Multidentate ligand approach for conjugation of perovskite quantum dots to biomolecules

Building compatible surface on perovskite quantum dots (PQDs) for applications like sensing analytes in aqueous medium is highly challenging and if achieved by simple means can revolutionize disease diagnostics. The present work reports the surface engineering of CsPbBr₃ QDs via "simple ligand exchange process" to achieve water-compatible QDs towards detection of biomolecules. The monodentate oleic acid ligand in CsPbBr₃ QDs is exchanged with dicarboxylic acid containing (bidentate) ligands such as folic acid (FA), ethylenediamine tetra-acetic acid (EDTA), succinic acid (SA) and glutamic acid (GA) to develop an efficient water-compatible PQD-ligand system. optical and theoretical studies showed the existence of a stronger binding between the perovskite and succinic acid ligand as compared to oleic acid (OA) and all other ligands. Replacement of OA with SA and retention of crystal structure is validated using spectroscopic and microscopic tools. It is observed that SA ligands facilitate better electronic coupling with PQDs and show significant improvement in fluorescence and stability. Further N-Hydroxy succinimide (NHS), which is a well-known compound to activate carboxyl groups, is used to bind onto SA PQDs as multidentate ligand, to form water stable PQDs. SA PQDs react with NHS (in water) to form multidentate ligand passivated PQDs that show very high photoluminescence (PL) as compared to OA PQDs in toluene. This also results in the formation of an NHS ester that allows bioconjugation with PQDs. This simple probe in water is further utilized for sensing a highly hydrophilic bovine serum albumin (BSA) protein as a model target to demonstrate the potential and effectiveness of this process to create compatible QDs for the successful conjugation of biomolecules. Although the focus of this work is to demonstrate bioconjugation and not achieving higher sensitivity levels, the intrinsic sensing level of these compatible QDs towards BSA shows a detection limit of 51.47 nM, which is above par with other reports in literature.