Latest ArticlesSpectroscopic study of water splitting by neutral metal clusters is crucial to understanding the microscopic mechanism of catalytic processes but has been proven to be a challenging experimental target due to the difficulty in size selection. Here, we report a size-specific infrared spectroscopic study of the reactions between neutral group 3 metals and water molecules based on threshold photoionization using a vacuum ultraviolet laser. Quantum chemical calculations were carried out to identify the structures and to assign the experimental spectra. All the M2O4H4 (M = Sc, Y, La) products are found to have the intriguing M2(μ2-O)(μ2-H)(μ2-OH)(η1-OH)2 structures, indicating that the HOH bond breaking, the MO/MH/MOH bond formation, and hydrogen production proceed efficiently in the reactions between laser-vaporized metals and water molecules. The joint experimental and theoretical results on the atomic scale demonstrate that the water splitting by neutral group 3 metals is both thermodynamically exothermic and kinetically facile in the gas phase. These findings have important implications for unravelling the structure-reactivity relationship of catalysts with isolated metal atoms/clusters dispersed on supports.
A pair of selenanthrene-bridged molecular cages have been constructed through a one-step cyclization reaction of a tetrakis(iodo) crown ether with selenium powder. The tubular belt-shaped cage has an intrinsic cavity which can adaptively transform to accommodate electron-deficient guests forming [2]pseudorotaxane complexes. The other product was determined to be an isomeric cage featuring a Möbius strip structure, which exhibits slower twist-migration dynamics than its thianthrene counterpart. The success of using selenanthrene as joints enables an alternative way to structural design and property regulation of molecular cages.
The sluggish conversion kinetics and shuttle effect of lithium polysulfides (LiPSs) severely hamper the commercialization of lithium–sulfur batteries. Numerous electrocatalysts have been used to address these issues, amongst which, transition metal dichalcogenides have shown excellent catalytic performance in the study of lithium–sulfur batteries. Note that dichalcogenides in different phases have different catalytic properties, and such catalytic materials in different phases have a prominent impact on the performance of lithium–sulfur batteries. Herein, 1T-phase rich MoSe2 (T-MoSe2) nanosheets are synthesized and used to catalyze the conversion of LiPSs. Compared with the 2H-phase rich MoSe2 (H-MoSe2) nanosheets, the T-MoSe2 nanosheets significantly accelerate the liquid phase transformation of LiPSs and the nucleation process of Li2S. In-situ Raman and X-ray photoelectron spectroscopy (XPS) find that T-MoSe2 effectively captures LiPSs through the formation of Mo-S and Li-Se bonds, and simultaneously achieves fast catalytic conversion of LiPSs. The lithium–sulfur batteries with T-MoSe2 functionalized separators display a fantastic rate performance of 770.1 mAh/g at 3 C and wonderful cycling stability, with a capacity decay rate as low as 0.065% during 400 cycles at 1 C. This work offers a novel perspective for the rational design of selenide electrocatalysts in lithium–sulfur chemistry.
Anti-counterfeiting labels with various fluorescent colors are of great importance in information encryption-decryption, but are still limited to static information display. Therefore, it is urgent to develop new materials and encryption-decryption logic for improving the security level of secret information. In this study, an organohydrogel made up of poly(N,N-dimethylacrylamide) (pDMA) hydrogel network and polyoctadecyl methacrylate (pSMA) organogel network that copolymerized with two fluorophores, 6-acrylamidopicolinic acid moieties (6APA, fluorescent ligand) and spiropyran units (SPMA, photochromic monomer), was prepared by a two-step interpenetrating method. As UV light of 365 nm and 254 nm can both cleave Cspiro-O bonds of SPMA, and the green fluorescence of 6APA-Tb3+ can only be excited by 254 nm light, the organohydrogel displays yellow and red under the irradiation of 254 nm and 365 nm, respectively. In addition to wavelength selectivity, these two fluorophores are thermal-responsive, leading to the fluorescence variation of the organohydrogel during heating process. As a result, secret information loaded on the organohydrogel can be decrypted by the irradiation of UV light, and the authenticity of the information can be further identified by thermal stimulation. Our fluorescent organohydrogel can act as an effective anti-counterfeiting label to improve the information security and protect the information from being cracked.
The transport of colloids and radionuclides is sophisticated because of the variety of charge properties between colloidal particles and host subsurface media, which causes great difficulty in establishing a reliable model of radionuclides migration by taking the colloid phase into consideration. In this work, the co-transport of illite colloids (IC) and Eu(Ⅲ) in the quartz sand and iron-coated sand porous media was investigated by column experiments to address the predominant mechanism of charge properties on co-transport. Results showed that Eu(Ⅲ) transport was driven by the illite colloids and electrostatic interaction was critical in governing the co-transport patterns. The promotion of Eu(Ⅲ) transport by IC was attenuated in the iron-coated sand systems; more IC-Eu(Ⅲ) complexes were retained uniformly in the column. The pore throat shrinkage caused by electrostatic attachment between aggregated IC and iron oxides exacerbated the physical straining and size exclusion effect of IC-Eu(Ⅲ) complexes. An aggravated irreversible retention of IC-Eu(Ⅲ) was detected in iron-coated sand column due to the electrostatic attraction of IC-Eu(Ⅲ) to host media. The findings are essential for improving the understanding on the potential transport, retention and release risk of colloids associated radionuclides, and imply that the positively charged permeable reactive barrier is an effective strategy to reduce the transport risk of colloid associated radionuclides.
The rational construction of high-performance and stable electrocatalyst for oxygen evolution reaction (OER) is a prerequisite for efficient water electrolysis. Herein, we develop a broccoli-like Ni3S2@NiFePx (Ni3S2@NFP) catalyst on nickel foam (NF) via a sequential two-step layer-by-layer assembly electrodeposition method. X-ray diffraction, in situ Raman and Fourier-transform infrared spectra have mutually validated the element segregation and phase refusion during OER condition. The reconstruction of double layer Ni3S2@NFP facilitates the formation of the active (oxy)hydroxides, which is modulated by the dual anionic layer with mixed sulfate and phosphate ions. As a result, the obtained Ni3S2@NFP electrode exhibits low overpotential (329 mV) and long-term durability (~500 h) for OER at current density of 500 mA/cm2. Moreover, the self-supported Ni3S2@NFP can act as an efficient and durable anode in alkaline anion exchange membrane water electrolysis device (AEMWE). This work provides a facile and scaled-up strategy to construct self-supported electrocatalyst and emphasizes the crucial role of anions in pre-catalyst reconstruction and enhancing OER performance.
Macrocyclic supramolecular complexes demonstrate the dynamic potential to solve global biomedical challenges, a promising cancer treatment modality. The macrocyclic system is an important heterocyclic system widely present in natural products and synthetic molecules. The unique structural feature of macrocyclic supramolecular complexes with desirable donor & acceptor characteristics is beneficial for readily binding with various enzymes and receptors in biological systems through diverse weak interactions, thereby exhibiting broad bioactivities. Macrocyclic-related research and macrocyclic moleculesbased medicinal chemistry developments have become rapidly developing areas of study. Numerous macrocyclic-based molecules as clinical drugs have been extensively used in the clinic to treat various diseases with high therapeutic potency. This critically analyzed work systematically reviews current developments of macrocyclic supramolecular complexes-based compounds in the range of medicinal chemistry as anticancer, anti-inflammatory, and other therapeutic agents, together with their potential applications in diagnostics and pathology. This review will be helpful for medicinal chemistry researchers to develop new thoughts in the quest for rational designs of more active and less toxic macrocyclic supramolecular complexes-based medicinal drugs, as well as more effective diagnostic agents and pathologic probes.
Chemical upcycling of end-of-life poly(lactide) plastics to lactide, lactate ester and new poly(lactide) has been achieved by using magnesium bis[bis(trimethylsilyl)amide] [Mg(HMDS)2] as promoter. Mg(HMDS)2 showed high efficiency in L-lactide polymerization and poly(lactide) depolymerization. Mg(HMDS)2/Ph2CHOH catalytic system displayed high ring-opening selectivity and the characteristic of immortal polymerization. Taking advantage of transesterification, depolymerizations of end-of-life poly(lactide) plastics to lactate ester (polymer to value-added chemicals) and lactide (polymer to monomer) were achieved with high yields. Besides, a new "depolymerization-repolymerization" strategy was proposed to directly transform poly(lactide) into new poly(lactide). This work provides a theoretical basis for the design of polymerization and depolymerization catalysts and promotes the development of degradable polymers.
To achieve smart and personalized medicine, the development of hydrogel dressings with sensing properties and biotherapeutic properties that can act as a sensor to monitor of human health in real-time while speeding up wound healing face great challenge. In the present study, a biocompatible dual-network composite hydrogel (DNCGel) sensor was obtained via a simple process. The dual network hydrogel is constructed by the interpenetration of a flexible network formed of poly(vinyl alcohol) (PVA) physical cross-linked by repeated freeze-thawing and a rigid network of iron-chelated xanthan gum (XG) impregnated with Fe3+ interpenetration. The pure PVA/XG hydrogels were chelated with ferric ions by immersion to improve the gel strength (compressive modulus and tensile modulus can reach up to 0.62 MPa and 0.079 MPa, respectively), conductivity (conductivity values ranging from 9 × 10-4 S/cm to 1 × 10-3 S/cm) and bacterial inhibition properties (up to 98.56%). Subsequently, the effects of the ratio of PVA and XG and the immersion time of Fe3+ on the hydrogels were investigated, and DNGel3 was given the most priority on a comprehensive consideration. It was demonstrated that the DNCGel exhibit good biocompatibility in vitro, effectively facilitate wound healing in vivo (up to 97.8% healing rate) under electrical stimulation, and monitors human movement in real time. This work provides a novel avenue to explore multifunctional intelligent hydrogels that hold great promise in biomedical fields such as smart wound dressings and flexible wearable sensors.
Simultaneous acquisition of fluorescence property and refractive index using a single surface plasmon coupled emission (SPCE) measurement has been achieved, thus achieving synchronicity in real time. The SPCE sensor was employed for monitoring the adsorption of volatile organic compounds (VOCs) by dye-encapsulated metal-organic frameworks (Dye@MOFs). Refractive index can reveal surface molecular adsorption and the fluorescence with information on refractive index can provide a comprehensive analysis of the adsorption events of VOCs on the interface. Meantime, the signal intensity can be amplified by combining the responses caused by changes in refractive index and the fluorescence property in parallel. This all-in-one method opens up a route to monitoring multiple processes simultaneously occurring on the interface.
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