Adsorption of rare bases on transition metal doped γ-graphyne nanosheets: a DFT study†

Detection of rare bases (RBs) is key to understanding biological complexity, rapidly diagnosing genetic diseases and advancing personalized medicine. Electrochemical sensors are one of the most promising methods for RB detection, but their low responsiveness limits their effectiveness. Therefore, enhancing selectivity and sensitivity is necessary. γ-Graphyne (γ-GY) has garnered significant attention due to its sp² and sp hybrid carbon bonds and layered two-dimensional planar structure, as well as its extensive conjugated system, and sizable triangular hole. In this study, the structural characteristics, electronic properties, and sensing parameters of the adsorption involving RBs with both γ-GY and transition metal (Fe, Co, and Ni)-doped γ-graphyne (TM-GY) nanosheets are investigated using density functional theory calculations to evaluate the potential of nanosheets for sequencing RBs in DNA. The result shows that the adsorption interaction between RBs and γ-GY is weak physical adsorption, making it difficult to distinguish RBs. In contrast, the adsorption of RBs with TM-GY is stronger chemisorption and can be completely separated by translocation time and sensing response. Through translocation time calculations, we demonstrate the high selectivity of Ni-GY for RBs. Furthermore, sensitivity analysis reveals that Fe-GY exhibits excellent responsiveness to RBs. Our work reveals that the TM-GY nanosheets hold promise for detecting RBs compared with the γ-GY, and may provide valuable insights for the design of graphyne-based biosensors and catalysts.