Remarkably selective and enantiodifferentiating sensing of histidine by a fluorescent homochiral Zn-MOF based on pyrene-tetralactic acid

Abstract

A highly luminescent and water-stable homochiral Zn-MOF, i.e., Zn-PLA, has been developed based on a pyrene-tetralactic acid, which inherently features concave shapes for guest inclusion, to explore sensing of amino acids by fluorescence quenching; the solid-state fluorescence quantum yield of the MOF was found to be 46%. The fluorescence of an aqueous suspension of Zn-PLA was shown to be quenched specifically by histidine amongst all the other amino acids. Selective sensing of histidine is of prime importance due to its relevance in a variety of biological functions. The lack of quenching of fluorescence of Zn-PLA by all the amino acids other than histidine has been rationalized based on the exchange of the cationic dimethylammonium species in the MOF crystals with histidine that is protonated in water; the latter is envisaged to quench the fluorescence via charge transfer in the excited state. Furthermore, the homochiral crystals of Zn-PLA were found to permit enantiodiscrimination in the quenching by the d- and l-forms such that the ratio of enantioselectivity, i.e., Kd/Kl, is 1.8, as determined by Stern-Volmer quenching plots. The highly selective as well as enantiodifferentiating sensing of amino acids by MOFs is unprecedented for any sensor type.