Hierarchical Self‐Assembly Molecular Building Blocks as Intelligent Nanoplatforms for Ovarian Cancer Theranostics

Hierarchical self‐assembly from simple building blocks to complex polymers is a feasible approach to constructing multi‐functional smart materials. However, the polymerization process of polymers often involves challenges such as the design of building blocks and the drive of external energy. Here, a hierarchical self‐assembly with self‐driven and energy conversion capabilities based on p‐aminophenol and diethylenetriamine building blocks is reported. Through β‐galactosidase (β‐Gal) specific activation to the self‐assembly, the intelligent assemblies (oligomer and superpolymer) with excellent photothermal and fluorescent properties are dynamically formed in situ, and thus the sensitive multi‐mode detection of β‐Gal activity is realized. Based on the overexpression of β‐Gal in ovarian cancer cells, the self‐assembly superpolymer is specifically generated in SKOV‐3 cells to achieve fluorescence imaging. The photothermal therapeutic ability of the self‐assembly oligomer (synthesized in vitro) is evaluated by a subcutaneous ovarian cancer model, showing satisfactory anti‐tumor effects. This work expands the construction of intelligent assemblies through the self‐driven cascade assembly of small molecules and provides new methods for the diagnosis and treatment of ovarian cancer. Inspired by biological self‐assembly in nature, a novel hierarchical self‐assembly polymer with fluorescence and photothermal properties is proposed. The self‐assembly process is activated under the specific action of enzymes, enabling dual‐mode liquid biopsy and in vitro selective imaging. The polymer achieves tumor ablation through photothermal treatment. The intelligent polymer self‐assembly platform enables the diagnosis and treatment of ovarian cancer.