"Hard" Emulsion-Induced Interface Super-Assembly: A General Strategy for Two-Dimensional Hierarchically Porous Metal-Organic Framework Nanoarchitectures.

Two-dimensional (2D) hierarchically porous metal-organic framework (MOF) nanoarchitectures with tailorable meso-/macropores hold great promise for enhancing mass transfer kinetics, augmenting accessible active sites, and thereby boosting performance in heterogeneous catalysis. However, achieving the general synthesis of 2D free-standing MOF nanosheets with controllable hierarchical porosity and thickness remains a challenging task. Herein, we present an ingenious "hard" emulsion-induced interface super-assembly strategy for preparing 2D hierarchically porous UiO-66-NH2 nanosheets with highly accessible pore channels, tunable meso-/macropore sizes, and adjustable thicknesses. The methodology relies on transforming the geometric shape of oil droplet templates within appropriate oil-in-water emulsions from conventional zero-dimensional (0D) "soft" liquid spheres to 2D "hard" solid sheets below the oil's melting/freezing point. Subsequent surfactant exchange on the surface of 2D "hard" emulsions facilitates the heterogeneous nucleation and interfacial super-assembly of in situ formed mesostructured MOF nanocomposites, serving as structural units, in a loosely packed manner to produce 2D MOF nanosheets with multimodal micro/meso-/macroporous systems. Importantly, this strategy can be extended to prepare other 2D hierarchically porous MOF nanosheets by altering metal-oxo clusters and organic ligands. Benefiting from fast mass transfer and highly accessible Lewis acidic sites, the resultant 2D hierarchically porous UiO-66-NH2 nanosheets deliver a fabulous catalytic yield of approximately 96% on the CO2 cycloaddition of glycidyl-2-methylphenyl ether, far exceeding the yield of approximately 29% achieved using conventional UiO-66-NH2 microporous crystals. This "hard" emulsion-induced interface super-assembly strategy paves a new path toward the rational construction of elaborate 2D nanoarchitecture of hierarchical MOFs with tailored physicochemical properties for diverse potential applications.

Regioselective Surface Assembly of Mesoporous Carbon on Zeolites Creating Anisotropic Wettability for Biphasic Interface Catalysis.

The anisotropic surface functionalization of microporous zeolites with mesoporous materials into hierarchically porous heterostructures with distinctive physical and chemical properties is expected to significantly extend their applicability to catalysis. However, the precise control of the surface chemistry of zeolite crystals through site-specific interconnection with mesoporous materials remains a grand challenge. Here, we report a regioselective surface assembly strategy for the region-specific growth of mesoporous polymer/carbon on zeolite nanocrystals. The approach enables controllable regioselective surface deposition of mesoporous polydopamine on the edges, curved surfaces, or/and flat surfaces of the silicalite-1 nanocrystals into exotic hierarchical nanostructures with diverse surface geometries. Upon carbonization, their derived heterostructures with anisotropic surface wettability show amphiphilic properties. As a proof of concept, Pt nanoparticle-encapsulated silicalite-1/mesoporous carbon nanocomposites are tested to be interface-active for forming Pickering emulsions. Significantly, the catalysts show superior catalytic performance in shape-selective hydrogenation of various nitroarenes in a series of biphasic tandem catalytic reactions, giving ∼100% yield of corresponding amine products. The results pave a path toward rational construction of high levels of surface structural complexity in hierarchically porous heterostructures for specific physical and chemical characteristics in diverse applications.

Construction of Three-Dimensional Dendritic Hierarchically Porous Metal-Organic Framework Nanoarchitectures via Noncentrosymmetric Pore-Induced Anisotropic Assembly.

As a unique class of modular nanomaterials, metal-organic framework (MOF) nanoparticles have attracted widespread interest for use in various fields because of their diverse chemical functionalities, intrinsic microporosity, and three-dimensional (3D) nanoarchitectures. However, endowing MOF nanomaterials with precisely controlled structural symmetries and hierarchical macro/mesoporosities remains a formidable challenge for the researchers. Herein, we report a facile noncentrosymmetric pore-induced anisotropic assembly strategy to prepare a series of 3D dendritic MOF (UiO-66) nanomaterials with highly controllable structural symmetries and hierarchical macro/meso/microporosities. The synthetic route of these nanomaterials depends on the anisotropic nucleation of MOF spherical nanocones with noncentrosymmetric center-radial channels and their oriented growth to isotropic nanospheres through a continuous increase in radius and solid angle. This strategy enables the controllable fabrication of asymmetric MOF nanostructures with abundant geometries and porous structures by regulating the concentration of amphiphilic triblock copolymer templates. Furthermore, the average pore diameter of the resultant MOF nanospheres can be systematically manipulated in a wide range from 35 to 130 nm by finely tuning the reaction temperature. Meanwhile, the strategy can also be extended to synthesize other MOF nanoparticles with similar architectures. Compared with microporous UiO-66 nanocrystals, the MOF nanoparticles with controllable structural symmetries and macro/meso/microporosities show enhanced catalytic activity in the CO2 cycloaddition reaction. The methodology provides new insights into the rational construction of sophisticated asymmetric open nanostructures of hierarchically porous MOFs for many potential applications.

Cepharanthine Dry Powder Inhaler for the Treatment of Acute Lung Injury.

Severe acute respiratory syndrome Coronavirus 2 (SARS-CoV-2) induces a severe cytokine storm that may cause acute lung injury/acute respiratory distress syndrome (ALI/ARDS) with high clinical morbidity and mortality in infected individuals. Cepharanthine (CEP) is a bisbenzylisoquinoline alkaloid isolated and extracted from Stephania cepharantha Hayata. It exhibits various pharmacological effects, including antioxidant, anti-inflammatory, immunomodulatory, anti-tumor, and antiviral activities. The low oral bioavailability of CEP can be attributed to its poor water solubility. In this study, we utilized the freeze-drying method to prepare dry powder inhalers (DPI) for the treatment of acute lung injury (ALI) in rats via pulmonary administration. According to the powder properties study, the aerodynamic median diameter (Da) of the DPIs was 3.2 µm, and the in vitro lung deposition rate was 30.26; thus, meeting the Chinese Pharmacopoeia standard for pulmonary inhalation administration. We established an ALI rat model by intratracheal injection of hydrochloric acid (1.2 mL/kg, pH = 1.25). At 1 h after the model's establishment, CEP dry powder inhalers (CEP DPIs) (30 mg/kg) were sprayed into the lungs of rats with ALI via the trachea. Compared with the model group, the treatment group exhibited a reduced pulmonary edema and hemorrhage, and significantly reduced content of inflammatory factors (TNF-α, IL-6 and total protein) in their lungs (p < 0.01), indicating that the main mechanism of CEP underlying the treatment of ALI is anti-inflammation. Overall, the dry powder inhaler can deliver the drug directly to the site of the disease, increasing the intrapulmonary utilization of CEP and improving its efficacy, making it a promising inhalable formulation for the treatment of ALI.

Cepharanthine Ameliorates Pulmonary Fibrosis by Inhibiting the NF-κB/NLRP3 Pathway, Fibroblast-to-Myofibroblast Transition and Inflammation.

Pulmonary fibrosis (PF) is one of the sequelae of Corona Virus Disease 2019 (COVID-19), and currently, lung transplantation is the only viable treatment option. Hence, other effective treatments are urgently required. We investigated the therapeutic effects of an approved botanical drug, cepharanthine (CEP), in a cell culture model of transforming growth factor-ß1 (TGF-ß1) and bleomycin (BLM)-induced pulmonary fibrosis rat models both in vitro and in vivo. In this study, CEP and pirfenidone (PFD) suppressed BLM-induced lung tissue inflammation, proliferation of blue collagen fibers, and damage to lung structures in vivo. Furthermore, we also found increased collagen deposition marked by α-smooth muscle actin (α-SMA) and Collagen Type I Alpha 1 (COL1A1), which was significantly alleviated by the addition of PFD and CEP. Moreover, we elucidated the underlying mechanism of CEP against PF in vitro. Various assays confirmed that CEP reduced the viability and migration and promoted apoptosis of myofibroblasts. The expression levels of myofibroblast markers, including COL1A1, vimentin, α-SMA, and Matrix Metallopeptidase 2 (MMP2), were also suppressed by CEP. Simultaneously, CEP significantly suppressed the elevated Phospho-NF-κB p65 (p-p65)/NF-κB p65 (p65) ratio, NOD-like receptor thermal protein domain associated protein 3 (NLRP3) levels, and elevated inhibitor of NF-κB Alpha (IκBα) degradation and reversed the progression of PF. Hence, our study demonstrated that CEP prevented myofibroblast activation and treated BLM-induced pulmonary fibrosis in a dose-dependent manner by regulating nuclear factor kappa-B (NF-κB)/ NLRP3 signaling, thereby suggesting that CEP has potential clinical application in pulmonary fibrosis in the future.

Bioavailability Enhancement of Cepharanthine via Pulmonary Administration in Rats and Its Therapeutic Potential for Pulmonary Fibrosis Associated with COVID-19 Infection.

Cepharanthine (CEP) has excellent anti-SARS-CoV-2 properties, indicating its favorable potential for COVID-19 treatment. However, its application is challenged by its poor dissolubility and oral bioavailability. The present study aimed to improve the bioavailability of CEP by optimizing its solubility and through a pulmonary delivery method, which improved its bioavailability by five times when compared to that through the oral delivery method (68.07% vs. 13.15%). An ultra-performance liquid chromatography tandem-mass spectrometry (UPLC-MS/MS) method for quantification of CEP in rat plasma was developed and validated to support the bioavailability and pharmacokinetic studies. In addition, pulmonary fibrosis was recognized as a sequela of COVID-19 infection, warranting further evaluation of the therapeutic potential of CEP on a rat lung fibrosis model. The antifibrotic effect was assessed by analysis of lung index and histopathological examination, detection of transforming growth factor (TGF)-ß1, interleukin-6 (IL-6), α-smooth muscle actin (α-SMA), and hydroxyproline level in serum or lung tissues. Our data demonstrated that CEP could significantly alleviate bleomycin (BLM)-induced collagen accumulation and inflammation, thereby exerting protective effects against pulmonary fibrosis. Our results provide evidence supporting the hypothesis that pulmonary delivery CEP may be a promising therapy for pulmonary fibrosis associated with COVID-19 infection.

Construction of Single-Crystalline Hierarchical ZSM-5 with Open Nanoarchitectures via Anisotropic-Kinetics Transformation for the Methanol-to-Hydrocarbons Reaction.

We report an anisotropic-kinetics transformation strategy to prepare single-crystalline aluminosilicate MFI zeolites (ZSM-5) with highly open nanoarchitectures and hierarchical porosities. The methodology relies on the cooperative effect of in situ etching and recrystallization on the evolution of pure-silica MFI zeolite (silicalite-1) nanotemplates under hydrothermal conditions. The strategy enables a controllable preparation of ZSM-5 nanostructures with diverse open geometries by tuning the relative rate difference between etching and recrystallization processes. Meanwhile, it can also be extended to synthesize other heteroatom-substituted MFI zeolite nanocages. Compared with conventional ZSM-5 microcrystals, nanocrystals, and nanoboxes, the ZSM-5 nanocages with single-crystalline nature, highly open nanoarchitectures, and hierarchical porosities exhibit remarkably enhanced catalytic lifetime and low coking rate in the methanol-to-hydrocarbons (MTH) reaction.

General Synthesis of Hierarchically Macro/Mesoporous Fe,Ni-Doped CoSe/N-Doped Carbon Nanoshells for Enhanced Electrocatalytic Oxygen Evolution.

Constructing hierarchical porosity and designing rational hybrid composition are effective strategies for enhancing the electrocatalytic performance of hybrid catalysts for electrochemical energy conversion. Here, we develop a multistep "molecule/ion-exchange" strategy toward the synthesis of hierarchically macro/mesoporous Fe,Ni-doped CoSe/N-doped carbon nanoshells with tunable pore structures and compositions. Polystyrene (PS)@Co-based amorphous coordination polymer (Co-CP) core-shell particles with hierarchically macro/mesoporous nanoshells are first prepared by ligand-molecule-exchange etching of the outer layers in PS@Co-based metal-organic framework precursors. Afterward, a liquid-solid dual-ion-exchange reaction of PS@Co-CP particles with [Fe(CN)6]3- and [Ni(CN)4]2- ions leads to the formation of PS@Co-CP/Co-Fe Prussian blue analogue (PBA)/Co-Ni PBA particles, which are further transformed into hierarchically macro/mesoporous Fe,Ni-doped CoSe/N-doped carbon particles via a vapor-solid selenization reaction. Moreover, this approach could be extended to synthesize different hierarchically porous core-shell composites with various morphologies and tailored compositions. Because of their unique hierarchically porous nanoarchitecture, these Fe,Ni-doped CoSe/N-doped carbon particles with optimized composition show enhanced performance for electrocatalytic oxygen evolution.

General Formation of Macro-/Mesoporous Nanoshells from Interfacial Assembly of Irregular Mesostructured Nanounits.

Mesoporous core-shell nanostructures with controllable ultra-large open channels in their nanoshells are of great interest. However, soft template-directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro-/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core-shell nanomaterials with controllable pore architectures. The obtained Fe,N-doped macro-/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition.

Carbon Dots in a Matrix: Energy-Transfer-Enhanced Room-Temperature Red Phosphorescence.

High-efficiency red room-temperature phosphorescence (RTP) emissions have been achieved by embedding carbon dots (CDs) in crystalline Mn-containing open-framework matrices. The rationale of this strategy relies on two factors: 1) the carbon source, which affects the triplet energy levels of the resulting CDs and thus the spectral overlap and 2) the coordination geometry of the Mn atoms in the crystalline frameworks, which determines the crystal-field splitting and thus the emission spectra. Embedding the carbon dots into a matrix with 6-coordinate Mn centers resulted in a strong red RTP with a phosphorescence efficiency of up to 9.6 %, which is higher than that of most reported red RTP materials. The composite material has an ultrahigh optical stability in the presence of strong oxidants, various organic solvents, and strong ultraviolet radiation. A green-yellow RTP composite was also prepared by using a matrix with 4-coordinate Mn centers and different carbon precursors.

Fluoride-free and seed-free microwave-assisted hydrothermal synthesis of nanosized high-silica Beta zeolites for effective VOCs adsorption.

High-silica Beta zeolites, typically synthesized by hydrothermal synthesis with the assistance of F- or seeds, are highly important in volatile organic compounds (VOCs) adsorption. Fluoride-free or seed-free synthesis of high-silica Beta zeolites attracts great attention. Herein, highly dispersed Beta zeolites with a size of 25-180 nm and Si/Al ratios of 9-∞ were successfully synthesized by a microwave-assisted hydrothermal strategy. We have for the first time revealed that microwave irradiation can induce the formation of hydroxyl free radicals (˙OH), promoting the formation of the Si-O-Si bond. Thanks to the high total surface area, pore volume, and excellent hydrophobicity, the as-prepared pure-silica Beta zeolite presents a higher toluene adsorption capacity in VOCs adsorption compared to other pure-silica Beta zeolites prepared by traditional methods. This work provides a facile avenue for fluoride-free and seed-free synthesis of nanosized high-silica zeolites, promising their important applications in VOCs adsorption.

Ultrasmall water-stable CsPbBr3 quantum dots with high intensity blue emission enabled by zeolite confinement engineering.

Ultrasmall CsPbBr3 perovskite quantum dots (PQDs) as promising blue-emitting materials are highly desired for full-color display and lighting applications, but their inferior efficiency and poor ambient stability hinder extensive applications. Herein, a "break-and-repair" strategy has been developed to tightly confine monodispersed ultrasmall CsPbBr3 PQDs in a zeolite. In this strategy, the CsPbBr3 PQDs are introduced into the zeolite via a high temperature evaporation method, wherein the perovskite precursors break the zeolite framework, and amino acids and silane are then used to fix the damaged framework and lock the perovskite QDs within the matrix. By modulating the synthetic conditions to control the growth of CsPbBr3, PQDs with ultrasmall size of 2 nm have been obtained in the zeolite, giving emission centered at 460 nm with a high quantum yield of 76.93%. Strikingly, the PQDs@zeolite composite exhibits water-induced reversible photoluminescence promoted by the coordination between the amino acids and PQDs in a dynamic manner, achieving enhanced water stability (14 days in aqueous solution). This work provides a new perspective for the synthesis of water-stable blue-emitting perovskite composites for potential applications in lighting fields.

A facile dual-template-directed successive assembly approach to hollow multi-shell mesoporous metal-organic framework particles.

Hollow multi-shell mesoporous metal-organic framework (MOF) particles with accessible compartmentalization environments, plentiful heterogeneous interfaces, and abundant framework diversity are expected to hold great potential for catalysis, energy conversion, and biotechnology. However, their synthetic methodology has not yet been established. In this work, a facile dual-template-directed successive assembly approach has been developed for the preparation of monodisperse hollow multi-shell mesoporous MOF (UiO-66-NH2) particles through one-step selective etching of successively grown multi-layer MOFs with alternating two types of mesostructured layers. This strategy enables the preparation of hollow multi-shell mesoporous UiO-66-NH2 nanostructures with controllable shell numbers, accessible mesochannels, large pore volume, tunable shell thickness and chamber sizes. The methodology relies on creating multiple alternating layers of two different mesostructured MOFs via dual-template-directed successive assembly and their difference in framework stability upon chemical etching. Benefiting from the highly accessible Lewis acidic sites and the accumulation of reactants within the multi-compartment architecture, the resultant hollow multi-shell mesoporous UiO-66-NH2 particles exhibit enhanced catalytic activity for CO2 cycloaddition reaction. The dual-template-directed successive assembly strategy paves the way toward the rational construction of elaborate hierarchical MOF nanoarchitectures with specific physical and chemical features for different applications.

Anisotropic Interface Successive Assembly for Bowl-Shaped Metal-Organic Framework Nanoreactors with Precisely Controllable Meso-/Microporous Nanodomains.

Colloidal metal-organic framework (MOF) nanoparticles, with tailored asymmetric nanoarchitectures and hierarchical meso-/microporosities, have significant implications in high-performance nanocatalysts, nanoencapsulation carriers, and intricate assembly architectures. However, the methodology that could achieve precise control over the anisotropic growth of asymmetric MOF particles with tailored distributions of meso- and microporous regions has not yet been established. In this study, we introduce a facile anisotropic interface successive assembly approach to synthesize asymmetric core-shell MOF (ZIF-67) nanobowls with worm-like mesopores in the core and intrinsic micropores in the shell. Our synthesis pathway relies on anisotropic nucleation of mesoporous MOF nanohemispheres on emulsion interfaces through the cooperative assembly of surfactants and MOF precursors. This is followed by the growth of microporous MOF layers on both interfaces of mesoporous cores and emulsion droplets, resulting in a hierarchically porous core-shell nanostructure. By utilizing this multi-interface-driven approach, we enable the creation of diverse geometries and distributions of mesopores and micropores in asymmetric MOF nanoarchitectures. The obtained bowl-like meso-/microporous core-shell ZIF-67 particles exhibit enhanced catalytic activity for CO2 cycloaddition, attributed to reactant accumulation within the bowl-like architecture, active site accessibility in the open mesoporous core, and improved structural stability. Overall, our study provides insights and inspiration for exploring the intricate asymmetric nanostructures of hierarchically porous MOFs with diverse potential applications.

Effects of radon exposure on gut microbiota and its metabolites short-chain fatty acids in mice.

Radon (222Rn) is a naturally occurring radioactive gas. Forty percent of the natural radiation to which the human body is exposed comes from radon gas. Long-term exposure to high concentrations of radon induces systemic damage. However, the effect of such exposure on gut microbiota still remains unclear. We explored the effects of radon exposure on gut microbiota and its metabolites short-chain fatty acids (SCFAs) in BALB/c mice by cumulative inhalation of radon at 30, 60, and 120 working level months (WLM). The radon-exposed mice showed slow body weight gain, decreased serum triglycerides and low-density lipoproteins, decreased diversity, lower community structure, and altered abundance of the gut microbiota. Lachnospiraceae, Amaricoccus, and Enterococcus could differentiate the IR30, 60, and 120 WLM groups, respectively. Meanwhile, radon exposure affected the metabolic functions of the gut microbiota, mainly carbohydrate, amino acid, and lipid metabolic pathways. The altered abundance of microbiota and resulting reduced levels of SCFAs may aggravate the damage caused by radon exposure.

Mesoporous Nanoarchitectures for Electrochemical Energy Conversion and Storage.

Mesoporous materials have attracted considerable attention because of their distinctive properties, including high surface areas, large pore sizes, tunable pore structures, controllable chemical compositions, and abundant forms of composite materials. During the last decade, there has been increasing research interest in constructing advanced mesoporous nanomaterials possessing short and open channels with efficient mass diffusion capability and rich accessible active sites for electrochemical energy conversion and storage. Here, the synthesis, structures, and energy-related applications of mesoporous nanomaterials are the main focus. After a brief summary of synthetic methods of mesoporous nanostructures, the delicate design and construction of mesoporous nanomaterials are described in detail through precise tailoring of the particle sizes, pore sizes, and nanostructures. Afterward, their applications as electrode materials for lithium-ion batteries, supercapacitors, water-splitting electrolyzers, and fuel cells are discussed. Finally, the possible development directions and challenges of mesoporous nanomaterials for electrochemical energy conversion and storage are proposed.

Red Room-Temperature Phosphorescence of CDs@Zeolite Composites Triggered by Heteroatoms in Zeolite Frameworks.

Carbon dots (CDs) with red-emitting room-temperature phosphorescence (RTP) are rarely reported because of the increasing nonradiative decay of the excited states and the decreasing energy gap between the excited states and ground states. Herein, we demonstrate a facile strategy for modulating the RTP properties of CDs in terms of donor-acceptor energy transfer (EnT) in the CDs-in-zeolite system. Upon tuning of the heteroatoms (Zn2+, Mn2+) doped in the aluminophosphate zeolite frameworks, CDs@zeolite composites with green and red phosphorescence have been prepared via in situ hydrothermal synthesis. In such composites, the zeolite matrix provides an efficient confinement role in stabilizing the triplet states of CDs. Significantly, the Mn-doped zeolite could act as an energy acceptor allowing EnT from excitons of CDs to the dopant in the host matrix, generating the intriguing red RTP behavior. This work provides an effective strategy for developing CD-based composite materials with special RTP emissions as well as new fields for applications.

Mesoporogen-Free Synthesis of Hierarchical SAPO-34 with Low Template Consumption and Excellent Methanol-to-Olefin Conversion.

Significant interest has emerged in the development of nanometer-sized and hierarchical silicoaluminophosphate zeolites (SAPO-34) because of their enhanced accessibility and improved catalytic activity for methanol-to-olefin (MTO) conversion. A series of nanometer-sized SAPO-34 catalysts with tunable hierarchical structures was synthesized in a Al2 O3 /H3 PO4 /SiO2 /triethylamine(TEA)/H2 O system by using a mesoporogen-free nanoseed-assisted method. The nanometer-sized hierarchical SH -3.0 catalyst (TEA/Al2 O3 =3.0) possessed the highest crystallinity, highest abundance of intracrystalline meso-/macropores, and the most suitable acidity among all obtained catalysts, showing the highest ethylene and propylene selectivity of 85.4 %. This is the highest reported selectivity for MTO reactions under similar conditions. Detailed analysis of the coke produced during the reaction revealed that the small-sized methyl-substituted benzene and bulky methyl-substituted pyrene were mainly located inside the crystals instead of on the surface of the crystals, which provided further insight into understanding the deactivation of the SAPO-34 catalyst during MTO reaction. Significantly, the simple and cost-effective synthetic process and superb catalytic performance of the nanometer-sized hierarchical SAPO-34 is promising for their practical large-scale application for MTO conversion.

Nanoseed-assisted synthesis of nano-sized SAPO-34 zeolites using morpholine as the sole template with superior MTO performance.

Nano-sized SAPO-34 catalysts have been for the first time prepared using morpholine as the sole template by using a one-pot nanoseed-assisted method. The obtained nano-sized SAPO-34 catalysts exhibit about 4-fold prolonged lifetime and nearly 5% increased selectivity for ethylene and propylene compared to conventional micron-sized counterparts in methanol-to-olefin reactions.