A Thiophene Functionalized Hf(IV)-Organic Framework for the Detection of Anti-Neoplastic Drug Flutamide and Biomolecule Hemin and Catalysis of Friedel-Crafts Alkylation.

Abstract

Development, rapid detection and quantification of anticancer drugs in biological samples are crucial for effective drug monitoring. The present work describes the design of a Hf(IV)-based metal-organic framework (MOF) (1) by the reaction between Hf(IV) ion and 2-(thiophene-2-carboxamido)terephthalic acid linker with the surface area of 571 m2 g-1. Desolvated MOF (1') displayed highly discriminative fluorescence sensing properties for the antineoplastic drug flutamide and biomolecule hemin in an aqueous medium in the presence of co-existing biomolecules and ions. The MOF's response time for sensing flutamide and hemin was less than 5 s with low detection limits of 1.5 and 0.08 nM, respectively. Additionally, 1' also demonstrated recyclability up to five cycles and maintained its sensing ability across different pH media, various water samples, and biological fluids. Experimental and theoretical analyses suggested photoinduced electron transfer and inner-filter effect in the presence of flutamide and Förster resonance energy transfer in the presence of hemin are most likely reasons behind the fluorescence quenching of MOF. Furthermore, the MOF demonstrated catalytic activity in Friedel-Crafts alkylation reactions, providing a 96 % yield with slight decay in its activity over four uses. The enhanced activity of 1' compared to Hf-BDC and Hf-BDC-NH2 (BDC: 1,4-benzenedicarboxylic acid) is due to the functionalized thiophene moieties through hydrogen bond donating sites, confirmed by a series of control experiments.