Biphasic interface templated synthesis of wrinkled MOFs for the construction of cascade sensing platform based on the encapsulated gold nanoclusters and enzymes

The design and construction of MOFs with flower-like structure could afford sufficient space for the immobilization of guests with large size and interconnected transport channels for their mass diffusion although it remains a challenge. Herein, wrinkled Ce-based hierarchically porous UiO-66 (Ce-WUiO-66) with good crystallinity was successfully synthesized for the first time using bicontinuous emulsion composed of 1-heptanol, water and F127 (PEO₁₀₆PPO₇₀PEO₁₀₆) surfactant as a template. F127 played a key role in the formation of emulsions as a stabilizer, and meanwhile its PEO segments interacted with MOF precursors to guide the evolvement of crystallized pore walls. Through controlling the ratios of heptanol to water and the salinity, the distances of the pleat openings and the morphology of the resultant Ce-WUiO-66 were facilely regulated. In virtue of its highly open radial structure, Ce-WUiO-66 could serve as an ideal platform for loading multiple substances to build a cascade sensing system. As a proof of concept, we designed an amino acid (AA) cascade probe by co-immobilizing gold nanoclusters (AuNCs) and LAA oxidase into Ce-WUiO-66. The aggregation-induced-emission enhancement resulted from the encapsulation of AuNCs into Ce-WUiO-66 significantly improved the detection sensitivity and the detection limit of corresponding substrates reached as low as 10^-8 M. The proposed biphasic interface assembly strategy is hopefully to provide a new route for the rational design of MOFs with various open pore structure and broaden their potential applications with multiple large-size substances involved besides the currently exemplified cascade sensing platform.