New cyclic C-geranylflavanones isolated from Paulownia fortunei fruits with their anti-proliferative effects on three cancer cell lines.

Seven new C-geranylated flavanones, fortunones F - L (1-7), were isolated from the fresh mature fruits of Paulownia fortunei (Seem.) Hemsl. Their structures were determined by extensive spectroscopic data interpretation (UV, IR, HRMS, NMR, and CD). These new isolated compounds were all with a cyclic side chain modified from the geranyl group. Among them, compounds 1-3 all possessed a dicyclic geranyl modification, which was described firstly for Paulownia C-geranylated flavonoids. All the isolated compounds were subjected to the cytotoxic assay on human lung cancer cell A549, mouse prostate cancer cell RM1 and human bladder cancer cell T24, respectively. Results indicated A549 cell line was more sensitive to C-geranylated flavanones than the other two cancer cell lines and compounds 1, 7 and 8 exhibited potential anti-tumor effects (IC50 ˂ 10 µM). Further research revealed the effective C-geranylated flavanones could exert their anti-proliferative activity on A549 cells by inducing apoptosis and blocking cells in G1 phase.

Tunable Sponge-Like Hierarchically Porous Hydrogels with Simultaneously Enhanced Diffusivity and Mechanical Properties.

Crosslinked polymers and gels are important in soft robotics, solar vapor generation, energy storage, drug delivery, catalysis, and biosensing. However, their attractive mass transport and volume-changing abilities are diffusion-limited, requiring miniaturization to avoid slow response. Typical approaches to improving diffusion in hydrogels sacrifice mechanical properties by increasing porosity or limit the total volumetric flux by directionally confining the pores. Despite tremendous efforts, simultaneous enhancement of diffusion and mechanical properties remains a long-standing challenge hindering broader practical applications of hydrogels. In this work, cononsolvency photopolymerization is developed as a universal approach to overcome this swelling-mechanical property trade-off. The as-synthesized poly(N-isopropylacrylamide) hydrogel, as an exemplary system, presents a unique open porous network with continuous microchannels, leading to record-high volumetric (de)swelling speeds, almost an order of magnitude higher than reported previously. This swelling enhancement comes with a simultaneous improvement in Young's modulus and toughness over conventional hydrogels fabricated in pure solvents. The resulting fast mass transport enables in-air operation of the hydrogel via rapid water replenishment and ultrafast actuation. The method is compatible with 3D printing. The generalizability is demonstrated by extending the technique to poly(N-tertbutylacrylamide-co-polyacrylamide) and polyacrylamide hydrogels, non-temperature-responsive polymer systems, validating the present hypothesis that cononsolvency is a generic phenomenon driven by competitive adsorption.

In Situ Biomimetic Mineralization on ZIF-8 for Smart Drug Delivery.

The exploration of metal-organic frameworks (MOFs) with good biocompatibility and physiological stability as carrier platforms for biomedical applications is of great importance but remains challenging. Herein, we developed an in situ biomimetic mineralization strategy on zeolitic imidazolate framework (ZIF) nanocrystals to construct a drug release system with favorable cytocompatibility, improved stability, and pH responsiveness. With lysozyme (Lys) wrapped on the surface of Zn-based ZIF (ZIF-8), Lys/ZIF-8 could strongly bond metal ions to promote nucleation and growth of bone-like hydroxyapatite (HAp), leading to formation of HAp@Lys/ZIF-8 composites. In vitro investigations indicate that the composites with a hollow Lys/ZIF-8 core and a HAp shell exhibited a high drug-loading efficiency (56.5%), smart pH-responsive drug delivery, cytocompatibility, and stability under physiological conditions. The proposed biomimetic mineralization strategy for designing MOFs-based composites may open a new avenue to construct advanced delivery systems in the biomedical field.

Multifunctional Electrocatalysis on a Porous N-Doped NiCo2O4@C Nanonetwork.

Developing a multifunctional electrocatalyst with eminent activity, strong durability, and cheapness for the hydrogen/oxygen evolution reaction (HER/OER) and oxygen reduction reaction (ORR) is critical to overall water splitting and regenerative fuel cells. Herein, a nitrogen-doped nanonetwork assembled by porous and defective NiCo2O4@C nanowires grown on nickel foam (N-NiCo2O4@C@NF) is crafted via biomimetic mineralization and following carbonization of phase-transited lysozyme (PTL)-coupled NiCo2O4. The as-obtained N-NiCo2O4@C@NF electrocatalysts exhibit an exceptional catalytic activity with ultralow overpotentials for the HER (42 mV) and OER (242 mV) to afford 10 mA cm-2 while maintaining good stability in alkaline media. Meanwhile, the N-NiCo2O4@C electrocatalysts presents a superior catalytic activity for ORR and a favorable four-electron pathway. The unprecedented catalytic performance arises from a highly porous structure and abundant defects and synergistic effects of components. This work may offer a new possibility in the exploration of multifunctional electrocatalysts for various energy-related electrocatalytic reactions.

Phase-Transited Lysozyme-Driven Formation of Self-Supported Co3O4@C Nanomeshes for Overall Water Splitting.

The development of highly efficient catalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is of paramount importance in water splitting. Herein, a phase-transited lysozyme (PTL) is employed as the platform to synthesize nitrogen-doped Co3O4@C nanomesh with rich oxygen vacancies supported on the nickel foam (N-Co3O4@C@NF). This PTL-driven N-Co3O4@C@NF integrates the advantages of porous structure, high exposure of surface atoms, strong synergetic effect between the components and unique 3D electrode configuration, imparting exceptional activity in catalyzing both HER and OER. Remarkably, an alkaline electrolyzer assembled by N-Co3O4@C@NF as both cathode and anode delivers a current density of 10 mA cm-2 at an ultralow cell voltage of 1.40 V, which is not only much lower than that of the commercially noble Pt/C and IrO2/C catalyst couple (≈1.61 V) but also a new record for the overall water splitting. The finding may open new possibilities for the design of bifunctional electrocatalysts for application in practical water electrolysis.