Ordered-Pore-Structure Engineering of Dual-Emissive Lanthanide-Based Metal–Organic Frameworks for Boosting Sensing Performance of Tumor Marker

Accurate identification of tumor metabolic markers is of great significance for the early screening of cancer. Luminescent lanthanide-based metal-organic frameworks (Ln-MOFs) are a fascinating assay platform for biomarkers, but the influence of their pore parameters on detection performance remains largely unexplored due to the lack of Ln-MOFs with an adjustable micro- and mesoporous structure. Herein, two isoreticular dual-emissive Ln-MOF-based sensors with microporous and hierarchically micromesoporous structures, namely, Eu-MMOF-BTC and Eu-HMMOF-BTC, respectively, are first constructed to systematically investigate their detection properties for adenosine (ADO, an important tumor marker in the diagnosis and prognosis of cancer). Remarkably, compared with the Eu-MMOF-BTC with micropores only, the Eu-HMMOF-BTC featuring both intrinsic micropores and large ordered mesopores affords greatly enhanced photoresponse efficiency and sensitivity toward ADO under both signal channels, benefiting from the facilitated access to active sites and improved preconcentration. Moreover, such an optimized dual-channel Eu-HMMOF-BTC sensor realizes real-time (15 s) and specific recognition of ADO in a complex urine environment without the interference of coexisting species, inherently improving the analysis reliability and accuracy. This study not only provides a facile strategy to regulate the sensing performance of MOF-based probes by ordered-pore-structure engineering but also provides inspiration for the design of high-accuracy probes for the noninvasive early screening of cancers.