High Sensitive and Discriminating Colorimetric Assay for S2- Overload in Adaptogenic Herbs Utilizing ZnS Nanoparticle-Enhanced S, N-Doped Eggshell Membrane-Derived Biochar

Background

With the rapid development of industrialization, the excessive emission of S²⁻ have become increasingly serious, leading to a surge in the content of S²⁻ in nature. Rapid and accurate detection of S^2- contamination in natural adaptogens is crucial for food safety. Annually, discarded eggshell waste, rich in organic and inorganic materials, poses environmental risks if landfilled. Utilizing waste eggshell membrane biomass for S^2- detection is cost-effective, yet designing biochar materials for sensors requires balancing catalytic enhancement and anti-interference capabilities. Improving the catalytic performance of biochar for colorimetric S^2- detection without metal ion interference presents a challenging issue.

Results

We first modified biochar (EBc) derived from waste eggshell membranes using a combination of thiourea and ZnS nanoparticles, fabricating ZnS-decorated, S-N co-doped biochar (ZnS-SN-EBc) nanozymes, which were applied for the colorimetric assay detection of S^2- contamination. The addition of thiourea significantly increases the proportion of pyridinic-N in biochar, enhancing the peroxidase-like activity of the nanozyme. The growth of ZnS nanoparticles on the biochar not only enhances the catalytic performance by increasing the S content but also reduces the content of oxidized S, thereby improving resistance to interference. The detection range for S^2- was expanded from 0.1 to 45 μM for EBc to 0.05 to 225 μM for ZnS-SN-EBc, and the limit of detection improved to 0.0397 μM. Additionally, ZnS-SN-EBc significantly enhanced metal ion interference resistance. S^2- detection in five types of adaptogenic herbs verified the accuracy and practicality of the colorimetric assay, with recovery rates comparable to national standards.

Significance

We innovatively repurposed waste eggshell membranes to develop a selective and catalytic peroxidase-like nanozyme, ZnS-decorated S-N co-doped biochar (ZnS-SN-EBc). The developed colorimetric assay utilizing ZnS-SN-EBc demonstrates significant potential for the detection of sulfur ions in adaptogenic herbs, thus contributing to both waste resource utilization and the advancement of food safety detection technologies.