Deletion of the first glycosylation site promotes Lassa virus glycoprotein-mediated membrane fusion.

The Lassa virus (LASV) is endemic in West Africa and causes severe hemorrhagic Lassa fever in humans. The glycoprotein complex (GPC) of LASV is highly glycosylation-modified, with 11 â€‹N-glycosylation sites. All 11 N-linked glycan chains play critical roles in GPC cleavage, folding, receptor binding, membrane fusion, and immune evasion. In this study, we focused on the first glycosylation site because its deletion mutant (N79Q) results in an unexpected enhanced membrane fusion, whereas it exerts little effect on GPC expression, cleavage, and receptor binding. Meanwhile, the pseudotype virus bearing GPCN79Q was more sensitive to the neutralizing antibody 37.7H and was attenuated in virulence. Exploring the biological functions of the key glycosylation site on LASV GPC will help elucidate the mechanism of LASV infection and provide strategies for the development of attenuated vaccines against LASV infection.

Screening and Identification of Lassa Virus Entry Inhibitors from a Fragment-Based Drug Discovery Library.

Lassa virus (LASV) is a highly pathogenic virus that is categorized as a biosafety level-4 pathogen. Currently, there are no approved drugs or vaccines specific to LASV. In this study, high-throughput screening of a fragment-based drug discovery library was performed against LASV entry using a pseudotype virus bearing the LASV envelope glycoprotein complex (GPC). Two compounds, F1920 and F1965, were identified as LASV entry inhibitors that block GPC-mediated membrane fusion. Analysis of adaptive mutants demonstrated that the transient mutants L442F and I445S, as well as the constant mutant F446L, were located on the same side on the transmembrane domain of the subunit GP2 of GPC, and all the mutants conferred resistance to both F1920 and F1965. Furthermore, F1920 antiviral activity extended to other highly pathogenic mammarenaviruses, whereas F1965 was LASV-specific. Our study showed that both F1920 and F1965 provide a potential backbone for the development of lead drugs for preventing LASV infection.

Electron Crystallographic Investigation of Crystals on the Mesostructural Scale.

The precise structural solution of crystals on a mesostructural scale is challenging due to the difficulties in obtaining electron diffraction and the complicated relationship between the crystal structure factors (CSFs) and the conventional underfocus phase-contrast transmission electron microscopy (TEM) images due to the large unit cell and the complex structures. Here, we present the structural investigation of mesostructured crystals via the combination of electron crystallographic Fourier synthesis and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) that only relies on the mass-thickness contrast. The three-dimensional electrostatic potential is reconstructed from the amplitudes and phases extracted from the Fourier transforms of the corresponding HAADF-STEM images and merged into a set of CSFs. This method is verified on silica scaffolds following a shifted double-diamond surface network with space group I41/amd. The results indicate that electron crystallography reconstruction by HAADF-STEM images is more suitable and accurate in determining the structure in comparison with conventional TEM electron crystallography reconstruction. This approach transfers the contrast of mesostructured crystals to images more accurately and the relationship between the Fourier transforms of HAADF-STEM images and the CSFs is more intuitive. It shows great advantages for the structural solution of crystals on the mesostructural scale.

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.

Development and Application of Novel Sodium Silicate Microcapsule-Based Self-Healing Oil Well Cement.

A majority of well integrity problems originate from cracks of oil well cement. To address the crack issues, bespoke sodium silicate microcapsules were used in this study for introducing autonomous crack healing ability to oil well cement under high-temperature service conditions at 80 °C. Two types of sodium silicate microcapsule, which differed in their polyurea shell properties, were first evaluated on their suitability for use under the high temperature of 80 °C in the wellbore. Both types of microcapsules showed good thermal stability and survivability during mixing. The microcapsules with a more rigid shell were chosen over microcapsule with a more rubbery shell for further tests on the self-healing efficiency since the former had much less negative effect on the oil well cement strength. It was found that oil well cement itself showed very little healing capability when cured at 80 °C, but the addition of the microcapsules significantly promoted its self-healing performance. After healing for 7 days at 80 °C, the microcapsule-containing cement pastes achieved crack depth reduction up to ~58%, sorptivity coefficient reduction up to ~76%, and flexural strength regain up to ~27%. The microstructure analysis further confirmed the stability of microcapsules and their self-healing reactions upon cracking in the high temperature oil well cement system. These results provide a promising perspective for the development of self-healing microcapsule-based oil well cements.

3D Electron Diffraction Unravels the New Zeolite ECNU-23 from the "Pure" Powder Sample of ECNU-21.

A novel crystalline high-silica zeolite with 12×8-membered ring (R) channel system is prepared with the aid of the 3D electron diffraction (3D ED) technique. A crystal with the same topology as one of the predicted daughter structures of CIT-13 germanosilicate, named ECNU-23 (East China Normal University 23) was coincidentally detected by the 3D ED investigation during the structure characterization of the "pure" powder sample of existing one-dimension (1D) 10-R ECNU-21. By controlling the alkaline-assisted hydrolysis under moderate conditions, we purified the phase of ECNU-23 by selectively breaking and removing the chemically weak Ge(Si)-O-Ge and metastable Si-O-Si bonds. Its structure was determined based on the 3D ED data, and confirmed by high-resolution TEM images and powder X-ray diffraction (PXRD) data. The aluminosilicate Al-ECNU-23 shows unique catalytic properties in the isomerization/ disproportionation of m-xylene as solid-acid catalyst.

Topotactic Conversion of Alkali-Treated Intergrown Germanosilicate CIT-13 into Single-Crystalline ECNU-21 Zeolite as Shape-Selective Catalyst for Ethylene Oxide Hydration.

The conversion of the alkali-treated intergrowth germanosilicate CIT-13 into the single-crystalline high-silica ECNU-21 (named after East China Normal University) zeolite, with a novel topology and a highly crystalline zeolite framework, has been realized through a creative top-down strategy involving a mild alkaline-induced multistep process consisting of structural degradation and reconstruction. Instead of acid treatment, hydrolysis in aqueous ammonia solution not only readily cleaved the chemically weak Ge(Si)-O-Ge bonds located within the interlayer double four ring (D4R) units of CIT-13, but also cleaved the metastable Si-O-Si bonds therein. This led to extensive removal of the D4R units, and also generated silanol groups on adjacent silica-rich layers, which then condensed to form a novel daughter structure upon calcination. Individual oxygen bridges in the reassembled ECNU-21 replaced the germanium-rich D4R units in CIT-13, thereby eliminating the original intergrowth phenomenon along the b axis. With an ordered crystalline structure of 10-ring (R) channels as well as suitable germanium-related Lewis acid sites, ECNU-21 serves as a stable solid Lewis acid catalyst for the shape-selective hydration of ethylene oxide (EO) to ethylene glycol (EG) at greatly reduced H2 O/EO ratios and reaction temperature in comparison with the noncatalytic industrial process.

Structural reconstruction of germanosilicate frameworks by controlled hydrogen reduction.

Selective solid-gas reduction of the framework Ge ions has been carried out for the first time to induce a structural evolution in germanosilicates. Serving as a promising top-down post-synthesis strategy for constructing new zeolite structures, the controlled reduction of UTL germanosilicate with hydrogen successfully led to a series of novel structural analogs.

Dry Chemistry of Ferrate(VI): A Solvent-Free Mechanochemical Way for Versatile Green Oxidation.

The +6 oxidation state of iron generally exists in the form of ferrate(VI) with high redox potential and environmentally friendly nature. Although ferrate(VI) has been known for over a century, its chemistry is still limited to the solvent-based reactions that suffers from the insolubility/instability of this oxidant and the environmental issues caused by hazardous solvents. Herein, we explore the solvent-free reactivity of ferrate(VI) under mechanical milling, revealing that its strong oxidizing power is accessible in the "dry" solid state towards a broad variety of substrates, for example, aromatic alcohols/aldehydes and carbon nanotubes. More significantly, solvent-free mechanochemistry also reshapes the oxidizing ability of ferrate(VI) due to the underlying solvent-free effect and the promotive mechanical actions. This study opens up a new chemistry of ferrate(VI) with promising application in green oxidative transformation of both organic and inorganic substrates.

Fabrication of Photonic Bandgap Materials by Shifting Double Frameworks.

Biological organisms have evolved over millions of years to generate tremendously complex structures on a nanometer to micrometer scale. Among them, a range of three-dimensional (3D) biological photonic structures with minimal surface or constant mean curvature surfaces have been discovered in the wing scales of insects, attracting a great deal of interest because of their unique optical properties, such as structural color, antireflection, light collection, and photonic band gaps. Single-diamond and single-gyroid surface structures are considered to be excellent photonic crystals with complete band gaps. Although the corresponding bicontinuous architectures have been synthesized by self-assembly, single-framework structures are thermodynamically unfavorable and have been only achieved by physical fabrications and the alternating gyroid method. The production of materials derived from the thermodynamically stable double-framework structures provides a feasible solution for their chemical construction. This concept article highlights the significant progress in understanding 3D photonic structures by shifting double-frameworks to form low-symmetry structures, the physical properties of which can be greatly altered. Specifically, a complete photonic band gap can be achieved via a shifted double-diamond structure composed of materials with high dielectric contrast and high refractive index. We believe this concept will provide new insights in interdisciplinary research areas including the study of photonic structures, the self-assembly of amphiphilic molecules and the formation of biological architectures.

Confined Ultrathin Pd-Ce Nanowires with Outstanding Moisture and SO2 Tolerance in Methane Combustion.

An efficient strategy (enhanced metal oxide interaction and core-shell confinement to inhibit the sintering of noble metal) is presented confined ultrathin Pd-CeOx nanowire (2.4 nm) catalysts for methane combustion, which enable CH4 total oxidation at a low temperature of 350 °C, much lower than that of a commercial Pd/Al2 O3 catalyst (425 °C). Importantly, unexpected stability was observed even under harsh conditions (800 °C, water vapor, and SO2 ), owing to the confinement and shielding effect of the porous silica shell together with the promotion of CeO2 . Pd-CeOx solid solution nanowires (Pd-Ce NW) as cores and porous silica as shells (Pd-CeNW@SiO2 ) were rationally prepared by a facile and direct self-assembly strategy for the first time. This strategy is expected to inspire more active and stable catalysts for use under severe conditions (vehicle emissions control, reforming, and water-gas shift reaction).

Mesoporous MFI Zeolite with a 2D Square Structure Directed by Surfactants with an Azobenzene Tail Group.

Mesoporous MFI zeolites (MMZs) have been constructed by using the surfactant-containing azobenzene segment in the hydrophobic tail. The cylindrical π-π stacking of azeobenzene groups is considered to be the key factor to form the ordered mesostructure through cooperative structural matching and the rearrangement of MFI frameworks. The mesostructure has been tuned from a disordered hierarchical arrangement into an ordered 2D square p4mm structure by changing the length of the alkyl chain between the diquaternary ammonium head group and azobenzene group. The geometric matching between the MFI zeolitic framework and the alkyl chain length plays an important role in the construction of the crystallographically correlated mesostructure with 2D square ordering. A combination of X-ray diffraction patterns and electron microscopy studies provides visible evidence for the mesostructural transformation from a short-range hexagonal or lamellar ordering to 2D square mesostructure.

A Hierarchical MFI Zeolite with a Two-Dimensional Square Mesostructure.

A conceptual design and synthesis of ordered mesoporous zeolites is a challenging research subject in material science. Several seminal articles report that one-dimensional (1D) mesostructured lamellar zeolites are possibly directed by sheet-assembly of surfactants, which collapse after removal of intercalated surfactants. However, except for one example of two-dimensional (2D) hexagonal mesoporous zeolite, no other zeolites with ordered 2D or three-dimensional (3D) mesostructures have been reported. An ordered 2D mesoporous zeolite can be templated by a cylindrical assembly unit with specific interactions in the hydrophobic part. A template molecule with azobenzene in the hydrophobic tail and diquaternary ammonium in the hydrophilic head group directs hierarchical MFI zeolite with a 2D square mesostructure. The material has an elongated octahedral morphology, and quaternary, ordered, straight, square channels framed by MFI thin sheets expanded along the a-c planes and joined with 90° rotations. The structural matching between the cylindrical assembly unit and zeolite framework is crucial for mesostructure construction.

Growth of 2D Mesoporous Polyaniline with Controlled Pore Structures on Ultrathin MoS2 Nanosheets by Block Copolymer Self-Assembly in Solution.

The development of versatile strategies toward two-dimensional (2D) porous nanocomposites with tunable pore structures draws immense scientific attention in view of their attractive physiochemical properties and a wide range of promising applications. This paper describes a self-assembly approach for the directed growth of mesoporous polyaniline (PANi) with tunable pore structures and sizes on ultrathin freestanding MoS2 nanosheets in solution, which produces 2D mesoporous PANi/MoS2 nanocomposites. The strategy employs spherical and cylindrical micelles, which are formed by the controlled solution self-assembly of block copolymers, as the soft templates for the construction of well-defined spherical and cylindrical mesopores in the 2D PANi/MoS2 nanocomposites, respectively. With potential applications as supercapacitor electrode materials, the resultant 2D composites show excellent capacitive performance with a maximum capacitance of 500 F g-1 at a current density of 0.5 A g-1, good rate performance, as well as outstanding stability for charge-discharge cycling. Moreover, the 2D mesoporous nanocomposites offer an opportunity for the study on the influence of different pore structures on their capacitive performance, which helps to understand the pore structure-property relationship of 2D porous electrode materials and to achieve their electrochemical performance control.

Silica Scaffold with Shifted "Plumber's Nightmare" Networks and their Interconversion into Diamond Networks.

Bicontinuous structures with hyperbolic surfaces have been found in a variety of natural and synthetic systems. Herein, we present the synthesis and structural study of the shifted double-primitive networks, which is known as the rare "plumber's nightmare", and its interconversion into diamond networks. The scaffold was prepared by self-assembly of an amphiphilic triblock terpolymer and silica precursors. Electron crystallography indicates that the structure consists of two sets of hollow primitive networks shifted along 0.75b and 0.25c axes (2pcu(38 63), space group Cmcm). The "side-by-side" epitaxial relationship of the primitive and diamond networks with unit cell ratio of about 1.30 has been directly observed with the intermediate surface related to the rPD family. These results bring new insights to previous theoretical studies.

Tunable Self-Assembly of Diblock Copolymers into Colloidal Particles with Triply Periodic Minimal Surfaces.

We herein report the tunable self-assembly of simple block copolymers, namely polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymers, into porous cubosomes with inverse Im3‾m or Pn3‾m mesophases of controlled unit cell parameters as well as hexasomes with an inverse hexagonal (p6mm) structure, which have been rarely observed in polymer self-assembly. A new morphological phase diagram was constructed for the solution self-assembly of PS-b-PEO based on the volume fraction of the PS block against the initial copolymer concentration. The formation mechanisms of the cubosomes and hexasomes have also been revealed. This study not only affords a simple system for the controllable preparation and fundamental studies of ordered bicontinuous structures, but also opens up a new avenue towards porous architectures with highly ordered pores.