Materials Chemistry Frontiers最新文献

The cubic phase of tin monosulphide, π-SnS, is of significant interest due to its attractive properties, such as a wider band gap suitable for solar photovoltaic application and being easier to epitaxially deposit onto technologically relevant semiconductors compared to the thermodynamically stable orthorhombic phase of α-SnS. Recently, we reported cation-assisted phase control for obtaining π-SnS rather than α-SnS using Pb²⁺ cations with a concentration of ∼20 cation percent (cat%). However, replacing Pb²⁺ with alternative non-toxic, environmentally friendly cations for cubic phase stabilization would be clearly advantageous. We have computationally investigated the energetics and electronic properties of calcium ion impurities in both SnS polymorphs. We found that addition of Ca²⁺ cations enables phase control of SnS grown from solution from α-SnS to π-SnS. Experimentally, we observed compact films of π-SnS after incorporating Ca²⁺ cations. Computational results indicated that ∼11 cat% of Ca²⁺ ions are required for preferred growth of π-SnS over α-SnS. Furthermore, the presence of an intermediate layer of CaS is computationally predicted to significantly contribute to the stabilization of the π-SnS phase, thereby reducing the Ca concentration required, which aligns well with experimental observations. Subsequently, we find that CaS is a promising substrate for epitaxial growth of π-SnS in the (111) orientation. Moreover, the bandgap of π-SnS decreased slightly with increasing concentration of Ca cations in the material. These results can facilitate the bulk scale synthesis of π-SnS material, bringing it closer to practical utility for a range of applications.

Premature aging has evolved as one of the major clinical concerns globally because it reduces the working ability of human beings. Therefore, this work demonstrated the delaying of the aging process via sustained delivery of a low-molecular weight (MW) antilipolytic drug, 3,5-dimethylpyrazole (DMP, MW = 96.13 g mol⁻¹). Eventually, the sustained release of DMP is challenging due to rapid clearance, limiting therapeutic efficacy in metabolic disorders. Herein, we developed a DMP-encapsulated-chitosan-grafted-terpolymer (poly[itaconic acid-co-2-ethyl-2-((N-isopropylbutyramido)methyl)succinic acid-co-N-isopropylacrylamide) hydrogel (DCBH) through multi-stage statistical optimization for the sustained delivery of DMP. The mechanically robust DCBH successfully achieved 15-day sustained release of DMP following first-order kinetics, despite its low MW. DCBH demonstrated superior mechanical properties with an ultimate tensile strength of 697 ± 11.05 kPa and multifunctional therapeutic capabilities including significant antioxidant activity (88.38% H₂O₂ scavenging), antibacterial efficacy against S. aureus (inhibition zone: 3.31 ± 0.46 cm), electrical conductivity matching human skin (0.014-1.9 mS cm⁻¹), and Fe²⁺-chelation ability. Glucose consumption assay revealed potential metabolic regulatory effects, while cell studies showed enhanced migration (95.47% vs. 26.15% control), F-actin organization, and excellent biocompatibility with NIH3T3 cells. Senescence associated-β-galactosidase (SA-β-Gal) staining on NIH3T3 cells indicated DCBH's efficiency in combating cellular senescence and premature aging. The electroactivity of DCBH can facilitate cellular proliferation, migration, and angiogenesis through electrical stimulation, while contributing to cellular homeostasis maintenance via recycling of damaged cytoplasmic constituents. This multifunctional platform addresses the challenge of sustained delivery for low-MW therapeutics while providing synergistic therapeutic properties for comprehensive antiaging and biomedical applications.

Achieving stable, persistent room-temperature phosphorescence (RTP) within flexible and deformable elastomer matrices, particularly those that are amenable to advanced manufacturing techniques like 3D printing, is critical for developing future flexible sensors, yet it remains a significant challenge. Existing limitations often arise from quenching effects inherent to polymer motions, the poor solubility or dispersion of phosphors, and the difficulty in maintaining photophysical integrity under mechanical stress. Here, we address these challenges by introducing a versatile, generalisable approach to fabricate high-performance, 3D-printable RTP elastomers. N-Ethylcarbazole derivatives were developed as guest molecules doped into 3D-printable isobornyl acrylate (IBOA): benzyl acrylate (BA) resins. The resulting RTP elastomers exhibited exceptional photophysical properties under ambient atmospheric conditions. It is worthy of note that these elastomers retained their RTP properties consistently throughout both deformation under an external force and the fully recovered state and exhibited no observable alterations. This work provides a general, scalable solution for producing 3D printable RTP elastomers, establishing a foundation for exploring their applications in emerging fields such as flexible sensors and intelligent deformable structures.

Electrochemical nitrate reduction to ammonia (NRA) is an emerging sustainable technology that converts nitrate contamination in wastewater into the value-added chemical ammonia. Copper-based catalysts represent one of the most competitive non-noble NRA electrocatalysts due to their robust nitrate adsorption capability. In this study, we developed a series of Bi–Cu bimetallic oxides (BiCuO_x) with mixed oxidation states of Cu and Bi by tuning the surface oxygen vacancy (O_V) content via a one-pot solution-based in situ H*-mediated reduction method. The resulting BiCuO_x catalyst exhibits an enlarged surface area, abundant electrochemically active sites, and optimized O_V concentration, delivering a high NH₃ faradaic efficiency (FE) of 92.27% ± 3.47% and an NH₃ yield rate of 4331.25 ± 208.4 μg h⁻¹ mg_cat.⁻¹ at −0.8 V vs. RHE. Theoretical calculations reveal that the as-obtained BiCuO_x catalyst more effectively suppresses NO₂* intermediate poisoning on its surface compared to the single-component Cu catalyst owing to the favorable orbital hybridization between the intermediates and the catalyst surface, thereby facilitating the subsequent steps in the NRA reaction pathway. Furthermore, a zinc–nitrate battery is designed by integrating a BiCuO_x cathode with a zinc plate anode sourced from spent zinc–carbon batteries, achieving a peak power density of 1.706 mW cm⁻² and an NH₃ FE of 82.31%. This study highlights a low-cost and highly active oxygen vacancy-mediated catalyst for electrochemical NRA through one-pot solution synthesis, promoting green ammonia production via sustainable NRA.

Purely organic circularly polarized phosphorescence (CPP) materials are promising candidates for chiral optoelectronic and photonic applications but remain limited by challenges in achieving both high quantum efficiency and strong dissymmetry. Here, we report a high-performance CPP system based on brominated cholesteric liquid-crystalline (CLC) molecules that spontaneously self-assemble into left-handed chiral nematic (N*) phases. Among the series, Br10Ch exhibits bright blue CPP at 450 nm with a phosphorescent quantum yield of 36% and a dissymmetry factor of g_lum = +0.30, enabled by enhanced spin–orbit coupling and long-range helical ordering that suppress non-radiative decay. Furthermore, doping the N* matrix with an achiral fluorescent dye (8CNS) enables triplet-to-singlet Förster resonance energy transfer, yielding green circularly polarized fluorescence at 502 nm with inverted handedness (g_lum = −0.32) via selective reflection within the cholesteric host. This combined color tunability and handedness switching in a purely organic system provides a modular approach for tailoring chiroptical emission without heavy metals. Our findings establish CLCs as versatile supramolecular scaffolds for high-performance CPP, offering new opportunities for dynamic optical control in displays, data encryption, and advanced photonic devices.

Boron-based room-temperature phosphorescence (RTP) materials have garnered considerable attention due to their unique photophysical properties and diverse application potential. Nevertheless, systematic discussion on the design strategies, excited state control mechanisms, and practical applications of such molecules remains scarce. This review systematically analyzes the structure–property relationships in boron-based RTP materials, focusing on the influence of key structural factors such as their coordination modes, the number and position of substituents, and the design of host–guest systems. These factors enable precise control over the phosphorescence lifetime and the emission wavelength of the materials. Boron-based RTP materials demonstrate promising applications particularly in anti-counterfeiting, light-emitting displays, and biological imaging. Moreover, this review outlines future research directions and challenges, offering a theoretical foundation for the development of novel RTP materials.

A series of donor–oxygen–acceptor (D–O–A)-type polymers have been newly designed and synthesized, where benzophenone, 1,3-bis(phenylmethanone)-phenylene or 1,4-bis(phenylmethanone)-phenylene is selected as the acceptor combined with the acridine donor through an oxygen linkage. The characteristic geometry endows them with obvious phosphorescence at room temperature for both the neat and doped films. Meanwhile, their emission colors can be finely tuned with increasing electron withdrawing ability of the acceptor. As a consequence, the corresponding polymer light-emitting diodes achieve a bright sky-blue, green and yellow electroluminescence peaking at 482, 502 and 547 nm, respectively. The color modification via acceptor engineering clearly highlights the great universality and potential of the D–O–A design for efficient pure organic room-temperature electrophosphorescent polymers.

Purely organic room-temperature phosphorescence (RTP) materials show broad prospects for various applications due to their characteristics such as stimuli-responsiveness and high exciton utilization. A key challenge for improving the performance of purely organic RTP materials lies in suppressing non-radiative decay while enhancing spin–orbit coupling (SOC). To this end, we systematically combined benzophenone (BP) with thianthrene (TA) at different modification sites and with varying numbers of substituents, creating a class of high-efficiency RTP materials by leveraging the folded conformation of TA groups and introducing intramolecular charge transfer (ICT) to enhance SOC. Benefiting from the separated fluorescence–RTP dual emission of these materials, highly sensitive ratiometric optical oxygen sensing can be achieved with a Stern–Volmer coefficient of up to 10.65 kPa⁻¹. This study not only deepens the understanding of the structure–property relationship of TA-based RTP materials but also provides an effective strategy for performance enhancement and functional development of purely organic RTP materials.

An asymmetric indenone-fused tetraazatetracene based bent N-heteroarene is designed and synthesized. Its photophysical and electrochemical properties together with the packing structure are studied, and its charge transport properties in organic field-effect transistors are investigated. Structure–property relationships are illustrated through comparison with other reported asymmetric N-heteroarenes.

The Materials Chemistry Frontiers Emerging Investigators Series highlights the best research being conducted by scientists in the early stages of their independent careers. This editorial features the emerging investigators who contributed to this series in 2024. Each contributor was recommended as carrying out work with the potential to influence future directions in materials chemistry. Congratulations to all the researchers, we hope you enjoy reading their work.