Polyoxometalates for bifunctional applications: Catalytic dye degradation and anticancer activity.

Improving the efficiencies of organic compound degradations by catalytic materials is a challenging materials research field. In our research, we successfully synthesized cobalt-based polyoxometalates (CoV-POMs) via a simple crystallization-driven self-assembly method. The incorporation of the newly synthesized CoV-POMs into peroxymonosulphate (PMS), forming a mixture, greatly enhancing the catalytic activation for a complete degradation of dye solution. The positive synergic effect between CoV-POMs and PMS was substantiated by a relatively meager degradation of less than 10% in the system without CoV-POMs, in which CoV-POMs played a vital role to activate PMS towards free radicals generation for dye degradation. Methylene blue (MB) and rhodamine B (RB) dyes were completely decolorized under 60 min with the presence of 40 mg/L CoV-POMs and 150 mg/L PMS. The CoV-POMs/PMS system was pH dependance with a lower dye degradation efficiency at elevated pH. The effect of pH was more prominent in RB dye, in which the degradation efficiency dropped drastically from 93.3% to 41.12% with the increase in the solution pH from 7 to 11. The quenching tests suggested that sulfate radicals were the dominant active species involving in the dye degradation reaction. Besides MB and RB dyes, CoV-POMs/PMS system also showed significant activity towards the degradation of phenol red (PR) and methyl orange (MO) dyes. In the biological test, CoV-POMs exhibited non-toxic behavior towards normal cells that reduced safety concern for the large-scale wastewater treatment application. In addition, the testing divulged the anticancer property of CoV-POMs with more than 35 % of A549 lung adenocarcinoma and MDA-MB-231 breast adenocarcinoma were killed with 250 mg/L CoV-POMs. The selective lethality of CoV-POMs towards cancer cells was found to be caused by different extents of cellular apoptosis. In overall, the synthesized bifunctional CoV-POMs manifested superior activities in the examined applications, specifically dye degradation and anticancer.

Diatom-inspired 2D nitric oxide releasing anti-infective porous nanofrustules.

Two-dimensional (2D) nanomaterials (NM) have emerged as promising platforms for antibacterial applications. However, the inherent "flatness" of 2D NM often limits the loading of antimicrobial components needed for synergistic bactericidal actions. Here, inspired by the highly ornamented siliceous frustules of diatoms, we prepared 2D ultrathin (<20 nm) and rigid "nanofrustule" plates via the out-of-plane growth of cetyltrimethylammonium bromide (CTAB) directed silica mesostructures on the surfaces of 2D graphene oxide nanosheets. The nanofrustules were characterized by the presence of mesoporous channels with a pore size of 3 nm and a high specific surface area of 674 m2 g-1. S-nitrosothiol-modification on the silica surfaces enables the development of a novel anti-infective nitric oxide (NO) releasing NO-nanofrustule system. The cage-like mesoporous silica architecture enabled a controlled and sustainable release of NO from the NO-nanofrustules under physiological conditions. The NO-nanofrustules displayed broad antibacterial effects against Staphylococcus aureus and Escherichia coli with a minimum inhibitory concentration of 250 µg ml-1. Mechanistic studies revealed that the antibacterial property of NO-nanofrustules was attained via a unique "capture-and-release" mode-of-action. The first step entailed the capture of the bacteria by the NO-nanofrustules to form micro-aggregates. This was followed by the release of high levels of NO to the captured bacteria to elicit a potent anti-infective effect. In combination with the lack of cytotoxicity in human dermal cells, the 2D hybrid NO-nanofrustules may be utilized to combat wound infections in clinical settings.