磁性复合材料在固相萃取食品中环境类雌激素的应用进展EI北大核心CSCD

环境类雌激素作为食品中一类典型的污染物,严重影响人体内分泌系统的功能与代谢。磁性固相萃取因其简洁高效、富集倍数高、适用范围广等优点,已被广泛应用于食品中环境类雌激素的富集检测。Fe_(3)O_(4)纳米粒子作为经典的磁固相萃取材料,易于形成大分子团聚物,影响其选择吸附性能,限制了磁固相萃取技术在食品中环境类雌激素的痕量分析。新兴的磁性复合材料可有效地解决上述问题,已成为磁固相萃取技术的研究热点之一。本文综述了近5年来新兴的磁性聚合物复合材料、磁性碳基复合材料和磁性金属-有机骨架复合材料在食品中环境类雌激素富集检测的应用进展。     

羧酸类金属有机框架材料的合成及应用

金属-有机框架材料(Metal-Organic?Frameworks,简称MOFs)是由金属离子（簇）与有机桥接配体通过配位共价键或弱相互作用自组装形成的一类具有分子内孔隙的有机-无机杂化材料。羧酸类MOFs材料中金属中心和有机羧酸配体的可变性导致了其结构和功能的多样性,在气体的吸附与分离、荧光、传感、药物传输以及电催化等多个领域展现了独特的应用前景,并被认为是当今科学上最有前途的材料之一。对于有机配体的选择,从早期易坍塌的含氮杂环类配体过渡到了如今稳定性好的羧酸类配体,解决了不少以前出现的MOFs材料结构单一易坍塌问题。     

Enhancing Built-in Electric Fields for Efficient Photocatalytic Hydrogen Evolution by Encapsulating C60 Fullerene into Zirconium-Based Metal-Organic Frameworks

High-efficiency photocatalysts based on metal-organic frameworks (MOFs) are often limited by poor charge separation and slow charge-transfer kinetics. Herein, a novel MOF photocatalyst is successfully constructed by encapsulating C₆₀ into a nano-sized zirconium-based MOF, NU-901. By virtue of host-guest interactions and uneven charge distribution, a substantial electrostatic potential difference is set-up in C₆₀@NU-901. The direct consequence is a robust built-in electric field, which tends to be 10.7 times higher in C₆₀@NU-901 than that found in NU-901. In the catalyst, photogenerated charge carriers are efficiently separated and transported to the surface. For example, photocatalytic hydrogen evolution reaches 22.3 mmol g⁻¹ h⁻¹ for C₆₀@NU-901, which is among the highest values for MOFs. Our concept of enhancing charge separation by harnessing host-guest interactions constitutes a promising strategy to design photocatalysts for efficient solar-to-chemical energy conversion.     

A Robust Metal-Organic Framework with Scalable Synthesis and Optimal Adsorption and Desorption for Energy-Efficient Ethylene Purification

Adsorptive separation is an energy-efficient alternative, but its advancement has been hindered by the challenge of industrially potential adsorbents development. Herein, a novel ultra-microporous metal-organic framework ZU-901 is designed that satisfies the basic criteria raised by ethylene/ethane (C₂H₄/C₂H₆) pressure swing adsorption (PSA). ZU-901 exhibits an “S” shaped C₂H₄ curve with high sorbent selection parameter (65) and could be mildly regenerated. Through green aqueous-phase synthesis, ZU-901 is easily scalable with 99 % yield, and it is stable in water, acid, basic solutions and cycling breakthrough experiments. Polymer-grade C₂H₄ (99.51 %) could be obtained via a simulating two-bed PSA process, and the corresponding energy consumption is only 1/10 of that of simulating cryogenic distillation. Our work has demonstrated the great potential of pore engineering in designing porous materials with desired adsorption and desorption behavior to implement an efficient PSA process.     

Metal-Organic Frameworks for Photocatalytic Water Splitting and CO2 Reduction

Photocatalytic water splitting and carbon dioxide (CO₂) reduction provide promising solutions to global energy and environmental issues. In recent years, metal-organic frameworks (MOFs), a class of crystalline porous solids featuring well-defined and tailorable structures as well as high surface areas, have captured great interest toward photocatalytic water splitting and CO₂ reduction. In this review, the semiconductor-like behavior of MOFs is first discussed. We then summarize the recent advances in photocatalytic water splitting and CO₂ reduction over MOF-based materials and focus on the unique advantage of MOFs for clarifying the structure-property relationship in photocatalysis. In addition, some representative characterization techniques have been presented to unveil the photocatalytic kinetics and reaction intermediates in MOF-based systems. Finally, the challenges, and perspectives for future directions are proposed.     

Elaborating E/Z-Geometry of Alkenes via Cage-Confined Arylation Catalysis of Terminal Olefins

A visible light photosensitizing metal-organic cage is applied as an artificial supramolecular reactor to control the reaction of aryl radicals with terminal olefins under green light/solvent conditions, which facilitates selective transformation in the confined enzyme-mimicking environment to give a series of geometrically defined E/Z-alkenes. The hydrophobic cage displays good host–guest inclusion with aromatic substrates, promoting Meerwein arylation and protecting E-isomeric products during reaction; while a small amount of benzonitrile can turn on efficient E→Z isomerization. Besides π–π stacking, the hydrogen bonding and halogen bonding interactions also act as control forces for the arylation of aliphatic terminal olefins known as poor acceptors in classic Meerwein arylation. The application of this switchable cage-confined arylation catalysis has been demonstrated by the syntheses of Tapinarof and a marine natural product from the same substrate via controllable E/Z selectivity.     

Expanding Linker Dimensionality in Metal-organic Frameworks for sub-Ångstrom Pore Control for Separation Applications

Metal-organic frameworks (MOFs) are a class of porous materials with high surface areas, which are acquiring rapid attention on an exponential basis. A significant characteristic of MOFs is their ability to act as adsorbents to selectively separate component mixtures of similar size, thereby addressing the technological need for an alternative approach to conventional distillation methods. Recently, MOFs comprising a 3-Dimensional (3D) linker have shown outstanding capabilities for difficult separations compared to the parent 2-Dimensional (2D) analogue. 3D-linkers with a polycyclic core are underrepresented in the MOF database due to the widespread preferred use of 2D-linkers and the misconceived high-cost of 3D linkers. We summarize the recent research of 3D-linker MOFs and highlight their beneficial employment for selective gas and hydrocarbon adsorption and separation. Furthermore, we outline forecasts in this area to create a platform for widespread adoption of 3D-linkers in MOF synthesis.     

Synergistic Metal-Nonmetal Active Sites in a Metal-Organic Cage for Efficient Photocatalytic Synthesis of Hydrogen Peroxide in Pure Water

Photocatalytic synthesis of hydrogen peroxide (H₂O₂) is a potential clean method, but the long distance between the oxidation and reduction sites in photocatalysts hinders the rapid transfer of photogenerated charges, limiting the improvement of its performance. Here, a metal-organic cage photocatalyst, Co₁₄(L−CH₃)₂₄ , is constructed by directly coordinating metal sites (Co sites) used for the O₂ reduction reaction (ORR) with non-metallic sites (imidazole sites of ligands) used for the H₂O oxidation reaction (WOR), which shortens the transport path of photogenerated electrons and holes, and improves the transport efficiency of charges and activity of the photocatalyst. Therefore, it can be used as an efficient photocatalyst with a rate of as high as 146.6 μmol g⁻¹ h⁻¹ for H₂O₂ production under O₂-saturated pure water without sacrificial agents. Significantly, the combination of photocatalytic experiments and theoretical calculations proves that the functionalized modification of ligands is more conducive to adsorbing key intermediates (*OH for WOR and *HOOH for ORR), resulting in better performance. This work proposed a new catalytic strategy for the first time; i.e., to build a synergistic metal-nonmetal active site in the crystalline catalyst and use the host–guest chemistry inherent in the metal-organic cage (MOC)to increase the contact between the substrate and the catalytically active site, and finally achieve efficient photocatalytic H₂O₂ synthesis.     

Confinement-Driven Photophysics in Hydrazone-Based Hierarchical Materials

Confinement-imposed photophysics was probed for novel stimuli-responsive hydrazone-based compounds demonstrating a conceptual difference in their behavior within 2D versus 3D porous matrices for the first time. The challenges associated with photoswitch isomerization arising from host interactions with photochromic compounds in 2D scaffolds could be overcome in 3D materials. Solution-like photoisomerization rate constants were realized for sterically demanding hydrazone derivatives in the solid state through their coordinative immobilization in 3D scaffolds. According to steady-state and time-resolved photophysical measurements and theoretical modeling, this approach provides access to hydrazone-based materials with fast photoisomerization kinetics in the solid state. Fast isomerization of integrated hydrazone derivatives allows for probing and tailoring resonance energy transfer (ET) processes as a function of excitation wavelength, providing a novel pathway for ET modulation.     

Cover Picture: Supramolecular Self-Assembly as a Tool To Preserve the Electronic Purity of Perylene Diimide Chromophores (Angew. Chem. Int. Ed. 12/2023)

Organic semiconductors are promising for efficient, printable optoelectronics. However, strong excited-state quenching due to uncontrolled aggregation limits their use in devices. We report on the self-assembly of a supramolecular pseudo-cube formed from six perylene diimides (PDIs). The rigid, shape-persistent cage sets the distance and orientation of the PDIs and suppresses intramolecular rotations and vibrations, leading to non-aggregated, monomer-like properties in solution and the solid state, in contrast to the fast fluorescence quenching in the free ligand. The stabilized excited state and electronic purity in the cage enables the observation of delayed fluorescence due to a bright excited multimer, acting as excited-state reservoir in a rare case of benign inter-chromophore interactions in the cage. We show that self-assembly provides a powerful tool for retaining and controlling the electronic properties of chromophores, and to bring molecular electronics devices within reach.