Materials Chemistry Frontiers最新文献

Nature's fundamental processes have inspired the development of robotic systems. Living organisms generate movements through complex molecular mechanisms, particularly evident in muscle tissue, where natural protein motors generate motion across multiple length scales. While traditional rigid robots have achieved significant technological advances, the emergence of supramolecular soft robotics presents promising opportunities for functional applications in biomimetic and stimuli-responsive materials. However, the high structural requirements of supramolecular nanoassemblies in supramolecular soft robotic systems greatly hamper their rapid development. Herein, we demonstrate macroscopic movements of supramolecular visible-light driven soft robotic materials in aqueous media without high orientational order, high aspect ratio, and highly charged nature. Through delicate molecular design of indigo amphiphiles (IAs), the supramolecular assembly behavior of IAs was significantly influenced by altering the alkyl-linker chain lengths, resulting in nanostructures ranging from rod-like micelles to vesicles. Upon red-light laser irradiation to IA supramolecular soft robotic materials, the IA soft robotics bent towards the light source, enabled by transformation of IA nanoassemblies and water ejection from the soft robotics, achieving macroscopic photoactuation function with speed up to 25.4 ± 2.8° min⁻¹. The result paves the way for the design of next generation visible-light controlled biomimetic supramolecular soft robotic systems.

Aqueous proton batteries have garnered significant interest owing to their cost-effectiveness and enhanced safety. However, achieving all-organic rocking-chair proton batteries remains a challenge due to the lack of suitable organic electrode materials in acid electrolytes. This study presents an all-organic rocking-chair proton battery employing a diquinoxalino [2,3-a:2′,3′-c] phenazine (HATN) anode paired with a 2,6-dihydroxynaphthalene (2,6-DHN)@CMK-3 cathode, operating in 9.5 m H₃PO₄ electrolyte. Its working mechanism includes reversible –C–O–H/–CO conversion at the cathode coupled with –CN/–C–N–H conversion at the anode. Thanks to its rapid reaction kinetics, this proton battery exhibits a reversible discharge capacity of 101 mAh g⁻¹ at 1 A g⁻¹, a satisfactory energy density of 61 Wh kg⁻¹, and an exceptional cycling stability beyond 6000 cycles. Notably, benefiting from the low freezing point of the 9.5 m H₃PO₄ electrolyte, this proton battery sustains robust rate capability and stable cycling down to −50 °C, highlighting its suitability for operation under cold conditions.

Covalent organic frameworks (COFs) have demonstrated significant potential in visible-light-driven photocatalysis due to their tunable structures and adjustable bandgaps. However, most COFs exhibit a limited light absorption range and poor solar energy utilization, leading to low catalytic efficiency. Developing COFs with a broad absorption range is therefore crucial for enhancing solar utilization and photocatalytic reaction rates. This study constructed three benzothiadiazole-based donor–acceptor (D–A) COFs (HIAM-0032 to HIAM-0034) with fes topology, extending the light-absorption range into the near-infrared region. Among the three COFs, HIAM-0033 exhibited a remarkable photocatalytic hydrogen production rate of 7.8 mmol g⁻¹ h⁻¹ under visible light irradiation, which is 4.1 and 11.4 times higher than those of HIAM-0034 (1.9 mmol g⁻¹ h⁻¹) and HIAM-0032 (0.7 mmol g⁻¹ h⁻¹). Photoelectrochemical analyses revealed that the superior performance of HIAM-0033 originates from enhanced donor–acceptor interactions, which reduce the exciton binding energy, accelerate charge separation and migration, and increase carrier concentration. This work sheds light on the design and synthesis of COFs with broad light-harvesting capability to realize efficient photocatalysis.

The introduction of “heterogeneity within order” to metal–organic frameworks (MOFs) commonly leads to an increase in structural complexity, posing the question of whether it is possible to spatially arrange multiple components in a simple network. Here, we focus on the integration of quaternary components into a simple pcu-b (primitive cubic unit-biparticle) network using a [Zn₄O]-core cluster and paddle-wheel secondary building units (SBUs) alongside organic linkers. We systematically explore a design space of over 180 candidate configurations, identifying an optimal structure that balances synthetic feasibility and functional potential. Experimental validation confirmed the successful synthesis of the predicted framework, named MAC-5, which exhibits unique anisotropic modulation enabled by the controlled spatial arrangement of distinct Zn₄O(COO)₄(NN)₂ and paddle-wheel SBUs. Extending this approach, we synthesized a series of iso-reticular analogues, presenting the tailored multiple functions from different multicomponent frameworks. The hetero-SBU arrangement of MAC-5 enhanced the thermal and chemical stabilities and enabled programmable metal doping that defies expectations in pcu-based systems. This work establishes a reticular chemistry approach to engineering functional complexity within simple network topologies, providing a blueprint for the rational design of multicomponent MOFs with tailored properties.

The limited efficacy and potential off-target toxicity of nanotherapeutic drugs remain significant challenges in liver cancer treatment. To address these issues, a novel targeted therapy approach utilizing a multifunctional nanocomposite, DOX/Ti₃C₂/PDA/PEG–FA, was developed for combined photothermal/chemotherapy (PTT/CHT) tumor treatment. The folic acid (FA)-modified nanomaterial facilitated specific targeting of folate receptor-overexpressing liver tumor cells, ensuring enhanced accumulation of the drug within the tumor site. Upon near-infrared (NIR) laser irradiation, the Ti₃C₂/PDA core exhibited efficient photothermal conversion, leading to a rapid temperature elevation in the tumor region while simultaneously triggering controlled DOX release due to the photothermal and acidic stimulation, thereby promoting chemotherapy. In vitro results demonstrated that the DOX/Ti₃C₂/PDA/PEG–FA nanocomposites effectively inhibited the proliferation of HepG2 cells. Moreover, in vivo studies in the HepG2 xenograft mouse model showed a significant reduction in the tumor volume and complete tumor ablation with minimal side effects, indicating the high efficiency and low toxicity of the targeted PTT/CHT combination therapy. This study introduces a novel DOX/Ti₃C₂/PDA/PEG–FA nanoplatform, which paves the way for targeted cancer therapy through a synergistic mechanism, significantly improving therapeutic efficacy against liver cancer while concurrently reducing systemic adverse effects.

Biomass-derived hard carbon materials are considered promising anodes for sodium ion batteries (SIBs). Herein, we present a simple pre-oxidation strategy to prepare bamboo-derived hard carbon featuring a closed pore structure and pseudo-graphitic domains, with an expanded interlayer spacing of 0.39 nm. It exhibits outstanding performance and strong potential for SIB applications.

We report a combination strategy using small-molecule matrix and polymer matrix to tailor ultralong organic room temperature phosphorescence (UORTP). 5H-BTCz can be regarded as an excellent phosphorescence unit due to its characteristics of “large size + hetero atom + high rigidity”. When doped into small-molecule matrix, such as DBT and DMAP, 5H-BTCz displays observable green/yellowish-green UORTP with controllable intensity and lifetime as charge separation and charge recombination occur between 5H-BTCz and matrix molecules. In particular, the structural similarity between 5H-BTCz and DBT and the formation of strong π–π interactions significantly facilitate charge transfer between host and guest, leading to higher phosphorescence intensity but shorter phosphorescence lifetime of 5H-BTCz@DBT. Moreover, when 5H-BTCz is copolymerized into an MA/PETA crosslinked network, a self-standing UORTP film could be obtained owing to the moldability and oxygen isolation capacity of the polymer films. Furthermore, we couple the small-molecule matrix with the polymer matrix, and the advantages of both are realized in the newly doped UORTP system. The phosphorescence lifetime can be tuned in a wide range, and the phosphorescence quantum yield can be maximized to 22.18%. We believe that this work can provide a new strategy to efficiently regulate UORTP and lay the foundation for intelligent organic phosphorescence materials.

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.