Transferrin guided quasi-nanocuboid as tetra-enzymic mimics and biosensing applications

Given the promising prospect of nanozymes system with multi-enzyme mimetic activities, it is also a challenge for designing a controllable nanostructure as multi-enzymes mimics by protein-guided strategy. Here, transferrin (Trf)-directed manganese oxide with 3D nanomorphology was developed. Trf-Mn₃O₄ quasi-nanocuboids (NCs) was obtained by improved conditions for biomineralization, which employing Trf as biotemplate and Mn²⁺ as metal source in alkaline solution. Fortunately, not only was the controllable structure discovered, but Trf-Mn₃O₄ NCs also showed tetra-enzyme mimic activities involving peroxidase-, ascorbic acid oxidase-, catalase- and superoxide dismutase-mimic activities. Further, the catalytic properties and steady-state kinetic of Trf-Mn₃O₄ NCs was explored, systematically. Moreover, we develop simple colorimetric sensor based on the peroxidase-mimic activity of Trf-Mn₃O₄ NCs for the detection of gallic acid (GA) with the linear range within 0.1-40 μΜ, and the limit of detection was 41.2 nM (S/N = 3). Besides, a novel fluorimetric sensor for the detection of AA based on the ascorbic acid oxidase-mimic activity was proposed with the linear range of 0.5 μM-10 μM (R² = 0.9906) and 10 μM-5 mM (R² = 0.9927), and LOD of 0.24 μM (S/N = 3) was obtained. Both the proposed sensors showed outstanding detection performance, accuracy and repeatability, which realized the detection of GA and AA in real sample, respectively. The as-synthesized tetra-enzymic mimics not only enriched the species of nanozymes, particularly for the nanozymes with multi-enzyme mimic activities, the proposed sensors showed promising potential applications for biosensor in complex samples.