Recent Applications of Melanin-like Nanoparticles as Antioxidant Agents

Nanosized antioxidants are highly advantageous in terms of versatility and pharmacokinetics, with respect to conventional molecular ones. Melanin-like materials, artificial species inspired by natural melanin, combine recognized antioxidant (AOX) activity with a unique versatility of preparation and modification. Due to this versatility and documented biocompatibility, artificial melanin has been incorporated into a variety of nanoparticles (NP) in order to give new platforms for nanomedicine with enhanced AOX activity. In this review article, we first discuss the chemical mechanisms behind the AOX activity of materials in the context of the inhibition of the radical chain reaction responsible for the peroxidation of biomolecules. We also focus briefly on the AOX properties of melanin-like NP, considering the effect of parameters such as size, preparation methods and surface functionalization on them. Then, we consider the most recent and relevant applications of AOX melanin-like NPs that are able to counteract ferroptosis and be involved in the treatment of important diseases that affect, e.g., the cardiovascular and nervous systems, as well as the kidneys, liver and articulations. A specific section will be dedicated to cancer treatment, since the role of melanin in this context is still very debated. Finally, we propose future strategies in AOX development for a better chemical understanding of melanin-like materials. In particular, the composition and structure of these materials are still debated, and they present a high level of variability. Thus, a better understanding of the mechanism behind the interaction of melanin-like nanostructures with different radicals and highly reactive species would be highly advantageous for the design of more effective and specific AOX nano-agents

Extending photocatalysis to the visible and NIR: The molecular strategy

Photocatalysis exploits light to perform important processes as solar fuel production by water splitting, and CO2 reduction or water and air decontamination. Therefore, photocatalysis contributes to the satisfaction of the increasing needs for clean energy, environmental remediation and, most recently, sanification. Most of the efficient semiconductor nanoparticles (NP), developed as photocatalysts, work in the ultraviolet (UV) spectral region and they are not able to exploit either visible (Vis) or near infrared (NIR) radiation. This limitation makes them unable to fully exploit the broad band solar radiaton or to be applied in indoor conditions. Recently, different approaches have been developed to extend the spectral activity of semiconductor NP, like for example band-gap engineering, integration with upconversion NP and plasmonic enhancement involving also hot-electron injection. Nevertheless, the use of organic molecules and metal complexes, for enhancing the photoactivity in the Vis and NIR, was one of the first strategies proposed for sensitization and it is still one of the most efficient. In this minireview we highlight and critically discuss the most recent and relevant achievements in the field of photocatalysis obtained by exploiting dye sensitization either via dynamic or static quenching

Local Light-Controlled Generation of Calcium Carbonate and Barium Carbonate Biomorphs via Photochemical Stimulation

The authors thank the European Research Council under the European Union's Seventh Framework Program (FP7/20072013)/ERC grant agreement no 340863 and ERC PoC LACRYS (837874) as well as Junta de Andalucia for financing the project P18-FR-5008. HC thanks the Deutsche Forschungsgemeinschaft DFG for financial support of the work on Biomorphs (CO 194/28-1). M.M., A.M., and A.M.-P. thank MIUR, (PRIN 2017) 2017E44A9P. Open access funding enabled and organized by Projekt DEAL.Photochemical activation is proposed as a general method for controlling the crystallization of sparingly soluble carbonates in space and time. The photogeneration of carbonate in an alkaline environment is achieved upon photo-decarboxylation of an organic precursor by using a conventional 365 nm UV LED. Local irradiation was conducted focusing the LED light on a 300 μm radius spot on a closed glass crystallization cell. The precursor solution was optimized to avoid the precipitation of the photoreaction organic byproducts and prevent photo-induced pH changes to achieve the formation of calcium carbonate only in the corresponding irradiated area. The crystallization was monitored in real-time by time-lapse imaging. The method is also shown to work in gels. Similarly, it was also shown to photo-activate locally the formation of barium carbonate biomorphs. In the last case, the morphology of these biomimetic structures was tuned by changing the irradiation intensity.European Research Council under the European Union's Seventh Framework Program (FP7/20072013)/ERC grant 340863ERC PoC LACRYS 837874Junta de Andalucia P18-FR-5008German Research Foundation (DFG) CO 194/28-1Ministry of Education, Universities and Research (MIUR)Research Projects of National Relevance (PRIN) 2017E44A9PProjekt DEA