materials due to their extraordinary physical properties. However, the ability of nature to create these unbalanced surfaces has not been achieved in either lyotropic liquid crystals or block copolymer phases due to their thermodynamical instability in these systems. Here, we report the synthesis of a porous silica scaffold with a single-diamond-surface structure fabricated by self-assembly of the poly(ethylene oxide)-b-polystyrene-b-poly(L-lactide) and silica precursors in a mixed solvent of tetrahydrofuran and water. The single-diamond structure with tetrahedral interconnected frameworks was revealed by the electron crystallographic reconstruction. We assume that the formation of single networks is induced by the structural transition and related to the energetic change due to the fluctuations of the Gaussian curvature. This work may provide new insights into these biologically relevant surfaces and related self-assembly systems.

Library Creation of Ultrasmall Multi-metallic Nanoparticles Confined in Mesoporous MFI Zeolites.

The development of materials integrated with ultrasmall multi-metal nanoparticles (UMMNs) and mesoporous zeolite is a considerable challenge in chemistry and materials science. We designed a trifunctional surfactant, in which the pyridyl benzimidazole in the hydrophobic tail generates the mesopores through π-π stacking; the diquaternary ammonium in the hydrophilic headgroup direct the formation of MFI zeolite sheets and the nitrogen atoms in the heterocyclic rings coordinate with various metal ions to form UMMNs confined in the zeolite matrix after calcination and reduction. A library of 56 UMMNs confined within both micropores and mesopores of MFI zeolites (MMZs) with 4 mono-, 14 bi- and 38 tri-metallic nanoparticles (sizes of 1.3-4.7 nm) of combinations of Rh, Pd, Pt, Au, Fe, Co, Ni, Cu and Zn were made. An improved catalytic performance was exhibited in the sequence of Rh-MMZ

Chiral Mesostructured NiO Films with Spin Polarisation.

Spin polarisation is found in the centrosymmetric nonferromagnetic crystals, chiral mesostructured NiO films (CMNFs), fabricated through the symmetry-breaking effect of a chiral molecule. Two levels of chirality were identified: primary nanoflakes with atomically twisted crystal lattices and secondary helical stacking of the nanoflakes. Spin polarisation of the CMNFs was confirmed by chirality-dependent magnetic-tip conducting atomic force microscopy (mc-AFM) and magnetic field-independent magnetic circular dichroism (MCD). Electron transfer in the symmetry-breaking electric field was speculated to create chirality-dependent effective magnetic fields. The asymmetric spin-orbit coupling (SOC) generated by effective magnetic fields selectively modifies the opposite spin motion in the antipodal CMNFs. Our findings provide fundamental insights for directional spin control in unprecedented functional inorganic materials.

Discovery of single gyroid structure in self-assembly of block copolymer with inorganic precursors.

Triply periodic hyperbolic surfaces have attracted great attention due to their unique geometries and physical properties. Among them, the single gyroid (SG) is of significant interest due to its inherent chirality as well as the potential applications in energy and environmental science. However, the formation of the thermodynamically unstable structure is still unclear. In this work, we show the formation of SG structure in the structural transformation from the cylindrical to shifted double diamond (SDD) scaffold in a self-assembly system of diblock copolymer and silica precursors in solution. It has been found that the cylindrical tubes with zero Gaussian curvature were split and curved into hyperbolic surfaces and extruded to form SG structures and further evolved into the SDD networks. This growth or extrusion process suggests the SG structure is an intermediate phase of the cylindrical and SDD, and this transformation is found similar to the formation of butterfly wing scales (Thecla opisena), which has not been observed in neither the theoretical calculation nor the experimental self-assembly of amphiphilic molecules. We hope the structural relationship may bring new insights in understanding the formation of single networks in the biological system and the creation of new functional materials.

Enantiomeric Discrimination by Surface-Enhanced Raman Scattering-Chiral Anisotropy of Chiral Nanostructured Gold Films.

A surface-enhanced Raman scattering-chiral anisotropy (SERS-ChA) effect is reported that combines chiral discrimination and surface Raman scattering enhancement on chiral nanostructured Au films (CNAFs) equipped in the normal Raman scattering Spectrometer. The CNAFs provided remarkably higher enhancement factors of Raman scattering (EFs) for particular enantiomers, and the SERS intensity was proportional to the enantiomeric excesses (ee) values. Except for molecules with mesomeric species, all of the tested enantiomers exhibited high SERS-ChA asymmetry factors (g), ranging between 1.34 and 1.99 regardless of polarities, sizes, chromophores, concentrations and ee. The effect might be attributed to selective resonance coupling between the induced electric and magnetic dipoles associated with enantiomers and chiral plasmonic modes of CNAFs.

Synthesis of chiral mesostructured titanium dioxide films.

Chiral mesostructured TiO2 films (CMTFs) were synthesized by a hydrothermal method using l/d-mannitol as the symmetry-breaking agent and titanium foil as both the substrate and inorganic precursor. Five levels of hierarchical chirality exist in the CMTFs, exhibiting optical activity (OA) at ∼350 nm attributed to the electronic transitions in a dissymmetric electric field.

Crystal twinning of bicontinuous cubic structures.

Bicontinuous cubic structures in soft matter consist of two intertwining labyrinths separated by a partitioning layer. Combining experiments, numerical modelling and techniques in differential geometry, we investigate twinning defects in bicontinuous cubic structures. We first demonstrate that a twin boundary is most likely to occur at a plane that cuts the partitioning layer almost perpendicularly, so that the perturbation caused by twinning remains minimal. This principle can be used as a criterion to identify potential twin boundaries, as demonstrated through detailed investigations of mesoporous silica crystals characterized by diamond and gyroid surfaces. We then discuss that a twin boundary can result from a stacking fault in the arrangement of inter-lamellar attachments at an early stage of structure formation. It is further shown that enhanced curvature fluctuations near the twin boundary would cost energy because of geometrical frustration, which would be eased by a crystal distortion that is experimentally observed.

π-π Interactions Between Aromatic Groups in Amphiphilic Molecules: Directing Hierarchical Growth of Porous Zeolites.

The development of hierarchical macro- or mesoporous zeolites is essential in zeolite synthesis because the size of the micropores limits mass transport and their use as industrial catalysts for bulky molecules. Although major breakthroughs have been achieved, fabricating crystallographically ordered mesoporous zeolites using a templating strategy is still an unsolved challenge. This minireview highlights our recent efforts on the self-assembly of amphiphilic molecules to obtain ordered hierarchical MFI zeolites by introducing aromatic groups into the hydrophobic tail of the amphiphilic molecules. Owing to the geometric matching between the self-assembled aromatic tails and the MFI framework, a) single-crystalline mesostructured zeolite nanosheets (SCZNs), b) SCZNs with a 90° rotational intergrowth structure, c) a hierarchical MFI zeolite with a two-dimensional square P4mm mesostructure, and d) a single-crystalline mesoporous ZSM-5 with three-dimensional pores and sheetlike mesopores layered along the a-axis were successfully synthesized.

Spontaneous chiral self-assembly of achiral AIEgens into AIEgen-silica hybrid nanotubes.

Antipodal chiral AIEgen-silica hybrid mesostructures were fabricated by spontaneous chiral self-assembly of the achiral amphiphilic AIEgen 2-[4-(1,2,2-triphenylethenyl)phenoxy]-acetic acid via a co-structure directing route in the absence of any symmetry-breaking agent. The produced AIEgen-silica hybrid mesostructured nanotubes showed chiral features with optical activity originating from J-aggregation with an excess of one stereochemical hand of the helical conformation of the AIEgen.

One-Pot Synthesis and Formation Mechanism of Hollow ZSM-5.

Coffin-shaped hollow ZSM-5 zeolite (HZZ) particles with shell thickness of about 200 nm and hollow diameter of approximately 1.5 µm were synthesized in one pot by using tetrapropylammonium bromide (TPABr), aluminum triisopropoxide Al[OCH(CH3 )2 ]3 and tetraethoxysilane (TEOS) as the structure-directing agent (SDA), aluminum and silica source, respectively. The appropriate molar ratios of TPABr/SiO2 and Si/Al as well as suitable crystallization temperature are the key factors for the formation of HZZ. The formation of the HZZ can be attributed to the existence of intrinsic density variation inside the initial amorphous aggregates and the Al zoning in the outer surface of the ZSM-5 particles. Amorphous silica with low crystallinity formed at early stages and low Al concentration, which has been subsequently dissolved and recrystallized on the ZSM-5 particle surface through Ostwald ripening, leading to the formation of HZZ. This approach, which uses a high concentration of SDA, will provide new possibilities and insight into the prospective fabrication of hollow zeolites.