Spatial Distribution of Nitrogen Binding Sites in Metal-Organic Frameworks for Selective Ethane Adsorption and One-Step Ethylene Purification

The one-step purification of ethylene (C₂H₄) from mixtures containing ethane (C₂H₆) and acetylene (C₂H₂) is an industrially important yet challenging process. In this work, we present a site-engineering strategy aimed at manipulating the spatial distribution of binding sites within a confined pore space. We realized successfully by incorporating nitrogen-containing heterocycles, such as indole-5-carboxylic acid (Ind), benzimidazole-5-carboxylic acid (Bzz), and indazole-5-carboxylic acid (Izo), into the robust MOF-808 platform via post-synthetic modification. The resulting functionalized materials, namely MOF-808-Ind, MOF-808-Bzz, and MOF-808-Izo, demonstrated significantly improved selectivity for C₂H₂ and C₂H₆ over C₂H₄. MOF-808-Bzz with two uniformly distributed nitrogen binding sites gave the optimal geometry for selective ethane trapping through multiple strong C−H⋅⋅⋅N hydrogen bonds, leading to the highest C₂H₂/C₂H₄ and C₂H₆/C₂H₄ combined selectivities among known MOFs. Column breakthrough experiments validated its ability to purify C₂H₄ from ternary C₂H₂/C₂H₄/C₂H₆ mixtures in a single step.     

Back Cover: Metal-Organic Framework Supported Copper Photoredox Catalysts for Iminyl Radical-Mediated Reactions (Angew. Chem. Int. Ed. 21/2023)

Visible-light copper photocatalysis has recently emerged as a viable technology for building sustainable synthetic processes. To broaden the applications of phosphine-ligated copper(I) complexes, we describe herein an effective metal-organic framework (MOF)-supported copper(I) photocatalyst for multiple iminyl radical-mediated reactions. Due to site isolation, the heterogenized copper photosensitizer has a significantly higher catalytic activity than its homogeneous counterpart. Using a hydroxamic acid linker to immobilize copper species on MOF supports affords the heterogeneous catalysts with high recyclability. The post-synthetic modification sequence on MOF surfaces allows for the preparation of previously unavailable monomeric copper species. Our findings highlight the potential of using MOF-based heterogeneous catalytic systems to address fundamental challenges in the development of synthetic methodologies and mechanistic investigations of transition-metal photoredox catalysis.     

Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit

Performance enhancement induced by structural modification has long been the target in materials science fields. Direct evidence to witness the effectivity of one strategy is challenging and necessary. In this work, a tetrahedra-decoration strategy was proposed to improve the birefringent performance sharply, namely decorating the tetrahedra with a single linear [S₂] unit. The strategy was verified by comprehensive characterization of two thiogermanates K₂BaGeS₄ and K₂BaGeS₅, which crystallize in the same space group, have similar unit cells and the same units arrangements. Theoretical characterization verified that the [GeS₅] group has much larger polarization anisotropy than [GeS₄], further demonstrated that the linear [S₂] led to the sharp birefringence enlargement of K₂BaGeS₅ (0.19 vs 0.03 of K₂BaGeS₄). This work provides a new guiding thought to improve the birefringence performance.     

The Alarmone Diadenosine Tetraphosphate as a Cosubstrate for Protein AMPylation

Diadenosine polyphosphates (Ap_nAs) are non-canonical nucleotides whose cellular concentrations increase during stress and are therefore termed alarmones, signaling homeostatic imbalance. Their cellular role is poorly understood. In this work, we assessed Ap_nAs for their usage as cosubstrates for protein AMPylation, a post-translational modification in which adenosine monophosphate (AMP) is transferred to proteins. In humans, AMPylation mediated by the AMPylator FICD with ATP as a cosubstrate is a response to ER stress. Herein, we demonstrate that Ap₄A is proficiently consumed for AMPylation by FICD. By chemical proteomics using a new chemical probe, we identified new potential AMPylation targets. Interestingly, we found that AMPylation targets of FICD may differ depending on the nucleotide cosubstrate. These results may suggest that signaling at elevated Ap₄A levels during cellular stress differs from when Ap₄A is present at low concentrations, allowing response to extracellular cues.     

制备气相色谱仪的改进及应用研究进展

气相色谱已经成为一种常规的分析手段,但以制备为目的的气相色谱的应用还较少.目前尚没有商品化的制备气相色谱仪,需要对传统的分析型气相色谱仪加以改进,以达到高效分离制备目标化合物的目的.本文综述了国内外对制备气相色谱仪改进工作的研究进展,包括汽化室、色谱柱、分流装置、收集系统等的改进.另外,总结了制备气相色谱在各领域的应用...     

A Facile Strategy for the Development of Recyclable Multifunctional Liquid Crystal Polymers via Post-Polymerization Modification and Ring-Opening Metathesis Polymerization

Post-polymerization modification (PPM) offers a versatile approach for engineering multifunctional polymers, but this advantage has not been fully exploited to fabricate multifunctional liquid crystal polymers (LCPs). Here, we design a facile synthetic approach towards multifunctional LCP by combining the ring-opening metathesis polymerization (ROMP) with PPM, in which ROMP helps to prepare a reactive LCP precursor with high molecular weight, and PPM provides a facilitation to introduce functional groups into the precursor. Consequently, a photo- and humidity-responsive linear LCP (LLCP) is demonstrated to show the potential of this synthetic strategy to diversify functions of the LCPs. Under light irradiation and humidity changes, the deformation modes of the LLCP films are converted to complex shapes (bending, twisting, and curling). The obtained dual-responsive LLCP with high molecular weight possesses excellent processability and recyclability, making it possible to construct 3D shape actuators with programmable deformation behaviors under light/humidity.     

Controllable Topological Transformations of 818 Molecular Metalla-knots by Oxidation of Thiazole-Based Ligands

By exploiting coordination-driven self-assembly, high yields of two 8₁₈ molecular metalla-knots could be obtained using a thiazole-moiety-containing asymmetric dipyridyl ligand 2-(pyridin-4-yl)-5-(pyridin-4-ylethynyl)benzo[d]thiazole ( L₁ ), as confirmed using X-ray crystallographic analysis, electrospray ionization-time-of-flight/mass spectrometry (ESI-TOF/MS), and detailed liquid-state nuclear magnetic resonance (NMR) spectroscopy. To modulate the self-assembled structures, m-chloroperbenzoic acid (m-CPBA) was utilized to oxidize thiazole-based ligand L₁ to N-thiazole-oxide-based ligand 2-(pyridin-4-yl)-5-(pyridin-4-ylethynyl)benzo[d]thiazole 3-oxide ( L₂ ), which enabled the selective construction of the corresponding tetranuclear macrocycles. Notably, two molecular metalla-knots could be topologically transformed from 8₁₈ knots to simple monocycles because the L₁ alkyne bond was inert toward m-CPBA, as confirmed by liquid-state NMR spectroscopy, ESI-TOF/MS, and elemental analysis.     

Post-Assembly Modification of Homochiral Titanium–Organic Cages for Recognition and Separation of Molecular Isomers

A chiral metal–organic cage (MOC) was extended and fixed into a porous framework using a post-assembly modification strategy, which made it easier to study the host–guest chemistry of the solid-state MOC using a single-crystal diffraction technique. Anionic Ti₄L₆ (L=embonate) cage can be used as a 4-connecting crystal engineering tecton, and its optical resolution was achieved, thus homochiral ΔΔΔΔ- and ΛΛΛΛ-[Ti₄L₆] cages were obtained. Accordingly, a pair of homochiral cage-based microporous frameworks ( PTC-236(Δ) and PTC-236(Λ) ) were easily prepared by a post-assembly reaction. PTC-236 has rich recognition sites provided by the Ti₄L₆ moieties, chiral channels and high framework stability, affording a single-crystal-to-single-crystal transformation for guest structure analyses. Thus it was successfully utilized for the recognition and separation of isomeric molecules. This study provides a new approach for the orderly combination of well-defined MOCs into functional porous frameworks.     

Tunable Fluorescence from 2D Assemblies of LnW10 and P2W18 Polyoxometalates Clusters with Quaternary Ammonium-type AIEgens

Two-dimensional (2D) AIE-inorganic nanocomposites exhibit high stability and high fluorescence activity. However, limited by the types and properties of 2D inorganic materials, it's challenging to realize complex structures and functions. We designed a quaternary ammonium-type AIE ligand, TPECholine. We chose TPECholine and POM clusters as building blocks and synthesized a series of single-layer nanosheets (SLNSs) by assembling LnW₁₀ or P₂W₁₈ POM clusters with TPECholine. By regulating the types of POM clusters and ligands, the morphology and fluorescence intensity of the SLNSs can be finely tuned. Due to the restriction of the intramolecular motions of AIEgens by the SLNSs, nanosheets can exhibit promoted quantum yield (up to 76 %). In addition, thanks to the sub-nanometric sizes and excess surface charges, SLNSs exhibit excellent solvent compatibility, including water, chloroform, ethanol, etc. And the nanosheets showed high fluorescence intensity in these solvents.     

Chemoenzymatic Late-Stage Modifications Enable Downstream Click-Mediated Fluorescent Tagging of Peptides

Aromatic prenyltransferases from cyanobactin biosynthetic pathways catalyse the chemoselective and regioselective intramolecular transfer of prenyl/geranyl groups from isoprene donors to an electron-rich position in these macrocyclic and linear peptides. These enzymes often demonstrate relaxed substrate specificity and are considered useful biocatalysts for structural diversification of peptides. Herein, we assess the isoprene donor specificity of the N1-tryptophan prenyltransferase AcyF from the anacyclamide A8P pathway using a library of 22 synthetic alkyl pyrophosphate analogues, of which many display reactive groups that are amenable to additional functionalization. We further used AcyF to introduce a reactive moiety into a tryptophan-containing cyclic peptide and subsequently used click chemistry to fluorescently label the enzymatically modified peptide. This chemoenzymatic strategy allows late-stage modification of peptides and is useful for many applications.