Design and synthesis of heterobimetallic donor-acceptor chemodosimetric ensembles for the detection of sulfhydryl-containing amino acids and peptides.

A competitive indicator displacement assay has been successfully developed for the ratiometric determination of sulfhydryl-containing amino acids and peptides using heterobimetallic donor-acceptor complexes as chemodosimetric ensembles. Chromotropic cis-[ML2(CN)2](M = FeII, RuII, OsII; L = diimine) are used as signaling indicators and PtII(DMSO)Cl2 acceptor moiety is used as the receptor for the sulfhydryl-containing analytes. A series of three heterobimetallic donor-acceptor complexes: cis-FeII(bpy)2[CN-PtII(DMSO)Cl2]2 (1), cis-Ru(II)(bpy)2[CN-PtII(DMSO)Cl2]2 (2) and cis-Os(II)(bpy)2[CN-PtII(DMSO)Cl2]2 (3) are synthesized and characterized by X-ray crystallography. All the three ensembles are able to produce specific colorimetric/fluorimetric responses to sulfhydryl-containing amino acids (cysteine, homocysteine and methionine) as well as the sulfhydryl-containing small peptide glutathione. The mechanism of the competitive displacement assay is evaluated by examining the thermodynamics of formation of the donor-acceptor linkage and adducts between the acceptor metal and the sulfhydryl-containing analytes as well as by systematic variation of the donor and acceptor metals in the chemodosimetric ensembles.