Mimicking Natural Antioxidant Systems for Improved Photostability in Wide-Band-Gap Perovskite Solar Cells.

Fostered by the top power conversion efficiencies (PCEs) of lab-scale devices, industrialization of perovskite solar cells is underway. Nevertheless, the intrinsically poor stability of these materials still represents a major concern. Herein, inspired by Nature, the use of ß-carotene in perovskite solar cells is proposed to mimic its role as a protective pigment, as occurs in natural photosynthesis. Laser-mediated photostability (LMPS) assessment, Fourier-transform infrared spectra analysis acquired in attenuate total reflectance (ATR-FTIR), spectroscopy ellipsometry (SE), and time-resolved photoluminescence (TRPL) measurements under stress conditions prove that the inclusion of a thin ß-carotene interlayer promotes a high improvement in the photostability of the perovskite films against photooxidation. Importantly, this is accompanied by an improvement of the solar cell PCE that approaches 20% efficiency with no hysteresis, which is among the highest values reported for a mixed halide (I-Br) perovskite with a band gap of 1.74 eV, relevant for coupling with silicon in tandem cells.

Anticancer Effects of Plasma-Treated Water Solutions from Clinically Approved Infusion Liquids Supplemented with Organic Molecules.

Water solutions treated by cold atmospheric plasmas (CAPs) currently stand out in the field of cancer treatment as sources of exogenous blends of reactive oxygen and nitrogen species (RONS). It is well known that the balance of RONS inside both eukaryotic and prokaryotic cells is directly involved in physiological as well as pathological pathways. Also, organic molecules including phenols could exert promising anticancer effects, mostly attributed to their pro-oxidant ability in vitro and in vivo to generate RONS like O2-, H2O2, and a mixture of potentially cytotoxic compounds. By our vision of combining the efficacy of plasma-produced RONS and the use of organic molecules, we could synergistically attack cancer cells; yet, so far, this combination, to the best of our knowledge, has been completely unexplored. In this study, l-tyrosine, an amino acid with a phenolic side chain, is added to a physiological solution, often used in clinical practice (SIII) to be exposed to plasma. The efficacy of the gas plasma-oxidized SIII solution, containing tyrosine, was evaluated on four cancer cell lines selected from among tumors with poor prognosis (SHSY-5Y, MCF-7, HT-29, and SW-480). The aim was to induce tumor toxicity and trigger apoptosis pathways. The results clearly indicate that the plasma-treated water solution (PTWS) reduced cell viability and oxygen uptake due to an increase in intracellular ROS levels and activation of apoptosis pathways in all investigated cancer cells, which may be related to the activation of the mitochondrial-mediated and p-JNK/caspase-3 signaling pathways. This research offers improved knowledge about the physiological mechanisms underlying cancer treatment and a valid method to set up a prompt, adequate, and effective cancer treatment in the clinic.

Drug Delivery through Epidermal Tissue Cells by Functionalized Biosilica from Diatom Microalgae.

Diatom microalgae are a natural source of fossil biosilica shells, namely the diatomaceous earth (DE), abundantly available at low cost. High surface area, mesoporosity and biocompatibility, as well as the availability of a variety of approaches for surface chemical modification, make DE highly profitable as a nanostructured material for drug delivery applications. Despite this, the studies reported so far in the literature are generally limited to the development of biohybrid systems for drug delivery by oral or parenteral administration. Here we demonstrate the suitability of diatomaceous earth properly functionalized on the surface with n-octyl chains as an efficient system for local drug delivery to skin tissues. Naproxen was selected as a non-steroidal anti-inflammatory model drug for experiments performed both in vitro by immersion of the drug-loaded DE in an artificial sweat solution and, for the first time, by trans-epidermal drug permeation through a 3D-organotypic tissue that better mimics the in vivo permeation mechanism of drugs in human skin tissues. Octyl chains were demonstrated to both favour the DE adhesion onto porcine skin tissues and to control the gradual release and the trans-epidermal permeation of Naproxen within 24 h of the beginning of experiments. The evidence of the viability of human epithelial cells after permeation of the drug released from diatomaceous earth, also confirmed the biocompatibility with human skin of both Naproxen and mesoporous biosilica from diatom microalgae, disclosing promising applications of these drug-delivery systems for therapies of skin diseases.

Air- and water-stable and photocatalytically active germanium-based 2D perovskites by organic spacer engineering.

There is increasing interest in the role of metal halide perovskites for heterogeneous catalysis. Here, we report a Ge-based 2D perovskite material that shows intrinsic water stability realized through organic cation engineering. Incorporating 4-phenylbenzilammonium (PhBz) we demonstrate, by means of extended experimental and computational results, that PhBz2GeBr4 and PhBz2GeI4 can achieve relevant air and water stability. The creation of composites embedding graphitic carbon nitride (g-C3N4) allows a proof of concept for light-induced hydrogen evolution in an aqueous environment by 2D Ge-based perovskites thanks to the effective charge transfer at the heterojunction between the two semiconductors.

Lead-Free Metal Halide Perovskites for Hydrogen Evolution from Aqueous Solutions.

Metal halide perovskites (MHPs) exploitation represents the next big frontier in photovoltaic technologies. However, the extraordinary optoelectronic properties of these materials also call for alternative utilizations, such as in solar-driven photocatalysis, to better address the big challenges ahead for eco-sustainable human activities. In this contest the recent reports on MHPs structures, especially those stable in aqueous solutions, suggest the exciting possibility for efficient solar-driven perovskite-based hydrogen (H2) production. In this minireview such works are critically analyzed and classified according to their mechanism and working conditions. We focus on lead-free materials, because of the environmental issue represented by lead containing material, especially if exploited in aqueous medium, thus it is important to avoid its presence from the technology take-off. Particular emphasis is dedicated to the materials composition/structure impacting on this catalytic process. The rationalization of the distinctive traits characterizing MHPs-based H2 production could assist the future expansion of the field, supporting the path towards a new class of light-driven catalysts working in aqueous environments.

A Synergistic Effect of Reactive Oxygen and Reactive Nitrogen Species in Plasma Activated Liquid Media Triggers Astrocyte Wound Healing.

Astrocyte proliferation and migration toward injured Central Nervous System (CNS) areas are key features of astrogliosis and glial scar formation. Even though it is known that intracellular and environmental Reactive Oxygen and Nitrogen Species (RONS) affect astrocyte behaviour in physiological and pathophysiological conditions, their effects on the migration and growth of astrocytes are still unclear. Plasma-technologies are emerging in medicine as a tool to generate RONS for treating cells directly or through Plasma Activated Liquid Media (PALM). In this paper, we show for the first time how the use of PALM can modulate both astrocyte growth and migration as a function of active species produced by plasma in liquids. Our results show that PALM, generated by means of cold atmospheric pressure plasmas fed with N2, air or O2, can modulate astrocyte behaviour depending on the content of hydrogen peroxide and nitrite in the liquid. In particular, H2O2 enriched PALM induced a negative effect on cell growth associated with the mild wound healing improvement of primary astrocytes, in a scratch assay. Nitrite enriched PALM induced a selective effect on the wound healing without affecting cell growth. PALM containing a more balanced level of H2O2 and NO2- were able to affect cell growth, as well as significantly ameliorate wound healing. None of the PALM investigated induced upregulation of the gliotic inflammatory marker glial fibrillary acidic protein (GFAP), or of the astrocyte markers Aquaporin-4 (AQP4) and Connexin-43 (Cx-43) analysed by Western blot. Finally, immunofluorescence analysis revealed the presence of NO2- able to induce elongated protrusions at the front end of wounded astrocytes in the direction of cell migration. With our study we believe to have shown that PALM offer a novel tool to modulate astrocyte behaviour and that they are promising candidates for controlling astrogliosis in the case of CNS injuries.

Direct Exposure of Dry Enzymes to Atmospheric Pressure Non-Equilibrium Plasmas: The Case of Tyrosinase.

The direct interaction of atmospheric pressure non-equilibrium plasmas with tyrosinase (Tyr) was investigated under typical conditions used in surface processing. Specifically, Tyr dry deposits were exposed to dielectric barrier discharges (DBDs) fed with helium, helium/oxygen, and helium/ethylene mixtures, and effects on enzyme functionality were evaluated. First of all, results show that DBDs have a measurable impact on Tyr only when experiments were carried out using very low enzyme amounts. An appreciable decrease in Tyr activity was observed upon exposure to oxygen-containing DBD. Nevertheless, the combined use of X-ray photoelectron spectroscopy and white-light vertical scanning interferometry revealed that, in this reactive environment, Tyr deposits displayed remarkable etching resistance, reasonably conferred by plasma-induced changes in their surface chemical composition as well as by their coffee-ring structure. Ethylene-containing DBDs were used to coat tyrosinase with a hydrocarbon polymer film, in order to obtain its immobilization. In particular, it was found that Tyr activity can be fully retained by properly adjusting thin film deposition conditions. All these findings enlighten a high stability of dry enzymes in various plasma environments and open new opportunities for the use of atmospheric pressure non-equilibrium plasmas in enzyme immobilization strategies.

Biodegradable Carbon-based Ashes/Maize Starch Composite Films for Agricultural Applications.

The aim of this work is the development and characterization of biodegradable thermoplastic recycled carbon ashes/maize starch (TPAS) composite films for agricultural applications. A proper plasticizer, that is, glycerol, was added to a commercial maize starch in an amount of 35 wt.%. Carbon-based ashes were produced by the biomass pyro-gasification plant CMD ECO 20, starting from lignocellulosic wastes. The ashes were added to glycerol and maize native starch at different amounts ranging from 7 wt. % to 21 wt.%. The composite was mixed at 130 °C for 10 min and then molded. The effect of the different amounts of carbon based ashes on the thermal and physical-mechanical properties of the composite was assessed by using several techniques, such as rheology, wide- angle X-ray diffraction (WAXD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), moisture absorption, degradation and mechanical tests. The presence of the carbon waste ashes allows to improve thermal and durability performances of the thermoplastic starch (TPS) films. It reduces the water absorption of starch matrix and strongly decreases the deterioration of starch, independently from fillers amount, enhancing the lifetime of the TPS films in outdoor conditions. In addition, the waste carbon ashes/maize starch films present an advantage in comparison to those of neat starch; it can biodegrade, releasing the plant nutrients contained in the ashes into the soil. In conclusion, this approach for recycling carbon waste ashes increases the efficiency of industrial waste management, along with a reduction of its impact on the environment.

Initiated Chemical Vapor Deposition of Crosslinked Organic Coatings for Controlling Gentamicin Delivery.

A coating consisting of a copolymer of methacrylic acid and ethylene glycol dimethacrylate was deposited over a gentamicin film by initiated chemical vapor deposition with the aim of controlling the drug release. Gentamicin release in water was monitored by means of conductance measurements and of UV-vis Fluorescence Spectroscopy. The influence of the polymer chemical composition, specifically of its crosslinking density, has been investigated as a tool to control the swelling behavior of the initiated chemical vapor deposition (iCVD) coating in water, and therefore its ability to release the drug. Agar diffusion test and microbroth dilution assays against Staphylococcus aureus and Pseudomonas aeruginosa on cellulose coated substrates confirmed that the antibacterial activity of the drug released by the coating was retained, though the release of gentamicin was not complete.

Simple Processing Additive-Driven 20% Efficiency for Inverted Planar Heterojunction Perovskite Solar Cells.

Compositional engineering has been a strong tool to improve the quality of the perovskite materials and, in turn, the reproducibility of the solar cells. However, the control over the active layer uniformity, one of the most important requirements for the obtainment of efficient devices, is still a weak point of perovskite solar cells (PSCs) manufacturing. Here, we develop an approach to grow a uniform mixed cation perovskite layer, foreseeing its implementation in inverted solar cells endowing organic transporting layers, through the addition of a stoiochiometric amount of tropolone as chelating agent for the lead. Thanks to low melting and boiling temperatures, tropolone is present in the system only during the colloidal liquid phase, leaving the film during its formation; this unique characteristic promotes the obtainment of ideal perovskite surface morphologies and an increased short circuit current of photovoltaic devices. A maximum power conversion efficiency of 20% was obtained, with a 25% increase with respect to the reference.