Materials Chemistry Frontiers最新文献

We report the influence of post-thermal treatment on the thermomechanical and infrared (IR) optical properties of chalcogenide hybrid inorganic/organic polymers. Using 20 wt% of the tricyclopentadiene (TCPD) crosslinker, elemental sulfur was inverse vulcanized into as-synthesized poly(sulfur₈₀-random-TCPD₂₀) (S80T20) and then thermally treated under different conditions. 140 °C for 12 h was found to be optimal for improving both the thermomechanical and IR optical properties. It is due to the increase in crosslinking density after the reduction of unreacted ES and CC bonds in the crosslinker, while thermal degradation and oxidation were controlled. Glass transition temperature, storage modulus (at 25 °C), and mid-IR transmittance (1 mm-thick) values of S80T20 increased from 6.5 to 29.2 °C, 1.5 to 2.0 GPa, and 38.5 to 41.2%, respectively. Such a strategy could also be applied to S/Se chalcogen mixture-based CHIPs, endowing them with potential for IR optical applications.

Organic dyes in industrial wastewater are posing significant threats to global water resources and have raised concerns about negative impacts on human health. Hydrogels have attracted much attention among various absorbent materials due to their facile synthesis, high stability in water and large adsorption capacity. Herein, we have prepared a supramolecular polymer hydrogel adsorbent based on a water-soluble pillar[5]arene and poly(sodium 4-styrenesulfonate). Benefiting from pillararenes, the hydrogel adsorbent can remove a variety of organic dyes from water. In particular, this hydrogel exhibited excellent adsorption properties for Eriochrome black T (EBT) with a much higher adsorption rate than activated carbon. Importantly, the adsorption capacity is as high as 1818 mg g⁻¹. Furthermore, the hydrogel adsorbent showed excellent selectivity and recyclability when adsorbing organic dyes from water. These excellent results showed the great potential of the pillararene-based supramolecular hydrogel adsorbent in wastewater treatment.

X-ray scintillators are commonly used, with significant applications in scientific research and daily life. However, most commercial scintillators are based on expensive mechanically rigid inorganic crystalline arrays, which normally bear a long-lived afterglow that reduces the resolution in dynamic X-ray monitoring, while low X-ray absorbance and inefficient exciton utilization are deficiencies associated with traditional organic scintillators. Herein, we report a series of readily obtained pure organic single-component scintillators with halogen-enhanced X-ray absorbance, high fluorescence quantum yield, and short decay time. They can be easily prepared into flexible and transparent scintillating imaging films with a high light yield (approaching 20 000 photons MeV⁻¹) and high resolution (above 20 line pairs per mm) that are among the highest levels for organic scintillators reported thus far.

Photodynamic therapy (PDT) is widely used in tumor treatment because it has few side effects and good therapeutic specificity. However, its therapeutic effect is severely limited by the insufficient oxygen supply and high glutathione (GSH) concentration in the tumor environment. Recently, nitric oxide (NO) has been widely used as a physiological regulatory factor and tumor inhibitor in various pathological processes. NO can kill tumor cells by reacting with O₂˙⁻ to produce highly lethal ONOO⁻. Importantly, NO can promote vasodilation to improve hypoxia in the tumor environment and interfere with the antioxidant defense of GSH, improve the sensitivity of the tumor to ROS, and enhance the effect of PDT. However, since NO has a very short half-life and is gaseous, it cannot be used directly in the clinic. As a rule, the use of NO donors is required. L-Arginine (L-Arg) is a natural NO donor that can produce NO under the action of ROS, so that effective synergy of NO/PDT can be achieved by combining L-Arg and a photosensitizer. On this basis, cascade and synergistic NO/PDT antitumor therapy with L-Arg has been reported in recent years. However, a relevant review on cascade and synergistic NO/PDT based on the combination of L-Arg and photosensitizers has not been published. Therefore, in this review, we summarize the recent advances in synergistic NO/PDT for antitumor therapy based on the interaction of L-Arg and various photosensitizers in the last five years. The design idea, synergistic mechanism and application prospects of the two treatment methods are explained in detail. The remaining challenges and future opportunities in this field are also highlighted. We believe that this review will provide a better understanding of cascade and synergistic NO/PDT through multifunctional nanomaterials and advance nanoscience and nanotechnology step by step towards clinical applications.

A facile solution immersion was developed to construct three-dimensional (3D) vertically aligned zeolite imidazole framework ZIF-67 microrod arrays on 3D carbon cloth (CC) with commercial-level mass loading (12 mg cm⁻²). It was realized via in situ crystallization with the assistance of electrodeposited reactive cobalt layer and seed-oriented growth associated with a high concentration of Co²⁺. The as-obtained ZIF-67/CC hybrid featured a 3D/3D hetero-structure with easily accessible channels, abundant electroactive sites and highly conductive networks. As integrated electrodes for supercapacitors, they could achieve a high specific capacitance (3396 mF cm⁻² at 1 mA cm⁻²) with superior rate capability (91% at 10 mA cm⁻²) and long-term cyclic stability (over 99% after 10 000 cycles). Furthermore, the assembled asymmetrical supercapacitor delivered a maximum energy density of 380 mW h cm⁻² at a power density of 1600 mW cm⁻². Such characteristics suggest that the well-aligned ZIF-67 arrays on CC substrate have enormous potential for use in high-performance supercapacitors and can serve as an important platform for other applications, such as energy storage, catalysis and gas adsorption/separation.

The detrimental interfacial side reactions and irregular Zn dendrites may reduce the cycling life of Zn anodes and Zn-based energy storage devices. Regulating the interfacial microenvironment to eliminate harmful side reactions and achieve uniform Zn deposition is vital to develop high-performance Zn anodes. Here, a “hydrophilic-Zn²⁺ conductive” lanthanum phosphate (LaPO₄) interlayer is applied to realize an ultra-long-life Zn anode (LAP-Zn) and Zn²⁺ capacitors. The hydrophilic LaPO₄ can act as a microscopic “H₂O-reservoir” by preferentially adsorbing H₂O molecules (the adsorption energy of LaPO₄–H₂O is −1.17 eV, larger than that of Zn–H₂O). Consequently, a microscopic H₂O-poor environment on the Zn anode is formed, thus eliminating harmful side reactions including H₂ evolution and Zn corrosion. Simultaneously, Zn²⁺ de-solvation is promoted, facilitating accelerated interfacial migration and uniform flux of Zn²⁺. The Zn²⁺ migration number of LAP-Zn is 0.84 which is higher than that of pure Zn, demonstrating excellent Zn²⁺ conductivity. The LAP-Zn//LAP-Zn symmetrical cell operates efficiently for over 700 h at 5 mA cm⁻² and 2 mA cm⁻². The LAP-Zn//activated carbon capacitor exhibits an ultra-long life of 30 000 cycles at 1 A g⁻¹, with continuous operation for over 3600 h while maintaining a capacity retention ratio of 95%. Therefore, this “hydrophilic-Zn²⁺ conductive” LaPO₄ interlayer enables uniform Zn deposition and a highly reversible Zn plating/stripping process. This modification strategy using a “hydrophilic-Zn²⁺ conductive” rare earth-based interfacial layer is simple, long-term effective, and microcosmic, thus boosting the commercial application of Zn-based energy storage devices.

With the characteristics of nontoxicity and environmental benignity, aqueous zinc ion batteries (AZIBs) are rapidly emerging as potential competitors for high-performance energy-storage systems. Nevertheless, several issues hinder their further development, such as the sluggish electrochemical activity and inevitable dissolution of cathode materials. In this work, we introduced oxygen defects (O_d) into the NH₄V₄O₁₀ lattice, which facilitated the transport velocity of Zn²⁺ ions and enhanced their electrical conductivity. Zn//NHVO-O_d-1 batteries showed a reversible capacity of 475.3 mA h g⁻¹ at 0.2 A g⁻¹. At low temperature (0 °C), the cells also demonstrated a capacity retention of 100% after 1000 cycles at 1.0 A g⁻¹. Assembled soft-package devices presented favorable mechanical resilience at different bending conditions.

Volatile organic compounds (VOCs), are recognized as critical environmental contaminants and cancer biomarkers, highlighting the significance of their trace detection for environmental conservation and human health. Surface-enhanced Raman spectroscopy (SERS) technology has emerged as a promising tool in this domain, offering unparalleled sensitivity and the ability to provide molecular fingerprints for probes. Despite the inherent disadvantages of gaseous molecules being difficult to adsorb on solid substrates, researchers have made great efforts to overcome these obstacles. This comprehensive review delineates the recent advancements and applications of SERS technology in the detection of VOCs, encompassing environmental monitoring and the analysis of exhaled breath. A particular focus is placed on the innovative design of substrate materials and strategies for enhancing the capture of gas molecules, including metal–organic frameworks (MOFs), layered double hydroxides (LDHs), microfluidic chips, and other substrates. Finally, we summarized the current challenges confronting SERS technology in VOC detection and provided insights into potential prospects for future development.

The principle of the nanocatalytic medicine strategy is introducing nanocatalysts into tumor tissues and triggering specific chemical reactions through endogenous/exogenous stimuli to convert low/non-toxic exogenously delivered or endogenous substances into therapeutic products with high cytotoxicity. In recent years, the nanocatalytic medicine strategy has been proven to be effective in achieving tumor catalytic therapy, which is expected to reduce side effects and decrease the occurrence of drug resistance. This mini-review briefly outlines typical applications and recent advances in nanocatalyst-triggered in situ chemical reactions in tumor catalytic therapy. Special attention is paid to the design of nanocatalysts related to endogenous and exogenous stimuli (e.g., light, heat, ultrasound, etc.). Finally, challenges and future opportunities for advancing nanocatalysts are highlighted to facilitate the realization of early clinical applications of nanocatalytic medicine strategies.

Herein, we demonstrated a novel approach to construct pyrene-based, high-efficiency, red-emitting molecules. Both of the as-synthesized luminogens exhibited aggregation-induced enhanced emission (AIEE) properties and distinct mechanochromic behavior with a blue-shift for DCI-Py-1 (13 nm) and red-shift for DCI-Py-2 (29 nm). The typical, yet rare, pyrene-based, red-emitting molecules with λ_em = 686 nm open up new avenues to design near-infrared emitting pyrene-based photoelectric materials. Further studies revealed that both of these materials can be utilized for anti-counterfeiting stamps and fingerprint extraction.