Electrochemical Sensing Behavior of Graphdiyne Nanoflake Toward Uric Acid; A Quantum Chemical Approach

Abstract Though, the gas sensing applications of graphdiyne have widely reported; however, the biosensing utility of graphdiyne needs to be explored. This study deals with the sensitivity of graphdiyne nanoflake (GDY) towards the uric acid (UA) within the density functional framework. The uric acid is allowed to interact with graphdiyne nanoflake from all the possible orientations. Based on these interacting geometries, the complexes are differentiated with naming i.e., UA1@GDY, UA2@GDY, UA3@GDY and UA4@GDY (Figure 1). The essence of interface interactions of UA on GDY is derived by computing geometric, energetic, electronic and optical properties. The adsorbing affinity of complexes is evaluated at ωB97XD/6-31+G(d,p) level of theory. The stabilities of the complexes are quantified through the interaction energies (Eint) with reasonable accuracy. The calculated Eint of the UA1@GDY, UA2@GDY, UA3@GDY and UA4@GDY complexes are -31.13, -25.87, -20.59 and -16.54 kcal/mol, respectively. In comparison with geometries, it is revealed that the higher stability of complexes is facilitated by π-π stacking. Other energetic analyses including symmetry adopted perturbation theory (SAPT0), noncovalent interaction index (NCI) and quantum theory of atoms in molecule (QTAIM) provided the evidence of dominating dispersion energy in stabilizing the resultant complexes. The HOMO-LUMO energies, NBO charge transfer and UV-vis analysis justify the higher electronic transition in UA1@GDY, plays a role of higher sensitivity of GDY towards the π-stacked geometries over all other possible interaction orientations. The present findings bestow the higher sensitivity of GDY towards uric acid via π-stacking interactions.