Stepwise Post-Modification of Pyridine-Imine COFs for Enhanced Hydrolytic Stability and Proton Conductivity.

Emerging as a type of promising material for proton conduction, covalent organic frameworks (COFs) assembled from dynamic imine bonds face a challenge of surmounting hydrolytic instability to achieve long-term performance in humid environments. In this work, we report a post-synthetic strategy to simultaneously enhance the hydrolytic stability and hydrophilicity of a pyridine-imine-based COF, COF-LIFM7, without compromising its crystallinity and porosity. A bifunctional monomer containing amino and acetal groups was employed to construct the primary framework, which was subsequently modified via amide formation and pyridine N-oxidation to yield COF-LIFM7-Amide and COF-LIFM7-Amide-NO.

Merging One- and Multi-Photon Processes in Hydrogen-Bonded Organic Frameworks for Enhanced NIR Light-Driven Photothermal and Photochemical Conversions.

Direct application of near-infrared (NIR) light for solar-thermal and solar-chemical conversions is of emergent interest to improving efficiency in solar-energy utilization. Herein, we report a synthetic approach to NIR-responsive materials by self-assembly of hydrogen-bonded organic frameworks (HOF-1/2/3) from multifunctionalized Ru-components incorporating chiral, photoactive, H-bonding, π-stacking, and protonation/deprotonation subunits. Significantly, protonation of the imidazole-subunits in HOF-3 promotes densified packing to extend NIR absorption tail up to 1100 nm with a narrowed bandgap of 1.

Hot Interband Carrier Exploitation in a Ru/MOF Schottky Junction for Photocatalytic CO Reduction.

Visible light-driven photocatalytic reduction of CO to value-added fuels and chemicals has attracted extensive interest for decades. However, the emerging photocatalysis paradigm through an interband transition in non-plasmonic metals remains challenging. Herein, a new strategy, namely hot carrier exploitation is demonstrated, for highly efficient CO reduction through the interband transition in non-plasmonic Ru nanoparticles (NPs).

Twist-Promoted Photoredox Catalysis in Metal-Organic Framework for Defluorination Reactions.

The relatively short excited-state lifetime is one main drawback of organic photosensitizers, resulting in their restricted catalytic capability and high catalyst loadings. We herein report the design of a twisted ligand N,N,N,N-tetrakis[(1,1'-biphenyl)-4-carboxylic acid]-9,10-anthracene diamine (HTCPDA). Its twisted geometry significantly elongates the lifetime of charge-transfer state as substantiated by detailed ultrafast transient absorption (TA) spectroscopic and electrochemical studies.

Optimizing Pore Size and Polarity in Halogen-Functionalized Metal-Organic Frameworks for Efficient Xenon/Krypton Separation: A Synergistic Strategy.

High-purity xenon (Xe) is crucial in semiconductor manufacturing and medical imaging, but trace krypton (Kr) in Xe poses a significant challenge in separation due to their highly similar properties. Traditional gas separation methods are ineffective for Xe/Kr, necessitating innovative adsorbent materials. This study proposes an effective strategy using halogen-functionalized ligands to adjust the pore size and polarity in metal-organic framework (MOF) materials, achieving efficient Xe/Kr separation.

Achieving Diverse CO Conversions through On-Demand Installation of Multivariate Catalytic Sites into One Prototypical Metal-Organic Framework.

The programmable design and construction of multirole or swing-role metal-organic frameworks (MR/SR-MOFs) for variable CO conversions are appealing for green and sustainable chemistry. Herein, we describe a facile MR/SR-MOF synthetic strategy for on-demand engineering of the catalytic pore spaces in a primitive MOF for diverse CO chemical fixation. Distinct functional groups can be precisely and quantitively immobilized into prototypical LIFM-28 (-LIFM-28) by virtue of postsynthesis based on its solid-state dynamic attribute, generating different catalytic pore spaces suitable for hydrosilylation, -methylation, cycloaddition, and cyclization reactions of CO.

Synthesis and Modification of Formate Zr-MOF (ZrFA) Toward Scalable and Cost-Cutting Gas Separation.

The mass production of metal-organic frameworks (MOFs) with affordable cost is highly demanding yet limited for commercial applications, e.g., purification of polymer-grade ethylene (CH) via acetylene (CH) and carbon dioxide (CO) removal faces the challenge of developing low-cost and large-scale physisorbents with efficiency and recyclability.

Enantioselective dearomative ortho-cycloaddition transformation of unactivated arenes by cage-confined visible-light photocatalysis.

Photoinduced dearomatization of arenes is a powerful strategy in organic synthesis to disrupt the stable aromaticity; however, the asymmetric dearomatization photocatalysis of unactivated arenes remains highly challenging and rare. Herein we demonstrate an enzyme-mimicking cage-confined visible-light asymmetric photocatalysis method for intramolecular dearomative cycloaddition with electron-deficient β-aryl enones. Owing to the multi-functional synergy of chirality, energy transfer, and host-guest interactions in the confined microenvironments, the self-assembled chiral cage-photoreactor could pre-organize the arenes and activate the β-aryl enones to give stereoselectively fused cyclobutanes through visible-light induced [2 + 2] ortho-cycloaddition.

A Highly Charged Positive Cage Causes Simultaneous Enhancement of Type-II and O-Independent-Type-I Photodynamic Therapy via One-/Two-Photon Stimulation and Tumor Immunotherapy via PANoptosis and Ferroptosis.

To solve the oxygen dependence problem of photodynamic therapy (PDT), it is critical to explore photosensitizers that do not rely on O molecule to generate reactive oxygen species (ROS). Herein, a stable cationic metal-organic cage [Pd(RuL )](BF) (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 O-independent-Type-I PDT.

Ternary Metalation in a Copper-Covalent Organic Framework for Tandem Photocatalytic CO Reduction with High Selectivity.

Developing multifunctional photocatalysts with efficient synergistic effects for selective photocatalytic CO reduction is sought-after yet challenging. Herein, a tandem photocatalytic strategy has been developed through sequential post-synthetic metalation (SPSM) of variable Ru/Co-sites into a trinuclear Cu-based COF, Cu-BPY-COF, to construct a series of tri-metallized covalent-organic frameworks (COFs), Cu-BPY-COF(Ru/Co)-X (X = 1, 2, or 3, corresponding to the Ru:Co molar ratios of 1/39.6, 1/19.

Asymmetric Cascade Photocycloaddition-Acyloin Rearrangement Enabled by Cage-Confined Visible-Light Catalysis.

Enzymatic catalysis in biological systems is characterized by the specific pocket confinement imposed by various protein matrixes, enabling the synthesis of a diverse array of functional biomolecules. Development of new catalysts that incorporate multiple catalytic centers within the enzyme-mimic confined spaces presents a meaningful yet challenging project for synthetic chemists. Here, we present our recent achievement in synthesizing a chiral photosensitive metal-organic cage (cPMOC), -/-MOC-68-Ru, which possesses multiple chiral pockets that can facilitate the visible-light-induced asymmetric cascade intermolecular [2 + 2] cycloaddition/acyloin rearrangement for the first time.

Genome-Wide Identification, Gene Duplication, and Expression Pattern of Gene Family in .

Background: The Niemann-Pick C2 () gene family plays an important role in olfactory communication, immune response, and the recognition of host plants associated with environmental adaptation for insects.

Methods: In this study, we conducted a genomic analysis of the structural characteristics and physicochemical properties of the genes of eleven butterfly species available, focusing on the alpine species, especially , to investigate their duplication and expression patterns.

Results: Our results indicate that a significant expansion of genes was detected in compared to other butterflies; in addition, the expansion of these unevenly distributed chromosome genes was shaped by tandem duplication mediated by transposons.

Ni Single Atoms/Nanoparticles-Decided Spatial Adjustment of Photocatalytic Redox Sites Boosting CO Reduction in HO Vapour.

The kinetics matching of CO reduction and HO oxidation is required in sacrificial agent-free photocatalytic CO reduction. It indicates that the modification engineering on photocatalytic HO oxidation half-reaction except that on photocatalytic CO reduction half-reaction should be equally paid attention, which has been easily ignored in most of the literatures. Herein, Ni single atoms (NiSAs) and nanoparticles (NiNPs) co-loaded Ti-MOF-derived TiO having a flower-like nanosphere microstructure (NiSAs@NPs/TC) was developed for synchronous design of well-defined redox active sites of photocatalytic CO reduction and HO oxidation.

Celebrating the 100th anniversary of Sun Yat-Sen University.

Celebrating the 100th Anniversary of Sun Yat-Sen University (SYSU), this themed collection features 29 recent cutting-edge articles and reviews in organic synthesis, coordination complexes, energy catalysis, functional materials, and biochemistry by SYSU scholars, alumni, and collaborators.

Asymmetric Synthesis of Strained Multichiral Spirocyclobutanes through Cage-Confined Cross [2 + 2] Photocycloaddition.

Chiral spirocycles possess the ability to undergo diverse modifications in three-dimensional space, offering advantages in terms of physicochemical property and structural variability over conventional organic scaffolds and holding promising potential for the design of biologically active molecules and drugs. Among them, highly strained spirocyclobutanes with multiple chiral center-containing four-membered rings have attracted significant attention, but their viable and efficient synthesis poses a great challenge. By virtue of cage-confined asymmetric photocatalysis, we successfully construct spirocycle and bispirocycle compounds containing multiple quaternary and tertiary chiral carbon centers in cyclobutane rings through cross [2 + 2] photocycloaddition with visible-light-induced and mild reactions.

Blue Vane and Pan Traps Are More Effective for Profiling Multiple Facets of Bee Diversity in Subtropical Forests.

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.

Diphosphaenones: beyond the phosphorus analogue of enones.

Phosphaenones, like their carbon analogue enones (C[double bond, length as m-dash]C-C[double bond, length as m-dash]O), are promising building blocks for synthetic chemistry and materials science. However, in contrast to the α- and β-phosphaenones, structurally and spectroscopically well-defined diphosphaenones (DPEs) are rare. In this study, we disclose the isolation and spectroscopic characterization of N-heterocyclic vinyl (NHV) substituted acyclic DPEs 3a,b [NHV-P[double bond, length as m-dash]P-C(O)-NHV].

Unlocking Photocycloaddition Reactivity of Tropolone by Cage-Confined Visible-Light Photocatalysis for Multilevel Selective Transformation.

The precise asymmetric photochemical transformation of organic compounds containing multiple reactive sites presents significant progress in synthetic chemistry. Herein, we report an unprecedented visible-light-induced cascade transformation of tropolone cyclic triene derivatives by using chiral photoactive metal-organic cages (cPMOCs) as enzyme-mimicking multipocket photocatalysts. The cage-confined photocatalysis promotes three successive elementary steps, .

Promoting WLED-Excited High Temperature Long Afterglow by Orthogonally Anchoring Chromophores into 0D Metal-Organic Cages.

Afterglow materials have garnered significant interest due to distinct photophysical characteristics. However, it is still difficult to achieve long afterglow phosphorescence from organic molecules due to aggregation-caused quenching (ACQ) and energy dissipation. In addition, most materials reported so far have long afterglow emission only at room or even low temperatures, and mainly use UV light as an excitation source.

Interspecific and Intraspecific Transcriptomic Variations Unveil the Potential High-Altitude Adaptation Mechanisms of the Butterfly Species.

butterflies have significantly advanced our understanding of biogeography, insect-plant interactions, and other fields of ecology and evolutionary biology. However, to date, little is known about the gene expression patterns related to the high-altitude adaptation of species. In this study, we obtained high-throughput RNA-seq data of 48 adult individuals covering 10 species from 12 localities in China, and deciphered their interspecific and intraspecific expression patterns based on comparative transcriptomic analyses.

Complete mitochondrial genome of Grum-Grshimailo, 1891 (Lepidoptera: Pieridae) from montane region in northwestern China.

Grum-Grshimailo, 1891, is a typical montane butterfly species which occurs on the Qinghai-Tibet Plateau (QTP) and adjacent regions in China. In this study, the complete mitochondrial genome of this species was assembled from data generated by next-generation sequencing. The mitogenome was 15,151 bp in length and comprised 13 protein-coding genes (PCGs), 2 ribosomal RNA genes, 22 transfer RNA genes and a control region.

Multipocket Cage Enables the Binding of High-Order Bulky and Drug Guests Uncovered by MS Methodology.

Achieving high guest loading and multiguest-binding capacity holds crucial significance for advancement in separation, catalysis, and drug delivery with synthetic receptors; however, it remains a challenging bottleneck in characterization of high-stoichiometry guest-binding events. Herein, we describe a large-sized coordination cage (MOC-70-ZnPd) possessing 12 peripheral pockets capable of accommodating multiple guests and a high-resolution electrospray ionization mass spectrometry (HR-ESI-MS)-based method to understand the solution host-guest chemistry. A diverse range of bulky guests, varying from drug molecules to rigid fullerenes as well as flexible host molecules of crown ethers and calixarenes, could be loaded into open pockets with high capacities.

Stereochemical Control of Redox Co/Co-Cages with Switchable Cotton Effects Based on Labile-Static States.

The structural dynamics of artificial assemblies, in aspects such as molecular recognition and structural transformation, provide us with a blueprint to achieve bioinspired applications. Here, we describe the assembly of redox-switchable chiral metal-organic cages Λ/Δ-[Pd(CoL)] and Λ/Δ-[Pd(CoL)]. These isomeric cages demonstrate an on-off chirality logic gate controlled by their chemical and stereostructural dynamics tunable through redox transitions between the labile Co-state and static Co-state with a distinct Cotton effect.