Chemical transformations of nanoscale zinc oxide in simulated sweat and its impact on the antibacterial efficacy

Abstract Nanoscale zinc oxide (n-ZnO) is widely used in personal care products and textiles, thus, it would likely be released into human sweat. To better evaluate the potential human health risks of n-ZnO, it is essential to understand its chemical transformations in physiological solutions, such as human sweat, and the resulting changes in the n-ZnO bioavailability. Here, two types of n-ZnO, ZnO nanoparticles (ZnO-NPs) and nanorod-based ZnO nanospheres (ZnO-NSs) were synthesized and incubated in 3 types of simulated sweat with different pH values and phosphate concentrations. The content of Zn3(PO4)2 in the transformed n-ZnO was quantified by selective dissolution of Zn3(PO4)2 in 0.35 M ammonia solution where 100% and 5.5% of Zn3(PO4)2 and ZnO were dissolved, respectively. The kinetics analysis indicated that by 24-48 h the content of Zn3(PO4)2 reached the maximum, being 15-21% at pH 8.0 and 45-70% at pH 5.5 or 4.3. Interestingly, no correlation was observed between the rate constants of Zn3(PO4)2 formation and the specific surface areas of n-ZnO, implying that chemical transformations from n-ZnO to Zn3(PO4)2 in the simulated sweat might not be simply attributed to dissolution and precipitation. Using a variety of characterization techniques, we demonstrated the formation of a ZnO-Zn3(PO4)2 core-shell structure with the shell consisting of amorphous Zn3(PO4)2 at pH 8.0 and additionally of crystalline Zn3(PO4)2 and Zn3(PO4)2•4H2O at pH 5.5 or 4.3. The phosphate-induced transformation of n-ZnO in the simulated sweat at pH 5.5 and 4.3 greatly reduced the antibacterial efficacy of n-ZnO through moderating the nanoparticle dissolution, indicating limited bioavailability of the NPs upon transformation. The results improve the understanding of the fate and hazards of n-ZnO.