Gaoyang Wang

The simple, efficient, and low‐cost fabrication strategies for chiral inorganic thin films are highly desirable to expand their wide applications. Herein, we develop an electrochemically assisted approach for the controllable fabrication of high‐performance chiral silver (Ag) films, where L/D‐glutamine (Gln) molecules serve as chiral regulators to steer the asymmetric growth of Ag nanostructures. During electrochemical deposition, the L/D‐Gln breaks the structural symmetry of Ag crystals, while fine‐tuned electrochemical parameters precisely modulate the nucleation and growth process, eliminating the structural disorder of conventional Ag films and enabling the formation of uniform and stable three‐dimensional hierarchical chiral architectures. The well‐defined chiral configuration effectively optimizes the localized surface plasmon resonance (LSPR) behavior of Ag nanomaterials and strengthens chiral plasmonic coupling interactions among hierarchical nano units. Benefiting from the synergistic effect of chiral structural engineering and enhanced plasmonic coupling, the as‐prepared chiral Ag films achieve remarkably amplified and stable circular dichroism (CD) responses and superior chiroptical performance. The established structure–property correlation explicitly reveals the intrinsic mechanism of electrochemical regulation for improved chiroptical behaviors, clarifying the causal relationship between chiral molecular induction, structural evolution, plasmonic coupling, and optical enhancement. This work provides a facile and universal synthetic platform for high‐quality chiral inorganic thin films, offering great application potential in enantiomeric recognition, chiroptical modulation, and plasmonic chiral device fabrication.

Single-cell–level resolution tumor therapy represents an advanced strategy against glioblastoma but lacks suitable theranostic agents. Here, we developed a spatiotemporal-switchable, two-dimensional (2D), bismuthene-based second near-infrared window (NIR-II) nanozyme. In this platform, the bismuthene scaffold simultaneously directed the assembly of indocyanine green (ICG) into ordered J -aggregates and anchored monodispersed platinum (Pt) atoms. The resulting J -aggregates acted as an optical antenna with a long-wavelength absorption peak at 895 nanometers and high photobleaching resistance of 78.0%, enabling the identification of single tumor cells with a resolution of 44.3 micrometers at 1350 nanometers for precise glioma resection. Postoperatively, the spatiotemporal-switchable function was activated for therapeutic intervention, in which the photothermal effect amplified the original efficiency of the catalase-like activity of Pt atoms by threefold, driving a surge in intracellular oxygen to combat tumor hypoxia. Upon 808-nanometer irradiation, the induced oxygen release in the tumor microenvironment amplified ICG-mediated photodynamic therapy, and combined with bismuthene-mediated photothermal therapy, it effectively inhibited residual tumors. In an orthotopic glioma mouse model, this approach minimized recurrence and achieved increased survival without inducing neurological or motor deficits. This work provides an atomic-level and molecular-level design blueprint for NIR-II nanotheranostic agents, paving the way toward clinical translation of single-cell–level precision medicine for brain malignancies.

The self‐assembly of chiral inorganic hierarchical materials plays a pivotal role in natural systems. With the precise construction of multi‐level chiral substances as the core, the efficient fabrication of chiral inorganic hierarchical materials and reveal the relationship between chiral structure and unique functionalities are crucial tasks in physics, chemistry, and biology, and chiral materials are achieved through the application of interdisciplinary approaches cutting‐edge technology. Thus, it is extremely important for the mechanisms and laws of chiral generation, transmission, amplification, and regulation are revealed, and the structure‐function relationship of chiral hierarchical materials is elucidated. This perspective first reviews and discusses the preparation methods of chiral hierarchical structures, chiral assembly, and chiral assembly films, and the recent developments in the geometric control of chiral inorganic hierarchical material, with special attention paid to the quantitative understanding of the chiroptical structure‐property relationship. Based on this, a series of important applications in chiral imaging, chiral encryption, and chiral detection are discussed. It is anticipated that advanced chiral inorganic hierarchical materials will provide superior chiroptical properties for various emerging technological applications.

Achieving precise control over the construction of efficient charge transport channels through self-assembly engineering represents a highly effective strategy for the synthesis of organic supramolecular photocatalysts. Herein, tetragonal zinc meso-5,10,15,20-tetra(4-pyridyl) porphyrin (ZnTPyP) nanorods (T-ZnTPyPs) and hexagonal ZnTPyP nanowires (H-ZnTPyPs) were synthesized by varying the assembly temperature. H-ZnTPyPs demonstrated a photocatalytic hydrogen production rate (183 mmol/g/h) that was 14.62 times greater than that of T-ZnTPyP (13 mmol/g/h). This significantly enhanced activity is primarily attributed to the distinct and well-defined molecular arrangements of H-ZnTPyPs, which support continuous linear long-range electron transfer pathways through effective π-π stacking. Conversely, the heat manipulation used in the synthesis of T-ZnTPyPs limits the participation of water molecules in the crystalline stacking arrangements, leading to lattice distortions that disrupt the π-π stacking interactions and significantly impede long-range electron transfer pathways. This research presents a novel strategy for modulating π-π stacking to optimize charge transport in supramolecular photocatalysts.

Glioblastoma is the most common and devastating brain tumor owing to its high invasiveness and high-frequency drug resistance. Near infrared-II (NIR-II) imaging-guided phototherapy based on polymer luminogens provides a promising remedy against drug-resistant glioma, but it is difficult to maximize photoenergy utilization. Herein, we designed a series of semiconducting polymers to boost the visualization and ablation of glioblastoma. By subtly engineering the side chains or substituents on the phenothiazine and thiophene moieties, an NIR-II polymer luminogen with high-quality fluorescence performance, good solubility, superior photothermal conversion, and balanced reactive oxygen species generation is achieved. The optimal polymer possesses a branched alkyl chain and tetraphenylethylene pendant to manipulate the equilibrium between the radiative and nonradiative energy-dissipating channels. High-sensitivity NIR-II imaging was used to monitor the blood-brain barrier penetration and glioma cell targeting of apolipoprotein E-modified polymer nanoparticles. The NIR irradiation triggers and maximizes the photon utilization in prominent photodynamic/photothermal synergistic therapy in orthotopic drug-resistant glioblastoma.

Photoactive artificial nanocatalysts that mimic natural photoenergy systems can yield clean and renewable energy. However, their poor photoabsorption capability and disfavored photogenic electron–hole recombination hinder their production. Herein, we designed two nanocatalysts with various microstructures by combining the tailored self-assembly of the meso-tetra(p-hydroxyphenyl) porphine photosensitizer with the growth of titanium dioxide (TiO₂). The porphyrin photoabsorption antenna efficiently extended the absorption range of TiO₂ in the visible region, while anatase TiO₂ promoted the efficient electron–hole separation of porphyrin. The photo-induced electrons were transferred to the surface of the Pt co-catalyst for the generation of hydrogen via water splitting, and the hole was utilized for the decomposition of methyl orange dye. The hybrid structure showed greatly increased photocatalytic performance compared to the core@shell structure due to massive active sites and increased photo-generated electron output. This controlled assembly regulation provides a new approach for the fabrication of advanced, structure-dependent photocatalysts.

Currently used drugs for glioblastoma (GBM) treatments are ineffective, primarily due to the significant challenges posed by strong drug resistance, poor blood-brain barrier (BBB) permeability, and the lack of tumor specificity. Here, we report two cationic fluorescent anticancer agents (TriPEX-ClO4 and TriPEX-PF6) capable of BBB penetration for efficient GBM therapy via paraptosis and ferroptosis induction. These aggregation-induced emission (AIE)-active agents specifically target mitochondria, effectively triggering ATF4/JNK/Alix-regulated paraptosis and GPX4-mediated ferroptosis. Specifically, they rapidly induce substantial cytoplasmic vacuolation, accompanied by reactive oxygen species generation and intracellular Ca2+ overload, thereby disrupting metabolisms and inducing non-apoptotic cell death. In vivo imaging revealed that TriPEX-ClO4 and TriPEX-PF6 successfully traversed the BBB to target orthotopic glioma and initiated effective synergistic therapy post-intravenous injection. Our AIE drugs emerged as the pioneering paraptosis inducers against drug-resistant GBM, significantly extending survival up to 40 days compared to temozolomide (20 days) in drug-resistant GBM-bearing mice. These compelling results open up new venues for the development of fluorescent anticancer drugs and innovative treatments for brain diseases.