Hetero-Interface Engineering on 9.0 wt% CoOx -Doped CeO2 Nanorods as Electromagnetic Wave Absorber and Integrated into Multifunctional Aerogel.

Ceria (CeO2 ) becomes a promising candidate as electromagnetic wave absorbing materials (EWAMs) for their abundant natural source, rich oxygen vacancy, charge conversion, and electron transfer abilities. However, it remains challenging to regulate its nanoscale and atom-scale composition to optimize the absorbing performance and develop high-performance commercial devices. Herein, a facile method to large-scale synthesis CeO2 @Co-x% (x = 5, 7, 9, 11, 13) series EWAMs with diverse amounts of decorated CoOx is presented. By modulating the ratio of doped CoOx , a rational hetero-interface is created in CeO2 @Co-9% to enhance natural and exchange resonances, improving magnetic loss capability and optimizing impedance matching. Doped CoOx promotes the charge accumulation, interfacial polarization, and multiple scattering of the CeO2 for strengthening the EW absorption and attenuation, which display superb minimum reflective loss (RLmin ) of -74.4 dB with a wide effective absorbing bandwidth (EAB) of 5.26 GHz. Furthermore, a dual crosslinking strategy is employed to fabricate CeO2 @Co-9% into an aerogel device with integrated lightweight, heat insulation, compression resistance, and fame-retardant functions. This work presents an excellent example of large-scale fast synthesis of high-performance CeO2 -based EWAMs and multiplication 3D devices.

Multifunctional MoCx Hybrid Polyimide Aerogel with Modified Porous Defect Engineering for Highly Efficient Electromagnetic Wave Absorption.

Traditional electromagnetic absorbing materials (EWAMs) are usually single functions and can easily affect their performance in diverse application scenarios. Effective integration of EWAMs into multiple function components is a valuable strategy to achieve maximum absorption and multifunction performance while maintaining their indispensable physical and chemical properties. In this work, the polyoxometalates (POMs) serving as "guests" are embedded within the Co-MOFs to construct 3d/4d-bimetallic based crystalline precursors of dielectric/magnetic synergistic system. The proper pyrolysis temperature induced the homogeneously distributed metallic Co and MoCx hetero-units into carbon matrix with modified porous defect engineering to enhance electromagnetic wave (EW). Owing to the brilliant synergistic effect of polarization, magnetic loss, and impedance matching, the superior RLmin of -47.72 dB at 11.76 GHz at the thickness of 2.0 mm and a wide adequate absorption bandwidth (EAB) of 4.58 GHz (7.44-12.02 GHz) covered the whole X-band at the thickness of 2.5 mm for η-MoC/Co@NC-800 are observed. More importantly, the resulting MoCx hybrid polyimide (MCP) aerogel exhibits desirable properties such as structural robustness, nonflammability, excellent thermal insulation, and self-cleaning capabilities that are comparable to those of commercially available products. This work offers inspiration and strategy for creating multipurpose microwave absorbers with intricate structural designs.

Enhanced Photoinduced Carrier Separation in Fe-MOF-525/CdS for Photocatalytic Hydrogen Evolution: Improved Catalytic Dynamics with Specific Active Sites.

Single-atom metal-anchored porphyrin-based metal-organic frameworks (MOFs) have shown excellent light absorption, catalytic sites, and high stability during photocatalytic reactions, while there are still challenges for facile assembly with quantum dots to enhance catalytic dynamics. Herein, a kind of Fe single atom-doped MOF material (Fe-MOF-525) was ball milled with CdS in a proper ratio through Fe-N4 and Fe-N-C bonding, which showed the enhanced photoinduced carrier separation ability. As a result, extended light absorption ranges of CdS/Fe-MOF-5252.3 induced the promotion of the photocatalytic hydrogen (H2) value (3638.6 µmol g-1 h-1), which was 7.2 and 2.3 times higher than those of Fe-MOF-525 and CdS. In this work, the facile synthetic technique, specific active sites, and enhanced catalytic dynamics in the composite highlight the future research on MOF-based heterojunctions and their potential photocatalysis applications..

Stabilizing Solid-state Lithium Metal Batteries through In Situ Generated Janus-heterarchical LiF-rich SEI in Ionic Liquid Confined 3D MOF/Polymer Membranes.

Pursuing high power density lithium metal battery with high safety is essential for developing next-generation energy-storage devices, but uncontrollable electrolyte degradation and the consequence formed unstable solid-electrolyte interface (SEI) make the task really challenging. Herein, an ionic liquid (IL) confined MOF/Polymer 3D-porous membrane was constructed for boosting in situ electrochemical transformations of Janus-heterarchical LiF/Li3 N-rich SEI films on the nanofibers. Such a 3D-Janus SEI-incorporated into the separator offers fast Li+ transport routes, showing superior room-temperature ionic conductivity of 8.17×10-4  S cm-1 and Li+ transfer number of 0.82. The cryo-TEM was employed to visually monitor the in situ formed LiF and Li3 N nanocrystals in SEI and the deposition of Li dendrites, which is greatly benefit to the theoretical simulation and kinetic analysis of the structural evolution during the battery charge and discharge process. In particular, this membrane with high thermal stability and mechanical strength used in solid-state Li||LiFePO4 and Li||NCM-811 full cells and even in pouch cells showed enhanced rate-performance and ultra-long life spans.

Functional Roles of Polymers in Room-Temperature Phosphorescent Materials: Modulation of Intersystem Crossing, Air Sensitivity and Biological Activity.

Organic room-temperature phosphorescent (RTP) materials routinely incorporate polymeric components, which usually act as non-functional or "inert" media to protect excited-state phosphors from thermal and collisional quenching, but are lesser explored for other influences. Here, we report some exemplary "active roles" of polymer matrices played in organic RTP materials, including: 1) color modulation of total delayed emissions via balancing the population ratio between thermally-activated delayed fluorescence (TADF) and RTP due to dielectric-dependent intersystem crossing; 2) altered air sensitivity of RTP materials by generating various surface morphologies such as nano-sized granules; 3) enhanced bacterial elimination for enhanced electrostatic interactions with negatively charged bio-membranes. These active roles demonstrated that the vast library of polymeric structures and functionalities can be married to organic phosphors to broaden new application horizons for RTP materials.

Isolated Electron Trap-Induced Charge Accumulation for Efficient Photocatalytic Hydrogen Production.

The solar-driven evolution of hydrogen from water using particulate photocatalysts is considered one of the most economical and promising protocols for achieving a stable supply of renewable energy. However, the efficiency of photocatalytic water splitting is far from satisfactory due to the sluggish electron-hole pair separation kinetics. Herein, isolated Mo atoms in a high oxidation state have been incorporated into the lattice of Cd0.5 Zn0.5 S (CZS@Mo) nanorods, which exhibit photocatalytic hydrogen evolution rate of 11.32 mmol g-1 h-1 (226.4 µmol h-1 ; catalyst dosage 20 mg). Experimental and theoretical simulation results imply that the highly oxidized Mo species lead to mobile-charge imbalances in CZS and induce the directional photogenerated electrons transfer, resulting in effectively inhibited electron-hole recombination and greatly enhanced photocatalytic efficiency.

A 2-Fold Interpenetrated Nitrogen-Rich Metal-Organic Framework: Dye Adsorption and CO2 Capture and Conversion.

A bifunctional ligand strategy for modification of the functional pores is of great significance in the structural design of metal-organic frameworks (MOFs). Herein, a new 2-fold interpenetrated "pillared-layer" 3D Co-MOF, {[Co(HL)(4,4'-bipy)]·DMF·2H2O}n (1), was successfully synthesized by using two kinds of ligands, imidazolecarboxylic acid and pyridine. The metal-carboxylic layers are pillared by the 4,4'-bipy ligand, displaying a 3D framework with rectangular 3D channels (high BET surface of 190.9 m2 g-1 and maximum aperture of 3.9 Å) that are decorated with abundant uncoordinated N and O atoms. 1 shows good water stability and thermal stability (320 °C). The proper pores and active sites endowed 1 with a selective adsorption of Congo red in aqueous solution. In addition, a high CO2 adsorption capacity and an excellent CO2 chemical conversion were observed.

Hybrid Zeolitic Imidazolate Frameworks for Promoting Electrocatalytic Oxygen Evolution via a Dual-Site Relay Mechanism.

Developing efficient oxygen evolution reaction (OER) electrocatalysts is important for enhancing the water splitting efficiency. However, with the current catalysts containing one kind of active sites, it is challenging to achieve low overpotentials because of the four-electron transfer process. Herein is reported HZIF-2-CoMo, a new metal-organic framework with well-defined Co-Mo dual sites that can promote the OER process through an unconventional Mo6+/Co2+ dual-site relay mechanism. Theoretical calculations suggested that the Mo and Co sites stabilize the HO* and HOO* intermediates, respectively, and that the unique Co-O-Mo configuration induces the formation of a Co-O*-Mo transition intermediate, remarkably reducing the reaction free energy. As a result, HZIF-2-CoMo shows an overpotential of 277 mV at 10 mA cm-2 and a low Tafel slope of 70 mV dec-1 in alkaline solution, making it one of the best OER electrocatalysts reported to date.

An Organic Host-Guest System Producing Room-Temperature Phosphorescence at the Parts-Per-Billion Level.

Manipulation of long-lived triplet excitons in organic molecules is key to applications including next-generation optoelectronics, background-free bioimaging, information encryption, and photodynamic therapy. However, for organic room-temperature phosphorescence (RTP), which stems from triplet excitons, it is still difficult to simultaneously achieve efficiency and lifetime enhancement on account of weak spin-orbit coupling and rapid nonradiative transitions, especially in the red and near-infrared region. Herein, we report that a series of fluorescent naphthalimides-which did not originally show observable phosphorescence in solution, as aggregates, in polymer films, or in any other tested host material, including heavy-atom matrices at cryogenic temperatures-can now efficiently produce ultralong RTP (ϕ=0.17, τ=243 ms) in phthalimide hosts. Notably, red RTP (λRTP =628 nm) is realized at a molar ratio of less than 10 parts per billion, demonstrating an unprecedentedly low guest-to-host ratio where efficient RTP can take place in molecular solids.

Two-Dimensional Mesoporous Carbon Materials Derived from Fullerene Microsheets for Energy Applications.

Porous carbon materials rich in defects are promising candidates in energy storage and conversion applications. Herein, a facile template-free approach is reported for the synthesis of a two-dimensional (2 D) mesoporous carbon material derived from fullerene (C60 ) microsheets (FMSs) through simple heat treatment. The sample obtained at 1000 °C (FMS1000) shows a large surface area of 1507.6 m2 g-1 owing to the presence of mesopores and rich defects, which promote electron and mass transfer in the electrocatalytic process of the oxygen reduction reaction (ORR), showing an excellent performance with an onset potential of 0.95 V, a half-wave potential of 0.85 V, and long-term durability of 2000 cycles, comparable to the performance of commercial Pt/C. Moreover, FMS1000 displays a remarkable supercapacitive property with a specific capacitance of 330.7 F g-1 at 0.2 A g-1 and good long-term stability with a capacitance retention of 97 % over 50 000 cycles. Thus, a practical strategy for the production of mesoporous carbon materials with different morphological structures and porous defects as high-performance energy materials is advanced.

Persistent Radical Pairs between N-Substituted Naphthalimide and Carbanion Exhibit pKa -Dependent UV/Vis Absorption.

A new strategy was devised for estimating and screening pKa values among different carbon acids under ambient conditions by using the UV/Vis absorption spectrum of persistent radical pairs (PRPs), which are generated from an N-substituted naphthalimide (NNI) derivative in the presence of various carbanions in organic solutions. The electron paramagnetic resonance (EPR) spectroscopy was used to examine the presence of radicals. Unexpectedly, it was discovered that the UV/Vis spectrum of PRPs reveals a distinct linear relationship between the PRP absorption and the pKa value of a corresponding carbon acid, which is likely due to the energy difference among different RPRs. The finding may offer organic chemists an alternative reference to conduct carbanion-mediated reactions in various organic solutions.

Zeolitic Metal Cluster Carboxylic Framework for Selective Carbon Dioxide Chemical Fixation through the Superlarge Cage.

Metal-organic frameworks (MOFs) with zeolitic structure process fantastic structural metrics and display excellent applications in many aspects; however, they are difficult to assemble. Herein, on the basis of a tetrahedral Zn4O cluster and a 3,5-bis(2,4-dicarboxylphenyl)nitrobenzene (H4L) ligand, a novel sodalite (SOD) zeolitic cluster framework (ZCF), {[Zn4(O)(L)2]·4DMF·6H2O}n (ZCF-1; DMF = N,N-dimethylformamide), has been hydrothermally synthesized. Compared with the traditional SOD zeolitic framework of ZIF-8, the cage size of ZCF-1 is dramatically improved from 16.9 to 29.2 Å by the introduction of longer tetradentate carboxylic ligands. Moreover, because of the functional nitryl group in the ligand, ZCF-1 exhibits a high CO2/CH4 selectivity. Hence, further research on the chemical fixation of CO2 is implemented, which reveals excellent heterogeneous catalytic activity and durability. Especially, a unique selective catalytic performance with a high yield of 88.3% on a larger molecular size reactant (glycidyl phenyl ether) is observed, which is attributed to the stereoselection effect of the superlarge cage and abundant Zn4O catalytic clusters in ZCF-1.

An Unexpected Chromophore-Solvent Reaction Leads to Bicomponent Aggregation-Induced Phosphorescence.

Organic luminogens with persistent room-temperature phosphorescence (RTP) have found a wide range of applications. However, many RTP luminogens are prone to severe quenching in the crystalline state. Herein, we report a strategy to construct a donor-sp3 -acceptor type luminogen that exhibits aggregation-induced emission (AIE) while the donor-sp2 -acceptor counterpart structure exhibits a non-emissive solid state. Unexpectedly, it was discovered that a trace amount (0.01 %) of the structurally similar derivative, produced by a side reaction with the DMF solvent, could induce strong RTP with an absolute RTP yield up to 25.4 % and a lifetime of 48 ms, although the substance does not show RTP by itself. Single-crystal XRD-based calculations suggest that n-σ* orbital interactions as a result of structural similarity may be responsible for the strong RTP in the bicomponent system. This study provides a new insight into the design of multi-component, solid-state RTP materials from organic molecular systems.

Persistent Room-Temperature Radicals from Anionic Naphthalimides: Spin Pairing and Supramolecular Chemistry.

N-Substituted naphthalimides (NNIs) have been shown to exhibit highly efficient and persistent room-temperature phosphorescence from an NNI-localized triplet excited state, when the N-substitution is a sufficiently strong donor and mediates an intramolecular charge-transfer (ICT) state upon photo-excitation. This work shows that, when the electron-donating ability of the N-substitution is further increased in the presence of a carbanion or phenoxide, spontaneous electron transfer (ET) occurs and results in radical anions, verified with electron-paramagnetic resonance (EPR) spectroscopy. However, the EPR-active anion is surprisingly persistent and impervious to nucleophilic and radical reactions under anionic conditions. The stability is thought to originate from an intramolecular spin pairing between the N-donor and the NI acceptor post ET, which is demonstrated in supramolecular chemistry.

Isolation and Structural Characterization of Er@ C2 v(9)-C82 and Er@ C s(6)-C82: Regioselective Dimerization of a Pristine Endohedral Metallofullerene Induced by Cage Symmetry.

Two Er@C82 isomers have been isolated and unambiguously characterized as Er@ C2 v(9)-C82 and Er@ C s(6)-C82, respectively, by single-crystal X-ray diffraction. Er@ C s(6)-C82 is identified as a dimeric structure in the crystalline state, but dimerization does not occur for Er@ C2 v(9)-C82 under identical crystallization conditions, indicating a cage-symmetry-induced dimerization process. Density functional theory calculations reveal that the major unpaired spin resides on a special C atom of Er@ C s(6)-C82, which leads to regioselective dimerization. Calculations also found that the dimeric structure of Er@ C s(6)-C82·Ni(OEP) is much more stable than the two monomers, suggesting a thermodynamically favorable dimerization process. Vis-near-IR spectrometric and electrochemical results demonstrate that the electronic structure of Er@C82 isomers is Er3+@C823-, instead of the theoretically proposed Er2+@C822-.

Water-Stable Metal-Organic Frameworks with Selective Sensing on Fe3+ and Nitroaromatic Explosives, and Stimuli-Responsive Luminescence on Lanthanide Encapsulation.

Three water-stable luminescent MOFs [Zn4(bptc)2(NMP)3(DMF)(H2O)2] n (1-a), [Cd4(bptc)2(NMP)3(DMF)2(H2O)1] n (1-b), and {[Zn2(bptc)(DMA)(H2O)2]·(DMA)2·H2O} n (2), possessing similar chemical components (M2:L1:Sol3) and topology structures, were synthesized by solvents control. Their excellent sensing on iron(III) cation and nitroaromatic explosives (NACs) with great selectivity, sensitivity and a high Ksv (4.54 × 104 for 1-b on PNP) were observed by quenching effects. Furthermore, Zn-MOFs exhibit interesting stimuli-responsive luminescence enhancement after the encapsulation of a series of IIIB cations stimulated different luminescent emitting and intensity enhancement through host-guest processes of the pores in MOFs, especially for two distinct responses of Zn-MOF on a Tb3+ cation.

Isolation and Crystallographic Characterization of Lu3 N@C2n (2n=80-88): Cage Selection by Cluster Size.

The small Sc3 N cluster has only been found in such small cages as C2n (2n=68, 78, 80, 82), whereas the large M3 N (M=Y, Gd, Tb, Tm) clusters choose those larger cages C2n (2n=82-88). Herein, concrete experimental evidence is presented to establish the size effect of the internal metallic cluster on selecting the outer cage of endohedral metallofullerenes (EMFs) by using a medium-sized metal, lutetium, which possesses an ionic radius between Sc and Gd. A series of lutetium-containing EMFs have been obtained and their structures are unambiguously determined as Lu3 N@Ih (7)-C80 , Lu3 N@D5h (6)-C80 , Lu3 N@C2v (9)-C82 , Lu3 N@Cs (51365)-C84 , Lu3 N@D3 (17)-C86 , and Lu3 N@D2 (35)-C88 by single-crystal X-ray diffraction crystallography. It was confirmed that the encaged Lu3 N cluster always adopts a planar geometry in Lu3 N@C80-88 isomers to ensure substantial metal-cage/metal-nitrogen interactions. As a result, the Lu3 N cluster selects the C2v (9)-C82 cage, which also encapsulates Sc3 N, instead of the Cs (39663)-C82 cage which is more suitable for M3 N (M=Y, Gd, Tb, Tm). However, different from Sc3 N, Lu3 N can also template the C84-88 cages which are absent for Sc3 N-containing EMFs, confirming clearly the size effect of the internal cluster on selecting the outer cage.

Transcription factor AP-2ß suppresses cervical cancer cell proliferation by promoting the degradation of its interaction partner ß-catenin.

Transcription factor AP-2ß mediates the transcription of a number of genes implicated in mammalian development, cell proliferation, and carcinogenesis. Although the expression pattern of AP-2ß has been analyzed in cervical cancer cell lines, the functions and molecular mechanism of AP-2ß are unknown. Here, we found that AP-2ß significantly inhibits TCF/LEF reporter activity. Moreover, AP-2ß and ß-catenin interact both in vitro through GST pull-down assays and in vivo by co-immunoprecipitation. We further identified the interaction regions to the DNA-binding domain of AP-2ß and the 1-9 Armadillo repeats of ß-catenin. Moreover, AP-2ß binds with ß-TrCP and promotes the degradation of endogenous ß-catenin via the proteasomal degradation pathway. Immunohistochemistry analysis revealed a negative correlation between the two proteins in cervical cancer tissues and cell lines. Finally, functional analysis showed that AP-2ß suppresses cervical cancer cell growth in vitro and in vivo by inhibiting the expression of Wnt downstream genes. Taken together, these findings demonstrated that AP-2ß functions as a novel inhibitor of the Wnt/ß-catenin signaling pathway in cervical cancer.

2D-Graph of intermolecular interactions predicts radical character of anion-π* type charge-transfer complexes.

The molecular orbital (MO) theory is one of the most useful methods to describe the formation of a new chemical bond between two molecules. However, it is less often employed for modelling non-bonded intermolecular interactions because of the small charge-transfer contribution. Here we introduce two simple descriptors, the energy difference (EDA) of the HOMO of an electron donor and the LUMO of an acceptor against such HOMO-LUMO overlap integral (SDA), to show that the MO theory could give a unified charge-transfer picture of both bonding and non-bonding interactions for two molecules. It is found that similar types of interactions tend to be closer to each other in this 2D graph. Notably, in a transition region from strong bonding to single-electron transfer, the interacting molecular pairs appear to present a "hybrid" between chemical bonding and a radical pair, such as anion-π* interactions. It is concluded that the number of nodes in the HOMO and LUMO play a crucial role in determining the bonding character of the molecular pair.

Dual-Step Redox Engineering of 2D CoNi-Alloy Embedded B, N-Doped Carbon Layers Toward Tunable Electromagnetic Wave Absorption and Light-Weight Infrared Stealth Heat Insulation Devices.

2D layered metallic graphite composites are promising electromagnetic wave absorption materials (EWAMs) for their combined properties of abundant interlayer free spaces, rich metallic polarized sites, and high conductivity, but the controllable synthesis remains rather challenging. Herein, a dual-step redox engineering strategy is developed by employing cobalt boron imidazolate framework (Co-BIF) to construct 2D CoNi-alloy embedded B, N-doped carbon layers (2D-CNC) as a promising EWAM. In the first step, a chemical etching oxidation process on Co-BIF is used to obtain an optimized 2D-CoNi-layered double hydroxide (2D-CoNi-LDH) intermediate and in the second, high-temperature calcination reduction is implemented to modify graphitization of the degree of the 2D-CNC. The obtained sample delivers superior reflection loss (RLmin) of -60.1 dB and wide effective absorption bandwidth (EAB) of 6.24 GHz. The synergy mechanisms of interfacial/dipole polarization and magnetic coupling are in-depth evidenced by the hologram and Lorentz electron microscopy, revealing its significant contribution on multireflection and impedance matching. Further theoretical evaluation by COMSOL simulation in different fields based on the dynamic loss process toward the test ring reveals the in situ EW attenuation process. This work presents a strategy to develop multifunctional light-weight infrared stealthy aerogel with superior pressure-resistant, anti-corrosion, and heat-insulating properties for future applications.