Covalently grafting first-generation PAMAM dendrimers onto MXenes with self-adsorbed AuNPs for use as a functional nanoplatform for highly sensitive electrochemical biosensing of cTnT

Abstract

2D MXene-Ti3C2Tχ has demonstrated promising application prospects in various fields; however, it fails to function properly in biosensor setups due to restacking and anodic oxidation problems. To expand beyond these existing limitations, an effective strategy to for modifying the MXene by covalently grafting first-generation poly(amidoamine) dendrimers onto an MXene in situ (MXene@PAMAM) was reported herein. When used as a conjugated template, the MXene not only preserved the high conductivity but also conferred a specific 2D architecture and large specific surface areas for anchoring PAMAM. The PAMAM, an efficient spacer and stabilizer, simultaneously suppressed the substantial restacking and oxidation of the MXene, which endowed this hybrid with improved electrochemical performance compared to that of the bare MXene in terms of favorable conductivity and stability under anodic potential. Moreover, the massive amino terminals of PAMAM offer abundant active sites for adsorbing Au nanoparticles (AuNPs). The resulting 3D hierarchical nanoarchitecture, AuNPs/MXene@PAMAM, had advanced structural merits that led to its superior electrochemical performance in biosensing. As a proof of concept, this MXene@PAMAM-based nanobiosensing platform was applied to develop an immunosensor for detecting human cardiac troponin T (cTnT). A fast, sensitive, and highly selective response toward the target in the presence of a [Fe(CN)6]3−/4− redox marker was realized, ensuring a wide detection of 0.1–1000 ng/mL with an LOD of 0.069 ng/mL. The sensor’s signal only decreased by 4.38% after 3 weeks, demonstrating that it exhibited satisfactory stability and better results than previously reported MXene-based biosensors. This work has potential applicability in the bioanalysis of cTnT and other biomarkers and paves a new path for fabricating high-performance MXenes for biomedical applications and electrochemical engineering.