Effect of Anion-Directed Structural Tuning of Triazole-Containing Ag(I) Coordination Polymers for "Turn-on" Sensing of the Disulfide (-S-S-) Amino Acid over the Monosulfide (-SH) Form: Experiments and DFT Corroboration.

Abstract

Identification of disulfide-peptide-bond-containing glutathione (GSSG) over the monosulfide form (GSH) remains a very challenging task because of their identical chemical properties. Although GSH detection has been well documented, selective detection of GSSG has rarely been reported. Here, four cationic Ag-based coordination polymers (Ag CPs) were synthesized using newly synthesized monotriazole linker 3-amino-5-(4H-1,2,4-triazol-4-yl)pyridine to selectively screen GSSG over GSH. The judicious choice of the counteranion in the metal salt changes the architecture, which affects the detection limit at the parts per million level. The restriction of the photoinduced electron transfer process is the driving reason for the enhancement of the fluorescence, owing to the favorable energy band gap match of the Ag CPs with GSSG over GSH. The de novo strategy for incorporating polar heteroatoms (N) into the CP network plays a pivotal role in the host-guest noncovalent interactions with donor-acceptor transfer of electrons, which was supported by X-ray photoelectron spectroscopy and density functional theory studies. The Ag CPs are thermochemically robust, recyclable, and work efficiently in a very short time (within ∼14-18 s) in different pH ranges. Additionally, detection of GSSG in serum samples was carried out with appreciable detection limits and recovery percentages (94.40-117.89%).