Direct pore engineering of 2D imine covalent organic frameworks via sub-stoichiometric synthesis

Two-dimensional covalent organic frameworks(2D COFs)bearing various topologies can be precisely designed based on the symmetry of monomers.Their pore environment can be further regulated via either pre-functionalization of the monomers or post-modification of the skeleton.Among them,sub-stoichiometric synthesis is an efficient method which can mediate uncondensed functional moieties periodically arranged in the COF skeletons.Herein,a series of imine-linked 2D COFs with specifically decorated formyl or amino groups were selectively synthesized via sub-stoichiometric formyl transamination.The molar ratios of the monomers directly determine the structures of the resulting COFs with periodic vertex vacancies.The COF with polar amino sites could efficiently capture CO₂ and H₂O.This work demonstrates tuning the stoichiometry of the monomers could facilely modulate the functions of the pore channels.It also provides insights into constructing novel COFs with complex structures for targeted applications.     

Polyimidazolyl acetate ionic liquid grafted on cellulose filter paper as thin-film extraction phase for extraction of non-steroidal anti-inflammatory drugs from water

Recently, pharmaceuticals and personal care products in the water environment exhibited potential risks to both human and aquatic organisms. In order to improve the sensitivity and accuracy of pharmaceutical detection, the polyimidazolyl acetate ionic liquid was synthesized by Radziszewski reaction and coated on cellulose filter papers as a thin-film extraction phase for extraction of non-steroidal anti-inflammatory drugs from water. The attenuated total reflection-infrared spectrometry, thermogravimetric analysis, and scanning electron microscope analyses demonstrated that the polyimidazolyl acetate ionic liquid was successfully prepared and attached to the surface of the cellulose filter paper through chemical bonding. The adsorption capacity of the homemade thin-film extraction material for the four non-steroidal anti-inflammatory drugs was greater than 8898 ng/cm² under the optimum conditions, and the desorption rate was over 90%. Then, a paper-based thin-film extraction phase-high-performance liquid chromatography-tandem mass spectrometry method was established for the extraction of non-steroidal anti-inflammatory drugs in water. This method provided limits of detection and limits of quantification were in the range of 0.02–0.15 and 0.17–0.50 μg/L, respectively. Hence, the obtained thin-film extraction phase showed excellent recovery and reproducibility for the target non-steroidal anti-inflammatory drugs with carboxyl groups from water.     

An Electrochemical Way to Generate Amphiphiles from Hydrazones for the Synthesis of 1,2,4-Triazole Scaffold Cyclic Compounds

An electro-oxidative cyclization pathway in which hydrazones are selected as starting materials to generate amphiphiles by reacting with benzylamines and benzamides was reported. This strategy successfully prepared a series of 1,2,4-triazoles in satisfactory yields. Moreover, the use of cheap stainless steel as the anode, the feasibility to conduct the transformation as a one-pot reaction and the proof that scaling-up these reactions is possible make this transformation attractive for potential application in industry.     

Control of pore environment in highly porous carbon materials for C2H6/C2H4 separation with exceptional ethane uptake

Adsorptive separation of C₂H₆ from C₂H₄ by adsorbents is an energy-efficient and promising method to boost the polymer grades C₂H₄ production. However, that C₂H₆ and C₂H₄ display very similar physical properties, making their separation extremely challenging. In this work, by regulating the pore environment in a family of chitosan-based carbon materials (C-CTS-1, C-CTS-2, C-CTS-4, and C-CTS-6)- we target ultrahigh C₂H₆ uptake and C₂H₆/C₂H₄ separation, which exceeds most benchmark carbon materials. Explicitly, the C₂H₆ uptake of C-CTS-2 (166 cm³/g at 100 kPa and 298 K) has the second-highest adsorption capacity among all the porous materials. In addition, C-CTS-2 gives C₂H₆/C₂H₄ selectivity of 1.75 toward a 1:15 mixture of C₂H₆/C₂H₄. Notably, the adsorption enthalpies for C₂H₆ in C-CTS-2 are low (21.3 kJ/mol), which will facilitate regeneration in mild conditions. Furthermore, C₂H₆/C₂H₄ separation performance was confirmed by binary breakthrough experiments. Under different ethane/ethylene ratios, C-CTS-X extracts a low ethane concentration from an ethane/ethylene mixture and produces high-purity C₂H₄ in one step. Spectroscopic measurement and diffraction analysis provide critical insight into the adsorption/separation mechanism. The nitrogen functional groups on the surface play a vital role in improving C₂H₆/C₂H₄ selectivity, and the adsorption capacities depend on the pore size and micropore volume. Moreover, these robust porous materials exhibit outstanding stability (up to 800 °C) and can be easily prepared on a large scale (kg) at a low cost (～$26 per kg), which is very significant for potential industrial applications.     

An Iridium Complex as an AIE-active Photosensitizer for Image-guided Photodynamic Therapy

Image-guided photodynamic therapy (PDT) has received growing attention due to its non-invasiveness and precise controllability. However, the PDT efficiency of most photosensitizers are decreased in living system due to the aggregation-caused singlet oxygen (¹O₂) generation decreasing. Herein, we present an Iridium (III) pyridylpyrrole complex (Ir-1) featuring of aggregation-induced emission (AIE) and ¹O₂ generation characteristics for image-guided PDT of cancer. Ir-1 aqueous solution exhibits bright red phosphorescence peaked at 630 nm, large Stokes shift of 227 nm, and good ¹O₂ generation ability. The ¹O₂ generating rate of Ir-1 in EtOH/water mixture solution is 2.3 times higher than that of Rose Bengal. In vitro experimental results revealed that Ir-1 has better biocompatibility and higher phototoxicity compared with clinically used photosensitizers (Rose Bengal and Ce6), suggesting that Ir-1 can serve as a photosensitizer for image-guided PDT of cancer.     

Facile Surfactant-, Reductant-, and Ag Salt-free Growth of Ag Nanoparticles with Controllable Size from 35 to 660 nm on Bulk Ag Materials

Morphologically and dimensionally controlled growth of Ag nanocrystals has long been plagued by surfactants or capping agents that complicate downstream applications, unstable Ag salts that impaired the reproducibility, and multistep seed injection that is troublesome and time-consuming. Here, we report a one-pot electro-chemical method to fast (∼2 min) produce Ag nanoparticles from commercial bulk Ag materials in a nitric acid solution, eliminating any need for surfactants or capping agents. Their size can be easily manipulated in an unprecedentedly wide range from 35 to 660 nm. Furthermore, the Ag nanoparticles are directly grown on the Ag substrate, highly desirable for promising applications such as catalysis and plasmonics. The mechanistic studies reveal that the concentration of Ag⁺ in the diffusion layer nearby the surface, controlled by the magnitude and duration of voltage, is critical in governing the nanoparticle formation (<1.3 mM) and its dimensional adjustability.     

Localized surface plasmon resonance properties and biomedical applications of copper selenide nanomaterials

Nanomaterials with localized surface plasmon resonance (LSPR) locating in the near-infrared region have broad application prospects in the field of biomedicine. However, the biggest problem that limits the biomedical application of such nanomaterials lies in two aspects: First, the potential long-term in vivo toxicity caused by the metabolism of many nanomaterials with LSPR effect; Second, most of current nanomaterials with LSPR effect are difficult to achieve LSPR wavelength tunability in the near-infrared region to adapt to different biomedical applications. Copper selenide nanomaterials are composed of selenium and copper, which are necessary nutrient elements for human life. Because of the active and flexible chemical properties of selenium and copper, copper selenide nanomaterials can not only be effectively degraded and utilized in human body, but also be endowed with various physicochemical properties by chemical modification or doping. Recently, copper selenide nanomaterials have shown unique properties such as LSPR in the near-infrared region, making them attractive for near-infrared thermal ablation, photoacoustic imaging, disease marker detection, multimode imaging, and so on. Currently, to the best of our knowledge, there is no review on the LSPR properties of copper selenide nanomaterials and its biomedical applications. This review first discusses the relationship between the physicochemical properties and the LSPR of copper selenide nanomaterials and then summarizes the latest progress in the application of copper selenide nanomaterials in biological detection, diagnosis, and treatment of diseases. In addition, the advantages, and prospects of copper selenide nanomaterials in biomedicine are also highlighted.     

Selection of hydrogel electrolytes for flexible zinc–air batteries

Flexible zinc–air batteries attract more attention due to their high energy density, safety, environmental protection, and low cost. However, the traditional aqueous electrolyte has the disadvantages of leakage and water evaporation, which cannot meet application demand of flexible zinc–air batteries. Hydrogels possessing good conductivity and mechanical properties become a candidate as the electrolytes of flexible zinc–air batteries. In this work, advances in aspects of conductivity, mechanical toughness, environmental adaptability, and interfacial compatibility of hydrogel electrolytes for flexible zinc–air batteries are investigated. First, the additives to improve conductivity of hydrogel electrolytes are summarized. Second, the measures to enhance the mechanical properties of hydrogels are taken by way of structure optimization and composition modification. Third, the environmental adaptability of hydrogel electrolytes is listed in terms of temperature, humidity, and air composition. Fourth, the compatibility of electrolyte–electrode interface is discussed from physical properties of hydrogels. Finally, the prospect for development and application of hydrogels is put forward.     

An insight into the electrocatalytic properties of porous La0.3Sr0.7Fe0.7Cr0.3O3−δ electrodes towards oxygen reduction reaction

Journal of Solid State Electrochemistry - The electrocatalytic properties of porous La0.3Sr0.7Fe0.7Cr0.3O3−δ electrodes towards oxygen reduction reaction were investigated as a function...     

Flexible all-solid-state supercapacitor based on polyhedron C-ZIF-8/PANI composite synthesized by unipolar pulse electrodeposition method

Journal of Solid State Electrochemistry - In this work, the unipolar pulse electrodeposition (UPED) method is used to electrodeposit the conductive polyaniline (PANI) on the carbonized polyhedron...