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.

中文翻译：

---

稀有碱基在过渡金属掺杂γ-石墨炔纳米片上的吸附：DFT 研究


稀有碱基 （RB） 的检测是了解生物学复杂性、快速诊断遗传疾病和推进个性化医疗的关键。电化学传感器是最有前途的 RB 检测方法之一，但其低响应性限制了其有效性。因此，提高选择性和灵敏度是必要的。γ-石墨炔 （γ-GY） 因其 sp² 和 sp 杂化碳键和层状二维平面结构，以及广泛的共轭系统和相当大的三角形空穴而受到广泛关注。在本研究中，使用密度泛函理论计算研究了涉及 γ-GY 和过渡金属 （Fe、Co 和 Ni） 掺杂 γ-graphyne （TM-GY） 纳米片的 RBs 的吸附结构特性、电子性质和传感参数，以评估纳米片在 DNA 中 RBs 测序的潜力。结果表明，RBs与γ-GY之间的吸附相互作用是弱物理吸附，难以区分RBs。相比之下，TM-GY 对 RBs 的吸附具有更强的化学吸附能力，可以通过易位时间和感应响应完全分离。通过易位时间计算，我们证明了 Ni-GY 对 RBs 的高选择性。此外，敏感性分析表明 Fe-GY 对 RB 表现出优异的响应性。我们的工作表明，与 γ-GY 相比，TM-GY 纳米片有望检测 RBs，并可能为石墨炔基生物传感器和催化剂的设计提供有价值的见解。