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By incorporating soft materials into the architecture, flexible mechanical metamaterials enable promising applications, e.g., energy modulation, and shape morphing, with a well-controllable mechanical response, but suffer from spatial and temporal programmability towards higher-level mechanical intelligence. One feasible solution is to introduce snapping structures and then tune their responses by accurately tailoring the stress-strain curves. However, owing to the strongly coupled nonlinearity of structural deformation and material constitutive model, it is difficult to deduce their stress-strain curves using conventional ways. Here, a machine learning pipeline is trained with the finite element analysis data that considers those strongly coupled nonlinearities to accurately tailor the stress-strain curves of snapping metamaterialfor on-demand mechanical response with an accuracy of 97.41%, conforming well to experiment. Utilizing the established approach, the energy absorption efficiency of the snapping-metamaterial-based device can be tuned within the accessible range to realize different rebound heights of a falling ball, and soft actuators can be spatially and temporally programmed to achieve synchronous and sequential actuation with a single energy input. Purely relying on structure designs, the accurately tailored metamaterials increase the devices' tunability/programmability. Such an approach can potentially extend to similar nonlinear scenarios towards predictable or intelligent mechanical responses., (© 2024 Wiley‐VCH GmbH.)

Oligomerization is an important feature of proteins, which gives a defined quaternary structure to complete the biological functions. Although frequently observed in membrane proteins, characterizing the oligomerization state remains complicated and time-consuming. In this study, 0.05% (w/v) sarkosyl-polyacrylamide gel electrophoresis (05SAR-PAGE) was used to identify the oligomer states of the membrane proteins CpxA, EnvZ, and Ma-Mscl with high sensitivity. Furthermore, two-dimensional electrophoresis (05SAR/sodium dodecyl sulfate-PAGE) combined with western blotting and liquid chromatography-tandem mass spectrometry was successfully applied to study the complex of CpxA/OmpA in cell lysate. The results indicated that 05SAR-PAGE is an efficient, economical, and practical gel method that can be widely used for the identification of membrane protein oligomerization and the analysis of weak protein interactions., (© 2024 Wiley‐VCH GmbH.)

Light-driven carboxylation offers a promising approach for synthesizing valuable fine chemicals under mild conditions. Here we disclose a heterogeneous photocatalytic strategy of C(sp 2 )-H activation of formate for hydrocarboxylation of alkenes over zinc indium sulfide (ZnIn 2 S 4 ) under visible light. This protocol functions well with a variety of substituted styrenes with good to excellent yields; it also works for unactivated alkenes albeit with lower yields. Mechanistic studies confirm the existence of CO 2 ⋅ - as a key intermediate. It was found that C(sp 2 )-H activation of formate is induced by S⋅ species on the surface of ZnIn 2 S 4 via hydrogen atom transfer (HAT) instead of a photogenerated hole oxidation mechanism. Moreover, both cleavage of the C(sp 2 )-H of HCOO - and formation of a benzylic anion were found to be involved in the rate-determining step for the hydrocarboxylation of styrene., (© 2024 Wiley-VCH GmbH.)

Azametallacyclopentadienes are an important class of metallacycles as the key intermediates in metal-promoted or catalyzed carbon-carbon coupling reaction of nitriles and alkynes. Rare-earth azametallacyclopentadienes have shown unique reactivity toward benzonitriles. The reaction chemistry of azalutetacyclopentadienes toward 2-methylbenzonitriles has been investigated in this work, showing different reactivity. Experimental and computational studies reveal that the reaction selectively initiates with the remote activation of the benzylic C-H bond by the Lu-N bond, followed by the intramolecular nucleophilic attack from the deprotonated benzylic carbon to form a C-C bond. Subsequently, the high ring strain promoted the generation of the uncoordinated carbanion dissociated from the lutetium center, which then undergoes intramolecular nucleophilic attack toward C≡N triple bond to give the final product containing fused 7-5-6-membered azalutetacycle. This work not only achieves highly selective three-step cascade transformation to form a unique class of rare-earth metallacycle, but also reveals a novel reaction pattern of unsaturated substrates with C-H bonds that can be activated., (© 2024 Wiley‐VCH GmbH.)

As a critical radioactive anionic contaminant, traditional adsorbents primarily remove iodate (IO 3 - ) through ion exchange or hard acid-hard base interactions, but suffer from limited affinity and capacity. Herein, employing the synergistic effect of ion exchange and redox, we successfully synthesized a redox-active cationic polymer network (SCU-CPN-6, [C 9 H 10 O 2 N 5  ⋅ Cl] n ) by merging guanidino groups with ion-exchange capability and phenolic groups with redox ability via a Schiff base reaction. SCU-CPN-6 exhibits a groundbreaking adsorption capacity of 896 mg/g for IO 3 - . The inferior adsorption capacities of polymeric networks containing only redox (~0 mg/g) or ion exchange (232 mg/g) fragments underscore the synergistic "1+1>2" effect of the two mechanisms. Besides, SCU-CPN-6 shows excellent uptake selectivity for IO 3 - in the presence of high concentrations of SO 4 2- , Cl - , and NO 3 - . Meanwhile, a high distribution coefficient indicates its exemplary deep-removal performance for low IO 3 - concentration. The synergic strategy not only presents a breakthrough solution for the efficient removal of IO 3 - but also establishes a promising avenue for the design of advanced adsorbents for diverse applications., (© 2024 Wiley-VCH GmbH.)

Metal-organic framework (MOF) based heterostructures, which exhibit enhanced or unexpected functionality and properties due to synergistic effects, are typically synthesized using post-synthetic strategies. However, several reported post-synthetic strategies remain unsatisfactory, considering issues such as damage to the crystallinity of MOFs, presence of impure phases, and high time and energy consumption. In this work, we demonstrate for the first time a novel route for constructing MOF based heterostructures using radiation-induced post-synthesis, highlighting the merits of convenience, ambient conditions, large-scale production, and notable time and energy saving. Specifically, a new HKUST-1@Cu 2 O heterostructure was successfully synthesized by simply irradiating a methanol solution dispersed of HKUST-1 with gamma ray under ambient conditions. The copper source of Cu 2 O was directly derived from in situ radiation etching and reduction of the parent HKUST-1, without the use of any additional copper reagents. Significantly, the resulting HKUST-1@Cu 2 O heterostructure exhibits remarkable catalytic performance, with a catalytic rate constant nearly two orders of magnitude higher than that of the parent HKUST-1., (© 2024 Wiley-VCH GmbH.)

In vitro, 19 F NMR methodology is preferably selected as a complementary and straightforward method for unveiling the conformations, dynamics, and interactions of biological molecules. Its effectiveness in vivo has seen continuous improvement, addressing challenges faced by conventional heteronuclear NMR experiments on structured proteins, such as severe line broadening, low signal-to-noise ratio, and background signals. Herein, we summarize the distinctive advantages of 19 F NMR, along with recent progress in sample preparation and applications within the realm of in-cell NMR. Additionally, we offer insights into the future directions and prospects of this methodology based on our understanding., (© 2024 Wiley‐VCH GmbH.)

For the drawbacks of phase change materials such as poor shape stability and weak solar-thermal conversion ability, a rotunda-shaped carboxymethylcellulose/carbon nanotube aerogel (CA) with three-dimensional network was constructed by freeze casting with a special mold, and then impregnated with polyethylene glycol (PEG) in this work. The PEG/CA had an enthalpy of 183.21 J/g, and a thermal conductivity of 0.324 W m -1  K -1 , which was 57 % higher than the pure PEG. The ability of PEG/CA to convert solar energy to thermal energy was a positive correlation between the inclusion of CNTs and the composite material's thermal conductivity. Under simulated sunlight, its solar-thermal conversion efficiency reaches 94.41 %, and after 10 min of irradiation, the surface temperature can reach 65 °C and the internal temperature can reach 44.67 °C. This rotunda-shaped PEG/CA is promising for the efficient use of renewable solar energy due to its strong solar-thermal conversion and thermal storage capabilities., (© 2024 Wiley‐VCH GmbH.)

Activation of ubiquitous C(sp 3 )-H bonds is extremely attractive but remains a great challenge. Heterogeneous photocatalysis offers a promising and sustainable approach for C(sp 3 )-H activation and has been fast developing in the past decade. This Minireview focuses on mechanism and strategies for heterogeneous photocatalytic C(sp 3 )-H activation. After introducing mechanistic insights, heterogeneous photocatalytic strategies for C(sp 3 )-H activation including precise design of active sites, regulation of reactive radical species, improving charge separation and reactor innovations are discussed. In addition, recent advances in C(sp 3 )-H activation of hydrocarbons, alcohols, ethers, amines and amides by heterogeneous photocatalysis are summarized. Lastly, challenges and opportunities are outlined to encourage more efforts for the development of this exciting and promising field., (© 2024 Wiley-VCH GmbH.)

In mice, retrotransposon-associated long noncoding RNAs (lncRNA) play important regulatory roles in pre-implantation development; however, it is largely unknown whether they function in the pre-implantation development in pigs. The current study aims to screen for retrotransposon-associated lncRNA in porcine early embryos and identifies a porcine 8-cell embryo-specific SINE-associated nuclear long noncoding RNA named SAWPA. SAWPA is essential for porcine embryonic development as depletion of SAWPA results in a developmental arrest at the 8-cell stage, accompanied by the inhibition of the JNK-MAPK signaling pathway. Mechanistically, SAWPA works in trans as a transcription factor for JNK through the formation of an RNA-protein complex with HNRNPA1 and MED8 binding the SINE elements upstream of JNK. Therefore, as the first functional SINE-associated long noncoding RNAs in pigs, SAWPA provides novel insights for the mechanism research on retrotransposons in mammalian pre-implantation development., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Efficient adsorption of palladium ions from acid nuclear waste solution is crucial for ensuring the safety of vitrification process for radioactive waste. However, the limited stability and selectivity of most current adsorbents hinder their practical applications under strong acid and intense radiation conditions. Herein, to address these limitations, we designed and synthesized an aryl-ether-linked covalent organic framework (COF-316-DM) grafted dimethylthiocarbamoyl groups on the pore walls. This unique structure endows COF-316-DM with high stability and exceptional palladium capture capacity. The robust polyarylether linkage enables COF-316-DM to withstand irradiation doses of 200 or 400 kGy of β/γ ray. Furthermore, COF-316-DM demonstrates fast adsorption kinetics, high adsorption capacity (147 mg g -1 ), and excellent reusability in 4 M nitric acid. Moreover, COF-316-DM exhibits remarkable selectivity for palladium ions in the presence of 17 interference ions, simulating high level liquid waste scenario. The superior adsorption performance can be attributed to the strong binding affinity between the thioamide groups and Pd 2+ ions, as confirmed by the comprehensive analysis of FT-IR and XPS spectra. Our findings highlight the potential of COFs with robust linkers and tailored functional groups for efficient and selective capture of metal ions, even in harsh environmental conditions., (© 2023 Wiley-VCH GmbH.)

Transparent conductive electrodes (TCEs) are indispensable components of various optoelectronic devices such as displays, touch screen panels, solar cells, and smart windows. To date, the fabrication processes for metal mesh-based TCEs are either costly or having limited resolution and throughput. Here, a two-step surface energy-directed assembly (SEDA) process to efficiently fabricate high resolution silver meshes is introduced. The two-step SEDA process turns from assembly on a functionalized substrate with hydrophilic mesh patterns into assembly on a functionalized substrate with stripe patterns. During the SEDA process, a three-phase contact line pins on the hydrophilic pattern regions while recedes on the hydrophobic non-pattern regions, ensuring that the assembly process can be achieved with excellent selectivity. The necessity of using the two-step SEDA process rather than a one-step SEDA process is demonstrated by both experimental results and theoretical analysis. Utilizing the two-step SEDA process, silver meshes with a line width down to 2 µm are assembled on both rigid and flexible substrates. The thickness of the silver meshes can be tuned by varying the withdraw speed and the assembly times. The assembled silver meshes exhibit excellent optoelectronic properties (sheet resistance of 1.79 Ω/□, optical transmittance of ≈92%, and a FoM value of 2465) as well as excellent mechanical stability. The applications of the assembled silver meshes in touch screen panels and thermal heaters are demonstrated, implying the potential of using the two-step SEDA process for the fabrication of TCEs for optoelectronic applications., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Li-containing alloys and metallic deposits offer substantial Li + storage capacities as alternative anodes to commercial graphite. However, the thermodynamically in sequence, yet kinetically competitive mechanism between Li solubility in the solid solution and intermediate alloy-induced Li deposition remains debated, particularly across the multiple scales. The elucidation of the mechanism is rather challenging due to the dynamic alloy evolution upon the non-equilibrium, transient lithiation processes under coupled physical fields. Here, influential factors governing Li solubility in the Li-Zn alloy are comprehensively investigated as a demonstrative model, spanning from the bulk electrolyte solution to the ion diffusion within the electrode. Through real-time phase tracking and spatial distribution analysis of intermediate alloy/Li metallic species at varied temperatures, current densities and particle sizes, the driving force of Li solubility and metallic plating along the Li migration pathway are probed in-depth. This study investigates the correlation between kinetics (pronounced concentration polarization, miscibility gap in lattice grains) and rate-limiting interfacial charge transfer thermodynamics in dedicating the Li diffusion into the solid solution. Additionally, the lithiophilic alloy sites with the balanced diffusion barrier and Li adsorption energy are explored to favor the homogeneous metal plating, which provides new insights for the rational innovation of high-capacity alloy/metallic anodes., (© 2023 Wiley-VCH GmbH.)

Carbonylation of ethanol with CO 2 as carbonyl source into value-added esters is of considerable significance and interest, while remains of great challenge due to the harsh conditions for activation of inert CO 2 in that the harsh conditions result in undesired activation of α-C-H and even cleavage of C-C bond in ethanol to deteriorate the specific activation of O-H bond. Herein, we propose a photo-thermal cooperative strategy for carbonylation of ethanol with CO 2 , in which CO 2 is activated to reactive CO via photo-catalysis with the assistance of *H from thermally-catalyzed dissociation of alcoholic O-H bond. To achieve this proposal, an interfacial site and oxygen vacancy both abundant SrTiCuO 3-x supported Cu 2 O (Cu 2 O-SrTiCuO 3-x ) has been designed. A production of up to 320 μmol g -1  h -1 for ethyl formate with a selectivity of 85.6 % to targeted alcoholic O-H activation has been afforded in photo-thermal assisted gas-solid process under 3.29 W cm -1 of UV/Vis light irradiation (144 °C) and 0.2 MPa CO 2 . In the photo-driven activation of CO 2 and following carbonylation, CO 2 activation energy decreases to 12.6 kJ mol -1 , and the cleavage of alcoholic α-C-H bond has been suppressed., (© 2023 Wiley-VCH GmbH.)

Proton exchange membrane fuel cells (PEMFCs) have garnered significant attention due to their high efficiency and low emissions. However, PEMFC always suffers mass transfer and water management in performance improvement. Herein, an integrated gas diffusion layer (GDL) with wavy channel and micro-tunneled rib is designed and prepared to achieve faster and gentler mass transfer and excellent water management capability by laser engraving. Outstandingly, the new integrated GDL can use the back pressure of air as low as 0 and 50 kPa to respectively achieve 80% and 90% of fuel cell performance realized under pure oxygen. Such high performance is mainly due to the turbulent flow caused by wavy channel and express removing pathway of liquid water provided by micro-tunneled rib. Moreover, the new integrated GDL also shows wide humidity tolerance from 40% to 100% and a very high specific volume power density of 16,300 W L -1 due to the thin thickness of new integrated GDL. This new integrated GDL is expected to be widely used in PEMFC and other energy conversion devices., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Halide perovskites (HPs) recently have emerged as one class of competitive scintillators for X-ray detection and imaging owing to its high quantum efficiency, short decay time, superior X-ray absorption capacity, low cost, and ease of crystal growth. The tunable structure and versatile chemical compositions of halide perovskites provide distinguishable advantages over traditional inorganic scintillators for optimizing scintillation performance. Since the first observation of the scintillation phenomenon in HPs, substantial efforts have been devoted to expanding the inventory of HP scintillators and regulating material properties. Understanding the relationship between the structure and scintillation properties of HP scintillators is essential for developing materials with improved X-ray detection and imaging capacities. This review summarizes strategies for improving the light yield of HP scintillators and provides a roadmap for improving the X-ray imaging performance. Additionally, methods for controlling the light propagation direction in HP scintillators are highlighted for improving X-ray imaging resolution. Finally, we highlight the current challenge in HP scintillators and provide a perspective on the future development of this emerging scintillator., (© 2023 Wiley-VCH GmbH.)

The commercialization of fuel cells inevitably brings recycling problems. Therefore, achieving high recyclability of fuel cells is particularly important for their sustainable development. In this work, a recyclable standalone microporous layer (standalone MPL) with interpenetrating network that can significantly enhance the recyclability and sustainability of fuel cells is prepared. The interpenetrating network enables the standalone MPL to have high strength (17.7 MPa), gas permeability (1.55 × 10 -13  m 2 ), and fuel-cell performance (peak power density 1.35 W cm -2 ), providing the basic guarantee for its application in high-performance and highly recyclable fuel cells. Additionally, the standalone MPL is highly adaptable to various gas-diffusion backings (GDBs), providing high possibility to select highly recyclable GDBs. Outstandingly, anode standalone MPLs and GDBs can be easily detached from the spent membrane electrode assembly (MEA). This not only saves >90 vol% solvent in the recovery of the catalyst-coated membrane (CCM), but also extends the service life of the GDBs and the anode standalone MPL at least 138 times (2 760 000 h assuming 20 000 h of CCM) comparing to CCM. Therefore, the standalone MPL significantly enhances the recyclability and sustainability of fuel cells and is promising to be an indispensable component in the next-generation fuel cells., (© 2023 Wiley-VCH GmbH.)

The development of high-performance X-ray detectors requires scintillators with fast decay time, high light yield, stability, and X-ray absorption capacity, which are difficult to achieve in a single material. Here, we present the first example of a lanthanide chalcogenide of LaCsSiS 4  : 1 % Ce 3+ that simultaneously integrates multiple desirable properties for an ideal scintillator. LaCsSiS 4  : 1 % Ce 3+ demonstrates a remarkably low detection limit of 43.13 nGy air  s -1 and a high photoluminescence quantum yield of 98.24 %, resulting in a high light yield of 50480±1441 photons/MeV. Notably, LaCsSiS 4  : 1 % Ce 3+ exhibits a fast decay time of only 29.35±0.16 ns, making it one of the fastest scintillators among all lanthanide-based inorganic scintillators. Furthermore, this material shows robust radiation and moisture resistance, endowing it with suitability for chemical processing under solution conditions. To demonstrate the X-ray imaging capacity of LaCsSiS 4  : 1 % Ce 3+ , we fabricated a flexible X-ray detector that achieved a high spatial resolution of 8.2 lp mm -1 . This work highlights the potential of lanthanide chalcogenide as a promising candidate for high-performance scintillators., (© 2023 Wiley-VCH GmbH.)

Periodically arranging coordination-distinct actinides into one crystalline architecture is intriguing but of great synthetic challenge. We report a rare example of a heterobimetallic actinide metal-organic framework (An-MOF) by a unique reaction-induced preorganization strategy. A thorium MOF (SCU-16) with the largest unit cell among all Th-MOFs was prepared as the precursor, then the uranyl was precisely embedded into the MOF precursor under oxidation condition. Single crystal of the resulting thorium-uranium MOF (SCU-16-U) shows that a uranyl-specific site was in situ induced by the formate-to-carbonate oxidation reaction. The heterobimetallic SCU-16-U exhibits multifunction catalysis properties derived from two distinct actinides. The strategy proposed here offers a new avenue to create mixed-actinide functional material with unique architecture and versatile functionality., (© 2023 Wiley-VCH GmbH.)

In-cell NMR spectroscopy is an effective tool for observing proteins at atomic resolution in their native cellular environment. However, its utility is limited by its low sensitivity and the extensive line broadening caused by nonspecific interactions in the cells, which is even more pronounced in human cells due to the difficulty of overexpressing or delivering high concentrations of isotopically labeled proteins. Here, we present a high-sensitivity tag (wPSP-6F) containing two trifluoromethyl groups that can efficiently label globular proteins with molecular weights in the 6-40 kDa range under mild conditions. This tag allowed us to detect globular proteins in human cells at concentrations as low as 1.0 μM, which would not have been achievable with 15 N or 3-fluorotyrosine labeling. Moreover, we detected conformational changes and interactions of proteins in the cellular environment. The new sensitive 19 F NMR tag may significantly expand the scope of protein NMR in human cells., (© 2023 Wiley-VCH GmbH.)

Low crystalline photocatalysts with unsaturated active sites, such as oxygen vacancy (O v ), is reported to exhibit enhanced adsorption and activation of oxygen-containing small molecules, such as H 2 O and CO 2 , thus boosting the activity in photocatalytic H 2 evolution and CO 2 reduction. However, numerous low-crystalline photocatalysts show unsatisfactory stability due to the easily repaired surface O v . Herein, three SnNb 2 O 6 with different crystallinity were prepared by hydrothermal approach with similar precursors. Compared with bulk SnNb 2 O 6 and ultra-thin layered SnNb 2 O 6 , low-crystalline SnNb 2 O 6 (SNA) exhibits optimal visible-light-driven evolution rates of H 2 (86.04 μmol g -1  h -1 ) and CO from CO 2 (71.97 μmol g -1  h -1 ), which is mainly ascribed to the fast separation of the photogenerated carriers and enhanced photoreduction power caused by the surface O v . More importantly, the sharp decrease of photocatalytic activity of SNA after seven cycles is well restored by the hydrothermal treatment of recycled SNA, ascribed to the reactivated surface O v with the recovered low-crystalline structure. These works thus offer a promising strategy for developing low-crystalline and amorphous photocatalysts with high activity and stability., (© 2023 Wiley-VCH GmbH.)

Using benzylamines as the C4 source of 1,4-dihydropyridines (1,4-DHPs), a Cu-catalyzed oxidative [1+2+1+2] cascade cyclization for the synthesis of 1,4-DHPs was firstly developed. A broad range of easily available N,N-dimethyl enaminones and benzylamines are employed smoothly to provide a diverse range of 1,4-DHPs with high efficiency. This method is performed by a one-pot cascade C(sp 3 )-H bond functionalization/C(sp 3 )-N cleavage/cyclization strategy to form simultaneously two C(sp 3 )-C(sp 2 ) bonds, two C(sp 2 )-N bonds, and a 1,4-DHP ring., (© 2023 Wiley-VCH GmbH.)

Electromagnetic (EM) wave pollution is harmful to human health and environment, thus it is absolutely important to develop new electromagnetic wave absorbing materials. MAX phases have been attracted more attention as a potential candidate for electromagnetic wave absorbing materials due to their high conductivity and nanolaminated structure. Herein, two new magnetic MAX phases with multiprincipal elements ((Ti 1/3 Nb 1/3 Ta 1/3 ) 2 FeC and (Ti 0.2 V 0.2 Nb 0.2 Ta 0.2 Zr 0.2 ) 2 FeC) in which Fe atoms replace Al atoms in the A sites are successfully synthesized by an isomorphous replacement reaction of multiprincipal (Ti 1/3 Nb 1/3 Ta 1/3 ) 2 AlC and (Ti 0.2 V 0.2 Nb 0.2 Ta 0.2 Zr 0.2 ) 2 AlC MAX phases with Lewis acid salt (FeCl 2 ). (Ti 1/3 Nb 1/3 Ta 1/3 ) 2 FeC and (Ti 0.2 V 0.2 Nb 0.2 Ta 0.2 Zr 0.2 ) 2 FeC exhibit ferromagnetic behavior, and the Curie temperature (T c ) are 302 and 235 K, respectively. The dual electromagnetic absorption mechanisms that include dielectric and magnetic loss, which is realized in these multiprincipal MAX phases. The minimum reflection loss (RL) of (Ti 1/3 Nb 1/3 Ta 1/3 ) 2 FeC is -44.4 dB at 6.56 GHz with 3 mm thickness, and the effective bandwidth is 2.48 GHz. Additionally, the electromagnetic wave absorption properties of the magnetic MAX phases indicate that magnetic loss also plays an important role besides dielectric loss. This work shows a promising composition-design strategy to develop MAX phases with good EM wave absorption performance via simultaneously regulating dielectric and magnetic loss together., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

2D lamellar membranes (2DLMs) are used for efficient desalination and nanofiltration. However, weak interactions between adjacent stacked nanosheets result in susceptibility to swelling that limits practical applicability. Inspired by the super adhesion of multi-point suction cups on octopus tentacles, a 2DLM is constructed from Ti 3 C 2 T x MXene supported by the macrocyclic "multi-point" molecule cucurbit[5]uril (CB5) and demonstrated for nanofiltration of methyl blue (MB) and enrichment of uranyl carbonate. Experimental results and density functional theory calculations indicate that CB5 rivets to the surface of the nanoflakes through strong stable interactions between its multiple binding sites and surface hydroxyl functional groups on MXene nanosheets. This novel 2DLM exhibits excellent nanofiltration performance (69 L m -2 h -1 bar -1 permeance with 93.6% rejection for MB) and can be recycled at least 30 times without significant degradation. The 2DLM exhibits excellent swelling resistance at high salinity, with a demonstration of selective enrichment of uranyl carbonate from artificial water and natural seawater. The results provide a new strategy for constructing highly stable 2DLMs with interlayer spacing controllable from sub-nano to nanometer scales, for size-selective sieving of molecules and ions, high-efficiency nanofiltration, and other applications., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Small-scale soft robots are attracting increasing interest for visible and potential applications owing to their safety and tolerance resulting from their intrinsic soft bodies or compliant structures. However, it is not sufficient that the soft bodies merely provide support or system protection. More importantly, to meet the increasing demands of controllable operation and real-time feedback in unstructured/complicated scenarios, these robots are required to perform simplex and multimodal functionalities for sensing, communicating, and interacting with external environments during large or dynamic deformation with the risk of mismatch or delamination. Challenges are encountered during fabrication and integration, including the selection and fabrication of composite/materials and structures, integration of active/passive functional modules with robust interfaces, particularly with highly deformable soft/stretchable bodies. Here, methods and strategies of fabricating structural soft bodies and integrating them with functional modules for developing small-scale soft robots are investigated. Utilizing templating, 3D printing, transfer printing, and swelling, small-scale soft robots can be endowed with several perceptual capabilities corresponding to diverse stimulus, such as light, heat, magnetism, and force. The integration of sensing and functionalities effectively enhances the agility, adaptability, and universality of soft robots when applied in various fields, including smart manufacturing, medical surgery, biomimetics, and other interdisciplinary sciences., (© 2022 Wiley-VCH GmbH.)

Metal organic frameworks (MOFs) are a distinct family of crystalline porous materials finding extensive applications. Their synthesis often requires elevated temperature and relatively long reaction time. We report here the first case of MOF synthesis activated by high-energy (1.5 MeV) electron beam radiation from a commercially available electron-accelerator. Using ZIF-8 as a representative for demonstration, this type of synthesis can be accomplished under ambient conditions within minutes, leading to energy consumption about two orders of magnitude lower than that of the solvothermal condition. Interestingly, by controlling the absorbed dose in the synthesis, the electron beam not only activates the formation reaction of ZIF-8, but also partially etches the material during the synthesis affording a hierarchical pore architecture and highly crystalline ZnO nanoparticles on the surface of ZIF-8. This gives rise to a new strategy to obtain MOF@metal oxide heterostructures, finding utilities in photocatalytic degradation of organic dyes., (© 2022 Wiley-VCH GmbH.)

The coordination chemistry of f-block elements (lanthanide and actinide) in molten salts has become a resounding topic in view of its great importance to the research and development (R&D) of molten salt reactors and pyroprocessing. In this Review article, a general overview of the coordination chemistry of f-block elements in molten salts is provided including past achievements and recent advances. Particular emphases are placed on the oxidation state, speciation, and solution structure of f-block metal ions in molten salts, as well as their relationships with the salt composition. Furthermore, this review briefly discusses the spectroscopic and theoretical methods that complement each other in revealing the coordination properties., (© 2022 Wiley-VCH GmbH.)

Scintillators display radioluminescent properties when irradiated by high-energy photons and therefore play an essential role in radiation detection. The current inventory of scintillators is overwhelmingly represented by achiral structures, where the radioluminescence propagates isotropically after generation. Herein, we demonstrate that chiral perovskites of (R-3AP)PbBr 3 Cl⋅H 2 O (R-3APP) and (S-3AP)PbBr 3 Cl⋅H 2 O (S-3APP) emerge as a new type of scintillator displaying a distinct property of circularly polarized radioluminescence (CPRL). A high quantum yield of 27.6 %, high luminescence dissymmetric factors (g lum ) of 4×10 -2 , and high X-ray absorption coefficients were observed for these compounds. As proof of concept, we fabricated a polarized scintillator pair by assembling chiral scintillator crystals, which provides a new strategy to attenuate optical crosstalk between the scintillators by precisely controlling the radioluminescence propagation and improves the X-ray imaging quality at the boundary region., (© 2022 Wiley-VCH GmbH.)

The semiconductor based photocatalysis has become a hot spot of current research, and the key challenges are the construction of strong functional heterojunction photocatalysts, and insights on the working mechanism involved. In this work, we constructed a NiFe- LDHs/P-TCN heterojunction with P-dopant defects and interface synergy and elucidated its mesoscale mechanism among different constituent interfaces. The interface photoelectron transfer was detected by PAS, EPR and other methods, and the enhancing mechanism of the defect sites for interface electron transfer and photocatalytic activity was proposed. The interfacial electrons, photoelectric properties and photocatalytic activity are found to be positively correlated. The result is conducive for a better understanding on working mechanism of heterogeneous photocatalysts, which opened a broader research space for the rational design and construction of functional interfaces., (© 2022 Wiley-VCH GmbH.)

AlCl 3 -NaCl was utilized as an electrolyte in this work due to its low melting point and Lewis acidity, in which samarium exists in two oxidation states, Sm(III) and Sm(II), resulting in unique electrochemical behaviours. Sm metal dissolves in AlCl 3 -NaCl melt to form SmCl 2 , which is verified by electrochemical and spectroscopic techniques. As the Lewis acidity of the melt increases, the diffusion coefficient of Sm(II) gradually increases, and the activation energy of diffusion decreases. Moreover, an additional co-reduction peak of Sm 3+ and AlCl 4 - is observed to be more positive than that of Al(0)/Al(III) in Lewis basic melt, which may be tightly correlated with the variation of Sm(II) coordination in AlCl 3 -NaCl melt and ligand variation from Cl - to AlCl 4 - and Al 2 Cl 7 - as the Lewis acidity of the AlCl 3 -NaCl melt increases, according to the in situ electronic absorption spectra of Sm in this melt., (© 2022 Wiley-VCH GmbH.)

Dry reforming of methane (DRM) has provided an effective avenue to convert two greenhouse gases, CH 4 and CO 2 , into syngas. Here, we design a DRM photocatalyst Rh/Ce x WO 3 that invokes both photothermal and photoelectric processes, which overcomes the thermodynamic limitation of DRM under conventional conditions. In contrast to plasmonic or UV-response photocatalysts, our photocatalyst produces a superior light-to-chemical energy efficiency (LTCEE) of 4.65 % with a moderate light intensity. We propose that a light-induced metal-to-metal charge transfer plays a crucial role in the DRM reaction, which induces a redox looping between Ce to W species to lower the activation energy. Quantum mechanical studies reveal that a high oxygen mobility of Ce x WO 3 , accompanied with the formation of oxo-bridge species, results in a substantial elimination of deposited C species during the reaction. Our catalyst design strategy could offer a promising energy-efficient industrial process for DRM., (© 2022 Wiley-VCH GmbH.)

Although the reaction chemistry of transition metallacyclopropenes has been well-established in the last decades, the reactivity of rare-earth metallacyclopropenes remains elusive. Herein, we report the reaction of lutetacyclopropene 1 toward a series of unsaturated molecules. The reaction of 1 with one equiv. of PhCOMe, Ar 1 CHO (Ar 1 =2,6-Me 2 C 6 H 3 ), W(CO) 6 , and PhCH=NPh provided oxalutetacyclopentenes, metallacyclic lutetoxycarbene, and azalutetacyclopentene via 1,2-insertion of C=O, C≡O, or C=N bonds into Lu-C sp2 bond, respectively. However, the reaction between 1 and Ar 2 N=C=NAr 2 (Ar 2 =4-MeC 6 H 4 ) gave an acyclic lutetium complex with a diamidinate ligand by the coupling of one molecule of 1 with two carbodiimides, irrespective of the amount of carbodiimide employed. More interestingly, when 1 was treated with two equiv. of Ar 1 CHO, the reductive coupling of two C=O bonds was discovered to give a lutetium pinacolate complex along with the release of tolan. Remarkably, the reactivity of 1 is significantly different from that of scandacyclopropenes; these metallacycles derived from 1 all represent the first cases in rare-earth organometallic chemistry., (© 2021 Wiley-VCH GmbH.)

Measuring the changes in tumor cell surface temperature can provide insights into cellular metabolism and pathological features, which is significant for targeted chemotherapy and hyperthermic therapy. However, conventional micro-nano scale methods are invasive and can only measure the temperature of cells across a single plane, which excludes specific organelles. In this study, fluorescence quantum dots (QDs) are functionalized with the membrane transport protein transferrin (Tf) as a thermo-sensor specific for tumor cell membrane. The covalent conjugation is optimized to maintain the relative fluorescence intensity of the Tf-QDs to >90%. In addition, the Tf-QDs undergo changes in the fluorescence spectra as a function of temperature, underscoring its thermo-sensor function. Double helix point spread function imaging optical path is designed to locate the probe at nanoscale, and 3D thermal imaging technology is proposed to measure the local temperature distribution and direction of heat flux on the tumor cell surface. This novel targeted nanoscale 3D thermometry method can be a highly promising tool for measuring the local and global temperature distribution across intracellular organelles., (© 2021 Wiley-VCH GmbH.)

Luminescent covalent organic frameworks (COFs) find promising applications in chemical sensing, photocatalysis, and optoelectronic devices, however, the majority of COFs are non or weakly emissive owing to the aggregation-caused quenching (ACQ) or the molecular thermal motion-based energy dissipation. Here, we report a previously unperceived approach to improve luminescence performance of COFs by introducing isotope effect, which is achieved through substitution of hydrogen from high-frequency oscillators X-H (X=O, N, C) by heavier isotope deuterium. Combining the "bottom-up" and in situ deuteration methods generates the first deuterated COF, which exhibits an impressively 19-fold enhancement in quantum yield over that of the non-deuterated counterpart. These results are interpreted by theoretical calculations as the consequence of slower C/N-D and OD⋅⋅⋅O vibrations that impede the nonradiative deactivation process. The proposed strategy is proved applicable to many other types of emissive COFs., (© 2021 Wiley-VCH GmbH.)

Molten salt electrolysis is a vital technique to produce high-purity lanthanide metals and alloys. However, the coordination environments of lanthanides in molten salts, which heavily affect the related redox potential and electrochemical properties, have not been well elucidated. Here, the competitive coordination of chloride and fluoride anions towards lanthanide cations (La 3+ and Nd 3+ ) is explored in molten LiCl-KCl-LiF-LnCl 3 salts using electrochemical, spectroscopic, and computational approaches. Electrochemical analyses show that significant negative shifts in the reduction potential of Ln 3+ occur when F - concentration increases, indicating that the F - anions interact with Ln 3+ via substituting the coordinated Cl - anions, and confirm [LnCl x F y ] 3-x-y (y max =3) complexes are prevailing in molten salts. Spectroscopic and computational results on solution structures further reveal the competition between Cl - and F - anions, which leads to the formation of four distinct Ln(III) species: [LnCl 6 ] 3- , [LnCl 5 F] 3- , [LnCl 4 F 2 ] 3- and [LnCl 4 F 3 ] 4- . Among them, the seven-coordinated [LnCl 4 F 3 ] 4- complex possesses a low-symmetry structure evidenced by the pattern change of Raman spectra. After comparing the polarizing power (Z/r) among different metal cations, it was concluded that Ln-F interaction is weaker than that between transition metal and F - ions., (© 2021 Wiley-VCH GmbH.)

Zeolites are a well-known family of microporous aluminosilicate crystals with a wide range of applications. Their industrial synthetic method under hydrothermal condition requires elevated temperature and long crystallization time and is therefore quite energy-consuming. Herein, we utilize high-energy electron beam irradiation generated by an industrial accelerator as a distinct type of energy source to activate the formation reaction of Na-A zeolite. The initial efforts afford an attractive reaction process that can be achieved under ambient conditions and completed within minutes with almost quantitative yield, leading to notable energy saving of one order of magnitude compared to the hydrothermal reaction. More importantly, electron beam irradiation simultaneously exhibits an etching effect during the formation of zeolite generating a series of crystal defects and additional pore windows that can be controlled by irradiation dose. These observations give rise to significantly enhanced surface area and heavy metal removal capabilities in comparison with Na-A zeolite synthesized hydrothermally. Finally, we show that this method can be applied to many other types of zeolites., (© 2021 Wiley-VCH GmbH.)

Although oxygen vacancies (O v s) play a critical role for many applications of metal oxides, a controllable synthetic strategy for anisotropic O v s remains a great challenge. Here, a novel strategy is proposed to achieve the regional dual structure with anisotropic O v s at both the surface and in the interior of TiO 2 by constructing amorphous domains. The as-prepared black TiO 2 with amorphous domains exhibits superior activity in degrading rhodamine B (RhB) solutions, which can instantly decompose RhB with just a shake. First-principle simulations reveal that subsurface O v s in TiO 2 are energetically favored, resulting in the formation of amorphous domains in the interior region via diffusion of surface-formed O v s into the subsurface. The stable O v -induced amorphous domains in TiO 2 with enhanced catalytic performances provide a scalable strategy to practical O v engineering in functional metal oxides., (© 2021 Wiley-VCH GmbH.)

Ferroelectrics have been demonstrated as excellent building blocks for high-performance nonvolatile memories, including memristors, which play critical roles in the hardware implementation of artificial synapses and in-memory computing. Here, it is reported that the emerging van der Waals ferroelectric α-In 2 Se 3 can be used to successfully implement heterosynaptic plasticity (a fundamental but rarely emulated synaptic form) and achieve a resistance-switching ratio of heterosynaptic memristors above 10 3 , which is two orders of magnitude larger than that in other similar devices. The polarization change of ferroelectric α-In 2 Se 3 channel is responsible for the resistance switching at various paired terminals. The third terminal of α-In 2 Se 3 memristors exhibits nonvolatile control over channel current at a picoampere level, endowing the devices with picojoule read-energy consumption to emulate the associative heterosynaptic learning. The simulation proves that both supervised and unsupervised learning manners can be implemented in α-In 2 Se 3 neutral networks with high image recognition accuracy. Moreover, these heterosynaptic devices can naturally realize Boolean logic without an additional circuit component. The results suggest that van der Waals ferroelectrics hold great potential for applications in complex, energy-efficient, brain-inspired computing systems and logic-in-memory computers., (© 2021 Wiley-VCH GmbH.)

We disclose the intrinsic semiconducting properties of one of the largest mixed-valent uranium clusters, [H 3 O + ][U V (U VI O 2 ) 8 (μ 3 -O) 6 (PhCOO) 2 (Py(CH 2 O) 2 ) 4 (DMF) 4 ] (Ph=phenyl, Py=pyridyl, DMF=N,N-dimethylformamide) (1). Single-crystal X-ray crystallography demonstrates that U V center is stabilized within a tetraoxo core surrounded by eight uranyl(VI) pentagonal bipyramidal centers. The oxidation states of uranium are substantiated by spectroscopic data and magnetic susceptibility measurement. Electronic spectroscopy and theory corroborate that U V species serve as electron donors and thus facilitate 1 being a n-type semiconductor. With the largest effective atomic number among all reported radiation-detection semiconductor materials, charge transport properties and photoconductivity were investigated under X-ray excitation for 1: a large on-off ratio of 500 and considerable charge mobility lifetime product of 2.3×10 -4  cm 2  V -1 , as well as a high detection sensitivity of 23.4 μC Gy air -1  cm -2 ., (© 2021 Wiley-VCH GmbH.)

Splitting of alcohols into hydrogen and corresponding carbonyl compounds, also called acceptorless alcohol dehydrogenation, is of great significance for both synthetic chemistry and hydrogen production. Light-Driven Alcohol Splitting (LDAS) by heterogeneous photocatalysis is a promising route to achieve such transformations, and it possesses advantages including high selectivity of the carbonyl compounds, extremely mild reaction conditions (room temperature and irradiation of visible light) and easy separation of the photocatalysts from the reaction mixtures. Because a variety of alcohols can be derived from biomass, LDAS can also be regarded as one of the most sustainable approaches for hydrogen production. In this Review, recent advances in the LDAS catalyzed by the heterogeneous photocatalysts are summarized, focusing on the mechanistic insights for the LDAS and aspects that influence the performance of the photocatalysts from viewpoints of metallic co-catalysts, semiconductors, and metal/semiconductor interfaces. In addition, challenges and prospects have been discussed in order to present a complete picture of this field., (© 2021 The Authors. Chemistry - An Asian Journal published by Wiley-VCH GmbH.)

Six hybrid uranyl-transition metal compounds [UO 2 Ni(cptpy) 2 (HCOO) 2 (DMF)(H 2 O)] (1), [UO 2 Ni(cptpy) 2 (BTPA) 2 ] (2), [UO 2 Fe(cptpy) 2 (HCOO) 2 (DMF)(H 2 O)] (3), [UO 2 Fe(cptpy) 2 (BTPA) 2 ] (4), [UO 2 Co(cptpy) 2 (HCOO) 2 (DMF)(H 2 O)] (5), and [UO 2 Co(cptpy) 2 (BTPA) 2 ] (6), based on bifunctional ligand 4'-(4-carboxyphenyl)-2,2':6',2''-terpyridine (Hcptpy) are reported (H 2 BTPA = 4,4'-biphenyldicarboxylic acid). Single-crystal XRD revealed that all six compounds feature similar metalloligands, which consist of two cptpy - anions and one transition metal cation. The metalloligand M(cptpy) 2 can be considered to be an extended linear dicarboxylic ligand with length of 22.12 Å. Compounds 1, 3, and 5 are isomers, and all of them feature 1D chain structures. The adjacent 1D chains are connected together by hydrogen bonds and π-π interactions to form a 3D porous structure, which is filled with solvent molecules and can be exchanged with I 2 . Compounds 2, 4, and 6 are also isomers, and all of them feature 2D honeycomb (6,3) networks with hexagonal units of dimensions 41.91×26.89 Å, which are the largest among uranyl compounds with honeycomb networks. The large aperture allows two sets of equivalent networks to be entangled together to result in a 2D+2D→3D polycatenated framework. Remarkably, these uranyl compounds exhibit high catalytic activity for cycloaddition of carbon dioxide. Moreover, the geometric and electronic structures of compounds 1 and 2 are systematically discussed on the basis of DFT calculations., (© 2020 Wiley-VCH GmbH.)

The development of the uranyl cation as a powerful photocatalyst is seriously delayed in comparison with the advances in its fundamental and structural chemistry. However, its characteristic high oxidative capability in the excited state ([UO 2 ] 2+ * (+2.6 V vs. SHE; SHE=standard hydrogen electrode) combined with blue-light absorption (hv=380-500 nm) and a long-lived fluorescence lifetime up to microseconds have reveals that the uranyl cation approaches an ideal photocatalyst for visible-light-driven organic transformations. Described herein is the successful use of uranyl nitrate as a photocatalyst to enable C(sp 3 )-H activation and C-C bond formation through hydrogen atom transfer (HAT) under blue-light irradiation. In particular, this operationally simple strategy provides an appropriate approach to the synthesis of diverse and valuable diarylmethane motifs. Mechanistic studies and DFT calculations have provided insights into the detailed mechanism of the photoinduced HAT pathway. This research suggests a general platform that could popularize promising uranyl photocatalytic performance., (© 2020 Wiley-VCH GmbH.)

Radio-photoluminescence (RPL) materials display a distinct radiation-induced permanent luminescence center, and therefore find application in the detection of ionizing radiation. The current inventory of RPL materials, which were discovered by serendipity, has been limited to a small number of metal-ion-doped inorganic materials. Here we document the RPL of a metal-organic framework (MOF) for the first time: X-ray induced free radicals are accumulated on the organic linker and are subsequently stabilized in the conjugated fragment in the structure, while the metal center acts as the X-ray attenuator. These radicals afford new emission features in both UV-excited and X-ray excited luminescence spectra, making it possible to establish linear relationships between the radiation dose and the normalized intensity of the new emission feature. The MOF-based RPL materials exhibit advantages in terms of the dose detection range, reusability, emission stability, and energy threshold. Based on a comprehensive electronic structure and energy diagram study, the rational design and a substantial expansion of candidate RPL materials can be anticipated., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Semiconductive metal-organic frameworks (MOFs) have emerged in applications such as chemical sensors, electrocatalysts, energy storage materials, and electronic devices. However, examples of semiconductive MOFs within flexible electronics have not been reported. We present flexible X-ray detectors prepared by thermoplastic dispersal of a semiconductive MOF (SCU-13) through a commercially available polymer, poly(vinylidene fluoride). The flexible detectors exhibit efficient X-ray-to-electric current conversion with enhanced charge-carrier mobility and low trap density compared to pelleted devices. A high X-ray detection sensitivity of 65.86 μCGy air -1  cm -2 was achieved, which outperforms other pelleted devices and commercial flexible X-ray detectors. We demonstrate that the MOF-based flexible detectors can be operated at multiple bending angles without a deterioration in detection performance. As a proof-of-concept, an X-ray phase contrast under bending conditions was constructed using a 5×5 pixelated MOF-based imager., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Platinum (Pt) drugs are widely used in anti-cancer treatment although many reports advocated that tumor cells could inactivate Pt drugs via glutathione-Pt (GSH-Pt) adducts formation. To date, GSH chelated Pt molecules have not been assessed in cancer treatment because GSH-Pt adducts are not capable of killing cancer cells, which is widely accepted and well followed. In this report, endogenous biothiol is utilized to precisely synthesize a GSH chelated Pt molecule (Pt 6 GS 4 ). This Pt 6 GS 4 molecule can be well taken up by aggressive triple negative breast cancer (TNBC) cells. Subsequently, its metabolites could enter nuclei to interact with DNA, finally the DNA-Pt complex triggers TNBC cell apoptosis via the p53 pathway. Impressively, high efficacy for anti-cancer treatment is achieved by Pt 6 GS 4 both in vitro and in vivo when compared with traditional first-line carboplatin in the same dosage. Compared with carboplatin, Pt 6 GS 4 keeps tumor bearing mice alive for a longer time and is non-toxic for the liver and kidneys. This work opens a route to explore polynuclear Pt compound with accurate architecture for enhancing therapeutic effects and reducing systemic toxicity., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Printing of electronics has been receiving increasing attention from academia and industry over the recent years. However, commonly used printing techniques have limited resolution of micro- or sub-microscale. Here, a directed-assembly-based printing technique, interfacial convective assembly, is reported, which utilizes a substrate-heating-induced solutal Marangoni convective flow to drive particles toward patterned substrates and then uses van der Waals interactions as well as geometrical confinement to trap the particles in the pattern areas. The influence of various assembly parameters including type of mixing solvent, substrate temperature, particle concentration, and assembly time is investigated. The results show successful assembly of various nanoparticles in patterns of different shapes with a high resolution down to 25 nm. In addition, the assembly only takes a few minutes, which is two orders of magnitude faster than conventional convective assembly. Small-sized (diameter below 5 nm) nanoparticles tend to coalesce during the assembly process and form sintered structures. The fabricated silver nanorods show single-crystal structure with a low resistivity of 8.58 × 10 -5 Ω cm. With high versatility, high resolution, and high throughput, the interfacial convective assembly opens remarkable opportunities for printing next generation nanoelectronics and sensors., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Scintillators are a unique class of luminescent materials with specific applications towards radiation detection. The emitters within state-of-the-art scintillators are mostly limited to bismuth, cerium, europium, thallium, lead, tungsten, etc. A shared feature of these elements is the relatively high atomic number, which is responsible for high radiation stopping power and radiation-induced luminescence. Searching for new scintillating materials is an essential target aiming at specific applications. In this Concept article, we will discuss our recent works on the topic of "uranyl-bearing scintillators". As a virgin territory in this field, uranyl-bearing scintillators show intrinsic merits for designing new materials with X-ray detection capability, that is, the large photoelectric cross-section, high X-ray attenuation efficiency, and high crystal density. In addition, we also present challenges in the further development of the uranyl-bearing scintillators., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Mechanoluminescence (ML) and room-temperature photophosphorescence (RTP) were achieved in polymorphisms of a triphenylamine derivative with ortho-substitution. This molecular packing-dependent emission afforded crucial information to deeply understand the intrinsic mechanism of different emission forms and the possible packing-function relationship. With the incorporation of solid-state 13 C NMR spectra of single crystals, as well as the analysis of crystal structures, the preferred packing modes for ML and/or RTP were investigated in detail, which can guide the reasonable design of organic molecules with special light-emission properties., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Designability is an attractive feature for metal-organic frameworks (MOFs) and essential for reticular chemistry, and many ideas are significantly useful in the carboxylate system. Bi-, tri-, and tetra-topic phosphonate ligands are used to achieve framework structures. However, an efficient method for designing phosphonate MOFs is still on the way, especially for uranyl phosphonates, owing to the complicated coordination modes of the phosphonate group. Uranyl phosphonates prefer layer or pillar-layered structures as the topology extension for uranyl units occurs in the plane perpendicular to the linear uranium-oxo bonds and phosphonate ligands favor the formation of compact structures. Therefore, an approach that can construct three-dimensional (3D) uranyl phosphonate MOFs is desired. In this paper, a sterically hindered phosphonate ligand method (SHPL) is described and is successfully used to achieve 3D framework structures of uranyl phosphonates. Four MOF compounds ([AMIM] 2 (UO 2 )(TppmH 4 )⋅H 2 O (UPF-101), [BMMIM] 2 (UO 2 ) 3 (TppmH 4 ) 2 ⋅H 2 O (UPF-102), [Py14] 2 (UO 2 ) 3 (TppmH 4 ) 2 ⋅3 H 2 O (UPF-103), and [BMIM](UO 2 ) 3 (TppmH 3 )F 2 ⋅2 H 2 O (UPF-104); [AMIM]=1-allyl-3-methylimidazolium, [BMMIM]=1-butyl-2,3-dimethylimidazolium, [Py14]=N-butyl-N-methylpyrrolidinium, and [BMIM]=1-butyl-3-methylimidazolium) are obtained by ionothermal synthesis, with zero-dimensional nodes of uranyl phosphonates linked by steric tetra-topic ligands, namely tetrakis[4-(dihyroxyphosphoryl)phenyl]methane (TppmH 8 ), to give 3D framework structures. Characterization by PXRD, UV/Vis, IR, Raman spectroscopy, and thermogravimetry (TG) were also performed., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

99 Tc contamination at legacy nuclear sites is a serious and unsolved environmental issue. The selective remediation of 99 TcO 4 - in the presence of a large excess of NO 3 - and SO 4 2- from natural waste systems represents a significant scientific and technical challenge, since anions with a higher charge density are often preferentially sorbed by traditional anion-exchange materials. We present a solution to this challenge based on a stable cationic metal-organic framework, SCU-102 (Ni 2 (tipm) 3 (NO 3 ) 4 ), which exhibits fast sorption kinetics, a large capacity (291 mg g -1 ), a high distribution coefficient, and, most importantly, a record-high TcO 4 - uptake selectivity. This material can almost quantitatively remove TcO 4 - in the presence of a large excess of NO 3 - and SO 4 2- . Decontamination experiments confirm that SCU-102 represents the optimal Tc scavenger with the highest reported clean-up efficiency, while first-principle simulations reveal that the origin of the selectivity is the recognition of TcO 4 - by the hydrophobic pockets of the structure., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)