Bimetallic Zeolitic Imidazolate Framework as an Intrinsic Two-Photon Fluorescence and pH-Responsive MR Imaging Agent

Zeolitic imidazolate framework-8 (ZIF-8) has received wide attention in recent years as a potential drug vehicle for the treatment of cancer due to its acid-responsiveness and moderate biocompatibility. However, its congenital deficiency of intrinsic imaging capability limits its wider applications; therefore, a postsynthetic exchange approach was utilized to introduce paramagnetic manganese­(II) ions into the ZIF-8 matrix. As a result, bimetallic zeolitic imidazolate frameworks (Mn–Zn–ZIF) were thus fabricated and exhibited pH-responsive T1-weighted magnetic resonance imaging (MRI) contrast effect. Remarkably, we also found its own fluorescence derived from 2-methylimidazole, which is the first report of the intrinsic two-photon fluorescence imaging of ZIFs to our knowledge. Mn–Zn–ZIF still preserves the original properties of ZIF-8 of high surface areas, microporosity, and acid sensitivity. After further PEGylation of Mn–Zn–ZIF, the nanoparticles showed no obvious toxicity and its MRI contrast effect has also been enhanced. Our work highlights the promise of modified zeolitic imidazolate frameworks as potential cancer theranostic platforms.