Rational Construction of an Exceptionally Stable MOF Catalyst with Metal-Adeninate Vertices toward CO2 Cycloaddition under Mild and Cocatalyst-Free Conditions

CO₂ is considered as the primary greenhouse gas, resulting in a series of serious environmental problems that affect people's life and health. Carbon capture and sequestration has been implemented as one of the most appealing pathways to control and use CO₂. Here, we rationally integrate various functional sites within the confined nanospace of a microporous metal–organic framework (MOF) material, which is constructed by mixed-ligand strategy based on metal-adeninate vertices. It not only exhibits excellent stability but also can efficiently transform CO₂ and epoxides to cyclic carbonates under mild and cocatalyst-free conditions. Additionally, this catalyst shows extraordinary recyclability for the CO₂ cycloaddition reaction.     

Selective Excitation of Band Extrema in Valley Photonic Crystals

Flexible control of building blocks of photonic crystals enables achieving desirable band structures. Exploration of photonic band extrema has brought many fantastic features to design artificial optical materials, such as Brillouin‐zone‐corner extrema for valley photonic materials and zone‐center extremum for zero‐index metamaterials. However, two such kinds of extrema are always found independently in different photonic crystals. In this work, a kind of valley photonic crystals possessing both zone‐center and zone‐corner band extrema almost at the same frequency is proposed. Inspired by antennas theory, a three‐antenna array (TAA) source is devoted to individually manipulate each extremum. The correlation coefficient is given to determine the coupling efficiency between the TAA source and extrema eigenmodes. By using a source with a high correlation coefficient, these extrema bulk states are selectively excited consistent with their eigenfields. Furthermore, three control cases are shown that multiple extrema points are simultaneously excited, in order to confirm the validity of the correlation coefficient. Finally, a potential application of a beam‐steering device is proposed through selective excitation of ternary extrema. This work develops binary valley states into ternary mix states, rendering more degrees of freedom for on‐chip optical information transport, particularly for beam steering and mode division multiplexing.     

Structure and Mechanical Stability of Epoxy Modified Polyurethane Foam Under Heat and Stress

A series of phenolic epoxy resin (PEP) modified polyurethane foams (PUF) were prepared via an in-situ polymerization, one step process. It was found that the epoxy modified PUF foam exhibited a perforated network structure with larger cell size, higher open cell porosity and enhanced ovality compared with pure PUF. With increasing content of PEP, the tensile strength, elongation at break and low temperature modulus of PUF decreased. A single T_g was observed for PEP modified PUF, indicating that the two component phases of the polyurethane-epoxy were miscible. With increasing PEP content, the T_g of PUF shifted slightly to higher temperature, tan δ_max dropped to lower values, and the retention value of the storage modulus at ?20 and ?10?°C increased. For pure PUF, the cell walls degraded and the structure became disordered after aging under heat and stress, while for PUF/20wt%PEP, the degradation degree was obviously reduced, and an orientation of the cells along the stress direction and a density increase was observed. During aging at 200?°C, the retention of the mechanical properties of PUF/20wt% PEP was much higher than that of pure PUF, and it showed superior stability under heat and stress, attributed to incorporation of the thermally resistant oxazolidone rings and benzene rings in the PU backbones, the highly cross-linked networks of the polyurethane-epoxy systems and the obvious orientation of the cells under stress.     

Spherical hollow mesoporous silica supported phosphotungstic acid as a promising catalyst for α-arylstyrenes synthesis via Friedel-Crafts alkenylation

This work presents a scalable approach for preparing spherical hollow mesoporous silica with high surface area/pore volume, serving as outstanding support for supported phosphotungstic acid catalyst with much superior catalytic performance to the one on previously reported spherical mesoporous silica toward diverse transformations, ascribed to the strengthened mass transfer and the enlarged exposure degree of acidic sites to reactants those resulting from unique hollow and mesoporous morphology.     

Dose‐dependent exposure profile and metabolic characterization of notoginsenoside R1 in rat plasma by ultra‐fast liquid chromatography–electrospray ionization–tandem mass spectrometry

Notoginsenoside R₁ (NGR₁), a diagnostic protopanaxatriol‐type (ppt‐type) saponin in Panax notoginseng, possesses potent biological activities including antithrombotic, anti‐inflammatory, neuron protection and improvement of microcirculation, yet its pharmacokinetics and metabolic characterization as an individual compound remain unclear. The aim of this study was to investigate the exposure profile of NGR₁ in rats after oral and intravenous administration and to explore the metabolic characterization of NGR₁. A simple and sensitive ultra‐fast liquid chromatographic–tandem mass spectrometric method was developed and validated for the quantitative determination of NGR₁ and its major metabolites, and for characterization of its metabolic profile in rat plasma. The blood samples were precipitated with methanol, quantified in a negative multiple reaction monitoring mode and analyzed within 6.0 min. Validation parameters (linearity, precision and accuracy, recovery and matrix effect, stability) were within acceptable ranges. After oral administration, NGR₁ exhibited dose‐independent exposure behaviors with t_1/2 over 8.0 h and oral bioavailability of 0.25–0.29%. A total of seven metabolites were characterized, including two pairs of epimers, 20(R)‐notoginsenoside R₂/20(S)‐notoginsenoside R₂ and 20(R)‐ginsenoside Rh₁/20(S)‐ginsenoside Rh₁, with the 20(R) form of saponins identified for the first time in rat plasma. Five deglycometabolites were quantitatively determined, among which 20(S)‐notoginsenoside R₂, ginsenoside Rg₁, ginsenoside F₁ and protopanaxatriol displayed relatively high exploration, which may partly explain the pharmacodynamic diversity of ginsenosides after oral dose.     

Synthesis,characterization, and electrochemistry of monophosphine‐containing diiron propane‐1,2‐dithiolate complexes related to the active site of [FeFe]‐hydrogenases

Five monophosphine‐substituted diiron propane‐1,2‐dithiolate complexes as the active site models of [FeFe]‐hydrogenases have been synthesized and characterized. Reactions of complex [Fe₂(CO)₆{μ‐SCH₂CH(CH₃)S}] ( 1 ) with a monophosphine ligand tris(4‐methylphenyl)phosphine, diphenyl‐2‐pyridylphosphine, tris(4‐chlorophenyl)phosphine, triphenylphosphine, or tris(4‐fluorophenyl)phosphine in the presence of the oxidative agent Me₃NO·2H₂O gave the monophosphine‐substituted diiron complexes [Fe₂(CO)₅(L){μ‐SCH₂CH(CH₃)S}] [L = P(4‐C₆H₄CH₃)₃, 2 ; Ph₂P(2‐C₅H₄N), 3 ; P(4‐C₆H₄Cl)₃, 4 ; PPh₃, 5 ; P(4‐C₆H₄F)₃, 6 ] in 81%–94% yields. Complexes 2 – 6 have been characterized by elemental analysis, spectroscopy, and X‐ray crystallography. In addition, electrochemical studies revealed that these complexes can catalyze the reduction of protons to H₂ in the presence of HOAc.     

A self-penetrating and chemically stable zinc (ii)-organic framework as multi-responsive chemo-sensor to detect pesticide and antibiotics in water

Guided by the self-penetrating features can improve the stability of metal organic frameworks (MOFs), an unprecedented 3D self-penetrated framework, {[Zn (tptc)_0.5(bimb)]·H₂O}_n ( NUC-6 , here NUC corresponding to North University of China), with 3D (4,4)-c {8⁶} net, was designed. Benefit from the high chemical stability and excellent luminescent property, NUC-6 can be act as an efficient multi-response chemo-sensor in detecting dichloronitroaniline pesticide and nitrofuran antibiotics in water with the detection limits are 116 ppb for DCN pesticide, 16 ppb for NFT antibiotic, and 12 ppb for NTZ antibiotic. Besides, the mechanisms of luminescence quenching were revealed from the viewpoint of internal filter effect (IFE) and photo-induced electron transfer (PET), implied by the optical spectroscopy and quantum chemical calculation. This work provides a promising strategy to design stable MOFs by improving the self-penetrating features and to expand their practical applications in the detection of organic pollutants in aqueous medium.     

Proton conductivity study on three CS/IL@fle-MOF membranes

The low-cost, high specific surface area and porosity, controlled pore size, and chemical properties of metal–organic framework (MOF) materials have attracted much attention in the exploration of proton conduction. The method of chemically modifying MOF structures or introducing conductive medium into the holes can effectively improve the proton conductivities of the materials. Here, the structural tunability of ionic liquid (IL) and flexible MOF (fle-MOF) materials are matched to give full play to the conductivity of IL, the framework support, and the microporous effect of MOFs, which achieves the synergistic effect of performance and expands the temperature range of proton transfer. Three kinds of CS/IL@fle-MOF membranes were prepared by combining three fle-MOFs with 1-carboxymethyl-3-methylimidazole (CMMIM) in different proportions to obtain 15 pieces of membranes. The comparative analyses show that CS/IL@fle-MOF membranes have excellent proton conduction performance at a wider temperature range (263–353 K) and lower relative humidity (75% RH). Among them, the proton conductivities of CS/CMMIM@MIL-88A-25% and CS/CMMIM@MIL-88B-125% are up to 1.33 and 1.42 S cm⁻¹ at 75% RH and 353 K, respectively; whereas those of CS/CMMIM@MIL-53(Fe)-75% and CS/CMMIM@MIL-88B-125% reach up to 2.1 × 10⁻³ and 1.28 × 10⁻³ S cm⁻¹ at 75% RH and 263 K, respectively. The E_a of CS/CMMIM@fle-MOFs is in the range of 0.1–0.5 eV, suggesting that the proton transport follows predominantly the typical Grotthuss transfer mechanism. The results of this study indicate that the CS/CMMIM@fle-MOF membranes combinations offer great potential for the design of composite porous proton-conducting materials.     

Salen–Mg-doped NH2–MIL-101(Cr) for effective CO2 adsorption under ambient conditions

A novel metal-doped metal–organic framework (MOF) was developed by incorporating salen–Mg into NH₂–MIL-101(Cr) structure under ambient conditions. The Schiff base complex was successfully prepared by condensing salicylaldehyde with a free amino group and then coordinating metal ions. Such a structure can endow the sample with higher CO₂ adsorption performance. At 0°C and 1 bar, the salen–Mg-modified sample achieves the maximum adsorption capacity of 2.18 mmol g⁻¹ for CO₂, which was 5.8% higher than the pristine salen–MOF under the same conditions. Notably, the Freundlich model indicates that the CO₂ adsorption process of all samples conforms to reversible adsorption. However, the correlation coefficients (R²) of the Mg-doped sample are lower than that of the pristine sample. Besides, the CO₂/N₂ adsorption selectivity and isosteric heat also show a similar trend. These results indicate that the salen–Mg can enhance the interaction between the material and CO₂ molecules.