Co-N-C single-atom nanozymes with oxidase-like activity for highly sensitive detection of biothiols.

Biothiol detection is of great importance for clinical disease diagnosis. Previous nanozyme-based colorimetric sensors for biothiol detection showed unsatisfactory catalytic activity, which led to a high detection limit. Therefore, developing new nanozymes with the high catalytic activity for biothiol detection is extremely necessary. Recently, single-atom nanozymes (SAzymes) have attracted much attention in biosensing due to their 100% atom utilization and excellent catalytic activity. Most previous works focus on the peroxidase-like activity of Fe-based SAzymes by using unstable and destructive H2O2 as the oxidant. It is essential to develop new SAzymes with high oxidase-like activity for biosensing to break through the limitation. Herein, Co-N-C SAzymes with high oxidase-like activity are explored. Furthermore, Co-N-C SAzymes are used as a biosensor for colorimetric detection of biothiols (GSH/Cys) based on the inhibition of thiols toward the oxidase-like activity of Co-N-C SAzymes, which showed high sensitivity with a low detection limit of 0.07 µM for GSH and 0.06 µM for Cys. Besides, the method showed good reproducibility and high selectivity against other amino acids. This work offers new insights using Co-N-C SAzymes in the biosensing field.

Engineering DNA/Fe-N-C single-atom nanozymes interface for colorimetric biosensing of cancer cells.

Single atom nanozymes (SAzymes) represent the state-of-the-art technology in nanomaterial-based catalysis, which have attracted attentions in catalysis, cancer treatment, disinfection and biosensing fields. However, numerous SAzymes suffered from low aqueous dispersion and without recognition capacity, which impeded their applications in bioanalysis. Herein, we engineered DNA onto SAzymes to obtain the DNA/SAzymes conjugates, which significantly improved the aqueous dispersion and recognition ability of SAzymes. We synthesized iron SAzymes (Fe-N-C SAzymes) as the catalytic nanomaterials, and investigated the interactions between Fe-N-C SAzymes and DNA. We compared A15, T15 and C15 adsorption of Fe-N-C SAzymes in HEPES containing 2 mM MgCl2. We found that 50 µg mL-1 Fe-N-C SAzymes produced nearly 100% A15 adsorption, 90% T15 adsorption and only 69% C15 adsorption, indicating that adenine and thymine had higher adsorption affinity on Fe-N-C SAzymes. More importantly, DNA modification did not affect the peroxidase-like activity of Fe-N-C SAzymes and the bioactivity of the adsorbed DNA. Taking the advantage of the diblock DNA with one DNA sequence (adenine) binding to Fe-N-C SAzymes and the other DNA sequence (i.e., aptamer) binding to cancer cells, we designed Apt/Fe-N-C SAzymes for colorimetric detection of cancer cells, which offered new insights for the use of SAzymes in biomedicine.