The influence of nanomaterials on the ecological environment is becoming an increasingly hot research field, and many researchers are exploring the mechanisms of nanomaterial toxicity on microorganisms. Herein, we studied the effect of two different sizes of nanosilver (10 nm and 50 nm) on the soil nitrogen fixation by the model bacteria Azotobacter vinelandii. Smaller size AgNPs correlated with higher toxicity, which was evident from reduced cell numbers. Flow cytometry analysis further confirmed this finding, which was carried out with the same concentration of 10 mg/L for 12 h, the apoptotic rates were20.23% and 3.14% for 10 nm and 50 nm AgNPs, respectively. Structural damage to cells were obvious under scanning electron microscopy. Nitrogenase activity and gene expression assays revealed that AgNPs could inhibit the nitrogen fixation of A. vinelandii. The presence of AgNPs caused intracellular reactive oxygen species (ROS) production and electron spin resonance further demonstrated that AgNPs generated hydroxyl radicals, and that AgNPs could cause oxidative damage to bacteria. A combination of Ag content distribution assays and transmission electron microscopy indicated that AgNPs were internalized in A. vinelandii cells. Overall, this study suggested that the toxicity of AgNPs was size and concentration dependent, and the mechanism of antibacterial effects was determined to involve damage to cell membranes and production of reactive oxygen species leading to enzyme inactivation, gene down-regulation and death by apoptosis.

Phenolic contaminants (R-OH) are a category of highly toxic organic compounds that are widespread in aquatic ecosystems and can induce carcinogenic risk to wildlife and humans; natural enzymes as green catalysts are capable of step-polymerizing these compounds to produce diverse macromolecular self-coupling products via radical-mediated C–C and C–O–C bonding at either the ortho- or para-carbon position, thereby evading the bioavailability and ecotoxicity of these compounds. Intriguingly, certain artificial metal and metal-oxide nanomaterials are known as nanozymes. They not only possess the unique properties of nanomaterials but also display intrinsic enzyme-mimicking activities. These artificial nanozymes are expected to surmount the shortcomings, such as low stability, easy inactivation, difficult recycling, and high cost, of natural enzymes, thus contributing to eco-environmental restoration. This review highlights the available studies on the enzymatic characteristics and catalytic mechanisms of natural enzymes and artificial metal and metal-oxide nanozymes in the removal and transformation of R-OH. These advances will provide key research directions beneficial to the multifunctional applications of artificial nanozymes in aquatic ecosystems.

This is the first comprehensive overview of laccase-triggered anabolism from fundamental theory to biotechnology applications. Laccase is a typical biological oxidordeuctase that induces the one-electronic transfer of diverse substrates for engendering four phenoxy radicals with concomitant reduction of O₂ into 2H₂O. In vivo, laccase can participate in anabolic processes to create multifarious functional biopolymers such as fungal pigments, plant lignins, and insect cuticles, using mono/polyphenols and their derivatives as enzymatic substrates, and is thus conducive to biological tissue morphogenesis and global carbon storage. Exhilaratingly, fungal laccase has high redox potential (E° = 500–800 mV) and thermodynamic efficiency, making it a remarkable candidate for utilization as a versatile catalyst in the green and circular economy. This review elaborates the anabolic mechanisms of laccase in initiating the polymerization of natural phenolic compounds and their derivatives in vivo via radical-based self/cross-coupling. Information is also presented on laccase immobilization engineering that expands the practical application ranges of laccase in biotechnology by improving the enzymatic catalytic activity, stability, and reuse rate. Particularly, advances in biotechnology applications in vitro through fungal laccase-triggered macromolecular biosynthesis may provide a key research direction beneficial to the rational design of green chemistry.