ABSTRACT Ovarian cancer exhibits profound metabolic dependence on aerobic glycolysis, rendering hexokinase 2 (HK2), the rate‐limiting enzyme of this pathway, a key therapeutic vulnerability. However, therapeutic exploitation of HK2 silencing remains hindered by the intrinsic instability and inefficient intracellular delivery of siRNA. To overcome these limitations, we developed a folate‐functionalized core–shell tecto‐dendrimer (FA‐G5/G3) capable of selectively targeting HK2 through folate receptor‐mediated uptake and intracellular delivery of HK2 siRNA. The engineered nanocomplex exhibited favorable physicochemical properties, including stable architecture, appropriate particle size, and excellent biocompatibility. Following cellular internalization, FA‐G5/G3 facilitated intracellular delivery of HK2 siRNA, resulting in effective post‐transcriptional silencing of HK2 expression. This intervention disrupted glycolytic metabolism, reduced downstream LDHA expression, and markedly decreased extracellular lactate production. By suppressing a central glycolytic regulator, the FA‐G5/G3‐mediated HK2 silencing strategy reduced glycolytic activity and provided a potential approach for exploiting metabolic vulnerabilities in ovarian cancer. Collectively, this study establishes a targeted CSTD‐based siRNA delivery platform for glycolysis‐associated metabolic changes and provides a promising therapeutic strategy for overcoming metabolic vulnerabilities in ovarian cancer.
ABSTRACT Micro‐confinement of a filamentous hydrogel has been obtained in a fluid matrix. Microspheres are prepared emulsifying a one‐component luminescent lyotropic liquid crystal gel based on an Ir(III) complex in an immiscible polymeric matrix. The distribution of filaments inside microspheres, as a function of the Ir(III) complex concentration in water, and their degree of entanglement changes the interface and viscoelastic properties. By combining lyotropic liquid crystal gels and emulsions, this study introduces a new soft hybrid system and offers new possibilities of exploring functional water‐based liquid crystalline materials.
ABSTRACT The structural factors governing dispersion and precipitation in sulfur‐containing polymer systems remain poorly understood. Sulfur‐containing polymer microparticles are prepared by the dispersion copolymerization of 1,7‐octadiene diepoxide (OD) with polysulfide species generated in situ from elemental sulfur and sodium sulfide. Among the examined stabilizers, only poly(vinylpyrrolidone) enables particle formation, whereas the other stabilizers result in precipitation, allowing dispersed and precipitated fractions to coexist for structural comparison. The resulting PolyOD‐S n polymers possess structurally defined backbones, enabling the average sulfur rank, n , defined as the average number of consecutive sulfur atoms in a polysulfide segment, to be estimated using 1 H NMR chemical‐shift analysis combined with elemental‐composition analysis. Fractionation by natural sedimentation and filtration shows that polymers with higher average sulfur ranks preferentially precipitate, whereas those with lower average sulfur ranks remain dispersed. In contrast, no clear correlation is observed between molecular weight and fractionation behavior. These findings indicate that sulfur rank, rather than overall molecular weight, provides a distinct structural basis for the dispersion/precipitation behavior of sulfur‐containing polymers.
ABSTRACT In this work, we report the synthesis of a new family of fluorine‐free protic poly(ionic liquid)s via free‐radical cyclopolymerization of protic diallylammonium monomers. Protic ionic liquid monomers based on diallylmethylammonium (DAMAH + ) and diallylammonium (DAAH 2 + ), combined with different alkyl sulfonate counter‐anions, were first prepared. Cyclopolymerization yielded a systematic series of six poly(diallylammonium) cations, five of which are newly reported here, combining two polymer backbones—poly(DAMAH + ) and the newly incorporated poly(DAAH 2 + )—with three fluorine‐free sulfonate anions, namely mesylate (MsO − ), ethylsulfonate (EsO − ), and dodecylbenzenesulfonate (DBsO − ); the previously reported poly(DAMAH + MsO − ) analogue was included for direct comparison within the same series. Systematic characterization reveals how the interplay between polymer backbone and counter‐anion governs solubility in water and organic solvents, glass transition temperatures (20–55°C), thermal stability (up to 300°C), and ionic conductivity (up to 10 −3 S cm −1 at 100°C). The combination of their physicochemical properties, electrochemical stability, and water processability highlights these polymers as a versatile fluorine‐free platform for electrochemical technologies. To demonstrate this potential, selected polymers were evaluated as water‐processable binders for LiFePO 4 cathodes, where they delivered competitive rate capability and stable electrode performance compared to PVDF. Their protic ionic character further suggests opportunities for future applications toward proton‐conducting materials. Overall, this work introduces a sustainable platform for the development of fluorine‐free ionic polymers with broad potential for electrochemical technologies.
ABSTRACT Flexible wearable electronics face growing bacterial infection risks from prolonged skin contact, creating an urgent demand for flexible materials integrating efficient sensing and antibacterial functions. Herein, a novel phosphorus‐containing porphyrin covalent organic framework (P‐Por COF) was synthesized via a solvothermal Schiff‐base reaction, and incorporated into a polymerizable deep eutectic solvent to fabricate P‐Por COF/PDES composite gels through in‐situ UV polymerization. The resulting gel exhibited enhanced photothermal performance, improved mechanical properties, and excellent near‐infrared (NIR) triggered antibacterial activity. Under 730 nm NIR light irradiation, the P‐Por COF/PDES composite gel could reach 76 °C with 4 min, while showing excellent stability of photothermal cycle. Based on the synergistic effect of photodynamic production of singlet oxygen and photothermal effect, the P‐Por COF/PDES composite gel resulted in a high bactericidal rate of nearly 100% against both Staphylococcus aureus ( S. aureus ) and Escherichia coli ( E. coli ). The P‐Por COF/PDES composite gel delivered a fracture strain up to 2435.82% and 2.6‐fold higher toughness than pure PDES, along with stable, sensitive and self‐healable strain sensing for human motion monitoring. Overall, this work provides a simple and effective strategy for developing antibacterial materials and multifunctional gels with integrated therapeutic and sensing capabilities.
