Photochemically Enhanced Selective Adsorption of Gold Ions on Tannin-Coated Porous Polymer Microspheres.

Metal recovery from electronic waste and industrial wastewater has attracted increasing attention to recycle precious metals and inhibit the emission of hazardous heavy metals. However, the selective recovery of precious metals with a large quantity is still very challenging because wastewater contains a variety of different cations while precious metal ions are relatively scarce. Here, we introduce a simple method to selectively increase the adsorption of gold ions using tannin-coated porous polymer microspheres through photochemical reduction. Mesoporous poly(ethylene glycol dimethacrylate- co-acrylonitrile) microspheres with an average pore diameter of 13.8 nm were synthesized and used as an adsorbent matrix. Tannic acid (TA) was deposited onto the internal pores of the polymer matrix by simple immersion in an aqueous milieu. TA coatings increased the maximum number of adsorbed gold ions by 1.3 times because of the well-known metal ion chelation of TA. Under light illumination, the maximum number of adsorbed gold ions dramatically increased by 6.1 times. We examined two distinct mechanisms presumably involved in the enhanced adsorption: the photooxidation of TA and plasmon-induced hot electrons. Moreover, TA-coated microspheres exhibited remarkable selectivity for gold ions among competing metal ions commonly found in waste resources. This work suggests that the photochemically activated TA can serve as an excellent adsorbent for the selective and efficient recovery of gold ions from wastewater.

Tannin-Titanium Oxide Multilayer as a Photochemically Suppressed Ultraviolet Filter.

UV filters can initiate redox reactions of oxygen and water when exposed to sunlight, generating reactive oxygen species (ROS) that deteriorate the products containing them and cause biological damages. This photochemical reactivity originates from the high chemical potential of UV filters, which also determines the optical properties desirable for sunscreen applications. We hypothesize that this dilemma can be alleviated if the photochemical pathway of UV filters is altered to coupling with redox active molecules. Here, we employ tannic acid (TA) as a key molecule for controlling the photochemical properties of titanium dioxide nanoparticles (TiO2 NPs). TA provides an unusual way for layer-by-layer assembly of TiO2 NPs by the formation of a ligand-to-metal charge transfer complex that alters the nature of UV absorption of TiO2 NPs. The galloyl moieties of TA efficiently scavenge ROS due to the stabilization of ROS by intramolecular hydrogen bonding while facilitating UV screening through direct charge injection from TA to the conduction band of TiO2. The TiO2-TA multilayers assembled in open porous polymer microspheres substantially increased sun protection while dramatically reducing ROS under UV exposure. The assembled structure exhibits excellent in vivo anti-UV skin protection against epidermal hyperplasia, inflammation, and keratinocyte apoptosis without long-term toxicity.

Morphological Evolution of Gold Nanoparticles into Nanodendrites Using Catechol-Grafted Polymer Templates.

Morphology, dimension, size, and surface chemistry of gold nanoparticles are critically important in determining their optical, catalytic, and photothermal properties. Although many techniques have been developed to synthesize various gold nanostructures, complicated and multistep procedures are required to generate three-dimensional, dendritic gold nanostructures. Here, we present a simple method to synthesize highly branched gold nanodendrites through the well-controlled reduction of gold ions complexed with a catechol-grafted polymer. Dextran grafted with catechols guides the morphological evolution as a polymeric ligand to generate dendritic gold structures through the interconnection of the spherical gold nanoparticles. The reduction kinetics, which is critical for morphological changes, is controllable using dimethylacetamide, which can decrease the metal-ligand dissociation and gold ion diffusivity. This study suggests that mussel-inspired polymer chemistry provides a simple one-pot synthetic route to colloidal gold nanodendrites that are potentially applicable to biosensing and catalysis.

Bioinspired Synthesis of Mesoporous Gold-silica Hybrid Microspheres as Recyclable Colloidal SERS Substrates.

Noble metal nanostructures have been intensively investigated as active substrates for surface-enhanced Raman spectroscopy (SERS) from visible to near-IR wavelengths. However, metal nanoparticle-based SERS analysis in solutions is very challenging due to uncontrollable and irreproducible colloid aggregation. Here we report the templated synthesis of porous gold-silica hybrid microspheres and their application as reusable colloidal SERS substrates. Mesoporous polymer microspheres are synthesized and used as templates for the synthesis of non-aggregated gold nanoparticles, followed by polydopamine-mediated silicification to fabricate mesoporous gold-silica hybrid microspheres. The mesoporous hybrid particles detect crystal violet in the order of 10-8 M and provide the structural durability of the immobilized gold nanoparticles, allowing them to be recycled for repeated SERS analyses for analytes in a solution with the similar sensitivity. This work suggests that the mesoporous gold-silica hybrid microspheres are attractive SERS substrates in terms of reusability, sensitivity, and stability.