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To solve the oxygen dependence problem of photodynamic therapy (PDT), it is critical to explore photosensitizers that do not rely on O2 molecule to generate reactive oxygen species (ROS). Herein, a stable cationic metal‐organic cage [Pd6(RuLoz3)8](BF4)28 (MOC‐88) that possesses high +28 charges is designed. The cage‐confined positive microenvironment enables efficient generation of hydroxyl radicals and improved yield of the singlet oxygen under one‐/two‐photon excitation, showing excellent performance to concurrently enhance Type‐II and O2‐independent‐Type‐I PDT. Moreover, the effective ROS production and robust lipid peroxidation trigger a series of signaling pathways (inflammasome, cyclic guanosine monophosphate–adenosine monophosphate synthase stimulator of interferon genes, and NF‐κB) to evoke PANoptosis and ferroptosis in tumor cells, enabling MOC‐88 to simultaneously cause the loss of cell membrane integrity, release a series of inflammatory cytokines and damage‐associated molecular patterns, stimulate the maturation and antigen presentation ability of dendritic cells, and ultimately activate T‐cell‐dependent adaptive immunity in vivo to inhibit tumor growth.

The choice of trap in entomological surveys affects the composition of captured insects, though previous comparative studies have been limited in the types of composition measured, and the effects of environmental context. We assessed the sampling bias of several traps commonly used in pollinator monitoring: blue, yellow, and white pan traps, and blue vane traps, towards different taxonomic and functional groups and their efficiency in measuring taxonomic, phylogenetic, and functional diversity. Analyses were performed in monoculture and mixed forests to understand the environmental context of trap efficiency. We found that blue pan traps generally outperformed other types in bee capture and exhibited a preference for Halictidae bees. Blue pan traps yielded the highest species richness and phylogenetic diversity, while blue vane traps captured the highest functional richness. Bias differences were frequently detected in mixed forests compared with monoculture forests. We also found the combination of blue vane and pan traps consistently correlated highest with a complete survey among two-method combinations. Based on our findings, we recommend a combination of blue vane and pan traps to obtain a more comprehensive bee collection in an efficient manner. Additionally, it is crucial to consider habitat type when designing bee trapping protocols to ensure an accurate representation of bee communities.

Abstract Fluoro‐ and chlorofluorocabons (FC/CFCs) are important refrigerants, solvents, and fluoropolymers in industry while being toxic and carrying high global warming potential. Detection and reclamation of FC/CFCs based on adsorption technology with highly selective adsorbents is important to labor safety and environmental protection. Herein, the study reports an integrated method to combine capture, separation, enrichment, and analysis of representative FC/CFCs (chlorodifluoromethane(R22) and 1,1,1,2‐tetrafluoroethane (R134a)) by using the highly stable and porous Zr‐MOF, DUT‐67. Gas adsorption and breakthrough experiments demonstrate that DUT‐67 has high R22/R134a uptake (124/116 cm3 g−1) and excellent R22/R134a/CO2 separation performance (IAST selectivities of R22/CO2 and R134a/CO2 ranging from 51.4 to 33.3, and 31.1 to 25.8), even in rather low concentration and humid conditions. A semi‐quantitative analysis protocol is set up to analyze the low concentrations of R22/R134a based on the high selective R22/R134a adsorption ability, fast adsorption kinetics, water‐resistant utility, facile regeneration, and excellent recyclability of DUT‐67. In situ single‐crystal X‐ray diffraction, theoretical calculations, and in situ diffuse reflectance infrared Fourier transform spectra have been employed to understand the adsorption mechanism. This work may provide a potential adsorbent for purge and trap technique under room temperature, thus promoting the application of MOFs for VOCs sampling and quantitative analysis.

Despite the natural abundance and promising properties of Si, there are few examples of crystalline Si-based catalysts. Here, the authors report an epitaxial growth method to construct Co single atoms on Si for light driven CO2 reduction to syngas.

Monolepta is one of the diverse genera in the subfamily Galerucinae, including 708 species and 6 sub-species worldwide. To explore the information on the mitogenome characteristics and phylogeny of the section “Monoleptites”, especially the genus Monolepta, we obtained the newly completed mitochondrial genomes (mitogenomes) of four Monolepta species using high-throughput sequencing technology. The lengths of these four new mitochondrial genomes are 16,672 bp, 16,965 bp, 16,012 bp, and 15,866 bp in size, respectively. All four mitochondrial genomes include 22 transfer RNA genes (tRNAs), 13 protein-coding genes (PCGs), 2 ribosomal RNA genes (rRNAs), and one control region, which is consistent with other Coleoptera. The results of the nonsynonymous with synonymous substitution rates showed that ND6 had the highest evolution rate, while COI displayed the lowest evolution rate. The substitution saturation of three datasets (13 PCGs_codon1, 13 PCGs_codon2, 13 PCGs_codon3) showed that there was no saturation across all datasets. Phylogenetic analyses based on three datasets (ND1, 15 genes of mitogenomes, and 13 PCGs_AA) were carried out using maximum likelihood (ML) and Bayesian inference (BI) methods. The results showed that mitogenomes had a greater capacity to resolve the main clades than the ND1 gene at the suprageneric and species levels. The section “Monoleptites” was proven to be a monophyletic group, while Monolepta was a non-monophyletic group. Based on ND1 data, the newly sequenced species whose antennal segment 2 was shorter than 3 were split into several clades, while, based on the mitogenomic dataset, the four newly sequenced species had close relationships with Paleosepharia. The species whose antennal segment 2 was as long as 3 were split into two clades, which indicated that the characteristic of “antennal segment 2 as long as 3” of the true “Monolepta” evolved multiple times in several subgroups. Therefore, to explore the relationships among the true Monolepta, the most important thing is to perform a thorough revision of Monolepta and related genera in the future.

Developing high-performance, neutral-media H2-evolution electrocatalysts is important for clean and sustainable hydrogen energy, yet rare, expensive elements are most active. Here, authors show that metal-organic frameworks modified with single ruthenium atoms as high-performances catalysts.

Light-induced [2 + 2] cycloaddition is the most efficient way to generate cyclobutanes, while suffering from limitations of specific selectivity. Here the authors report a cage-confined photocatalytic [2 + 2] cycloaddition to enable the unusual production of syn-head-to-head cyclobutane derivatives selectively.

While water splitting electrocatalysis provides a means to store electrical energy as fuel, the water oxidation catalysts typically show low performances. Here, authors employ metal-organic frameworks with missing-linkers as highly active oxygen evolution electrocatalysts.

Metal–organic frameworks with highly ordered porosity have been studied extensively. In this paper, the effect of framework (pore) disorder on the gas sorption of azole-based isoreticular Cu(II) MOFs with rtl topology and characteristic 1D tubular pore channels is investigated for the first time. In contrast to other isoreticular rtl metal–organic frameworks, the Cu(II) metal–organic framework based on 5-(1H-imidazol-1-yl)isophthalate acid has a crystallographically identifiable disordered framework without open N-donor sites. The framework provides a unique example for investigating the effect of pore disorder on gas sorption that can be systematically evaluated. It exhibits remarkable temperature-dependent hysteretic CO2 sorption up to room temperature, and shows selectivity of CO2 over H2, CH4 and N2 at ambient temperature. The unique property of the framework is its disordered structure featuring distorted 1D tubular channels and DMF-guest-remediated defects. The results imply that structural disorder (defects) may play an important role in the modification of the performance of the material.

Abstract Conspicuously, metal–organic frameworks (MOFs) serve as homogenously and periodically atom‐dispersed self‐sacrificial template for in situ engineering of hierarchical porous carbon‐encapsulated micro/nanoheterostructure materials, integrating the merits of micro/nanostructure to high‐volumetric energy storage. Copper phosphide represents a promising candidate due to its compact material density compared to commercial graphite. Herein, micro/nanostructured Cu3P/Cu encapsulated by carbon‐nanotube‐assembled hierarchical octahedral carbonaceous matrix (Cu3P/Cu@CNHO) is constructed by an in situ MOF‐derived engineering for novel anode material in LIBs, which achieves an extraordinary cycling stability (a well‐maintained gravimetric/volumetric capacity of 463.2 mAh g−1/1878.4 mAh cm−3 at 1 A g−1 up to 1600 cycles) and distinguished rate capability (an ameliorated capacity of 317.7 mAh g−1 even at 10 A g−1), together with unprecedented heat‐resistant capability (an elevated temperature of 50 °C for 1000 cycles maintaining 434.7 mAh g−1 at 0.5 A g−1). The superior electrochemical performance of Cu3P/Cu@CNHO is credited to the large specific surface area, conductive carbon matrix and metallic copper dopants, synergistic effects of the intrinsic Cu3P/Cu heterostructure, and well‐defined micro/nanostructure, facilitating a boosted electrochemical conductivity and accelerated diffusion kinetics.

Two dimensional (2D) metal-organic frameworks have demonstrated unique photophysical properties compared to their bulk analogs. Here, the authors demonstrate that exfoliation of 2D MOFs can suppress interlayer exciton-related emission, allowing for modulation of the overall emission color and switching of optical memory states.

Fast and sensitive detection of water molecules in organic solvents and gases remains an important challenge. Here, Pan and co-workers design a metal-organic framework capable of ultrafast and reversible water sensing by photoluminescence switching via an excited state intramolecular proton transfer mechanism.

Photocatalytic water splitting is a promising route to hydrogen generation from renewable solar power. Here, the authors report a hydrogen-evolving photochemical molecular device based on a self-assembled coordination cage, which simultaneously incorporates multiple photosensitizing and catalytic metal centres.

Homochiral molecular capsules offer potential applications in chiral separation and stereospecific catalysis. Here, by pre-resolution of Δ/Λ-metalloligand precursors, the authors are able to assemble enantiopure supramolecular cages capable of stereoselective host-guest behaviour.

A rare example is reported in which discrete Ag2L2 ring and (AgL)∞ chain motifs [L = N,N′-bis(3-imidazol-1-yl-propyl)-pyromellitic diimide] co-crystallize in the same crystal lattice with varying ratios and degrees of disorder. Crystal structures obtained from representative crystals reveal compatible packing arrangements of the cyclic and polymeric isomers within the crystal lattice, which enables them to co-exist within a crystalline solid solution. A feasible pathway for transformation between the isomers is suggested via facile rotation of the coordinating imidazolyl groups. This chemical system could provide a chance for direct observation of ring-opening isomerization at the crystal surface. Mass spectrometry and 1H NMR titration show a dynamic equilibrium between cyclic and oligomeric species in solution, and a potential crystallization process is suggested involving alignment of precursors directed by aromatic stacking interactions between pyromellitic diimide units, followed by ring-opening isomerization at the interface between the solid and the solution. Both cyclic and oligomeric species can act as precursors, with interconversion between them being facile due to a low energy barrier for rotation of the imidazole rings. Thermogravimetric analysis and variable-temperature powder X-ray diffraction indicate a transition to a different crystalline phase around 120°C, which is associated with loss of solvent from the crystal lattice.

A tetradentate symmetric ligand bearing both coordination and hydrogen bonding sites, N1,N3-bis(1-(1H-benzimidazol-2-yl)-ethylidene)propane-1,3-diamine (H2bbepd) was utilized to synthesize a series of transition metal complexes, namely [Co(H2bbepd)(H2O)2]·2ClO4 (1), [Cu(H2bbepd)(OTs-)]·OTs- (2),[Cu(bbepd)(CH3OH)] (3), [Cd(H2bbepd)(NO3)2]·CH3OH (4), [Cd(H2bbepd)(CH3OH)Cl]·Cl (5), and [Cd(bbepd)(CH3OH)2] (6). These complexes show similar discrete pincer-like coordination units, possessing different arrangements of hydrogen bonding donor and acceptor sites. With or without the aid of uncoordinated anions and solvent molecules, such mononuclear units have been effectively involved in the construction of hierarchical hydrogen bonding assemblies (successively via level I and level II), leading to discrete binuclear ring (complex 2), one-dimensional chain or ribbon (complexes 3, 4 and 6) and two-dimensional layer (complexes 1 and 5) aggregates.

The natural gas upgrading applications involving CH4 purification and concurrent C3H8/n-C4H10 recovery are of great importance yet highly challenging for safe and efficient subsequent manufacturing of downstream commodities due to their similar physicochemical properties and ultra-low concentration. Herein, a robust Zr-MOF, LIFM-233, with optimized pore size/volume/surface ascribed to the introduction of π-electron-rich naphthalene moieties, has been constructed with 6-(4-carboxyphenyl)-2-naphthalenecarboxylate (L) and Zr6 cluster for natural gas upgrading. Based on the high pore volume, optimized pore size, and π-electron-rich pore surface, LIFM-233 presents high C3H8/n-C4H10 uptake capacity (229.3/262.8 cm³ g−1 at 298 K and 1 bar) and good C2–C4/CH4 selective adsorption performance, confirmed by single-component adsorption and dynamic breakthrough experiments. Additionally, high purity of C3H8 (>91.6%) or n-C4H10 (>94.0%) can be afforded through a single regeneration curve. The underlying gas-binding mechanism has been well established by theoretical simulations, which reveal that C–H⋯O hydrogen bonds (HBs) between gas and Zr–O clusters, and C–H⋯π interactions between gas and aromatic rings, collaboratively play pivotal roles in the selective separation of C2–C4 hydrocarbons from CH4, thus demonstrating the importance of the introduction of an appropriate aromatic system. [ABSTRACT FROM AUTHOR]