Photocatalysis (by semiconductors, molecules and ions) is used in such diverse applications as water hydrolysis for producing hydrogen as fuel, organic synthesis and the recovery of polluted effluents. This tutorial review discusses the common principles of such applications and their role in green chemistry.
A systematic investigation of two well-known and popular commercial suncreams reveals significant degradation when exposed to simulated UV sunlight at an irradiance corresponding to natural sunlight. We have examined the photochemistry of two widely used sunscreen active agents in pure solvents separately and together (in solution), and in neat form, as well as their photochemistry when present in the actual suncream emulsion (as thin films on a glass substrate) since their combination typically produces suncreams with high sun protection factors (SPF): (1a) octyl methoxycinnamate (OMC; octinoxate) and (2a) 4-tert-butyl-4'-methoxydibenzoylmethane (also known as avobenzone and Parsol 1789), present in the two suncream formulations in combination with others (one also contained TiO2). Intermediates and/or photoproducts were identified by UV/visible spectroscopy, HPLC and liquid chromatographic/mass spectral methods, and by both 1H and 13C-NMR techniques. Structural assignments of the substrates produced were aided by examining model systems {viz. ethyl cinnamate (1b) and dibenzoylmethane (2b)} of the two sunscreen active agents. Irradiation of the cinnamates and the diketones together led to a [2 + 2] photocycloaddition process yielding cinnamate dimers and cyclobutylketone photoadducts that subsequently fragmented into substituted oxopentanoates and oxobutanoates. Similar findings were observed when the two active agents were simultaneously present in the same suncream emulsion.
Reducing the use of non-renewable resources is a key strategy of a circular economy. Mycelium-based foams and sandwich composites are an emerging category of biocomposites relying on the valorization of lignocellulosic wastes and the natural growth of the living fungal organism. While growing, the fungus cements the substrate, which is partially replaced by the tenacious biomass of the fungus itself. The final product can be shaped to produce insulating panels, packaging materials, bricks or new-design objects. Only a few pioneer companies in the world retain a significant know-how, as well as the ability to provide the material characterization. Moreover, several technical details are not revealed due to industrial secrecy. According to the available literature, mycelium-based biocomposites show low density and good insulation properties, both related to acoustic and thermal aspects. Mechanical properties are apparently inferior in comparison to expanded polystyrene (EPS), which is the major synthetic competitor. Nevertheless, mycelium-based composites can display an enormous variability on the basis of: fungal species and strain; substrate composition and structure; and incubation conditions. The aim of the present review is to summarize technical aspects and properties of mycelium-based biocomposites focusing on both actual applications and future perspectives.
This work presents a systematic study of cellulose (CLS) as a sacrificial biomass for photocatalytic H2 evolution from water. The idea is indeed to couple a largely available and not expensive biomass, and water, with a renewable energy like solar radiation. An aqueous CLS suspension irradiated either at 366 nm (UV-A) or under sunlight in the presence of Pt/TiO2 behaves as a H2 evolving system. The effects of irradiation time, catalyst and CLS concentrations, pH and water salinity are studied. Addition of CLS to the sample significantly improved H2 evolution from water splitting, with yields up to ten fold higher than those observed in neat water. The mechanism of the photocatalytic process relies on the TiO2-mediated CLS hydrolysis, under irradiation. The polysaccharide depolymerisation generates water-soluble species and intermediates, among them 5-hydroxymethylfurfural (HMF) was identified. These intermediates are readily oxidized following the glucose photoreforming, thus enhancing water hydrogen ion reduction to give gas-phase H2. The formation of "colored" by-products from HMF self-polymerization involves a sort of "in situ dye sensitization" that allows an effective photoreaction even under solar light. The procedure is evaluated and successfully extended on cellulosic biomasses, i.e. rice husk and alfalfa (Medicago sativa) stems, not previously investigated for this application.
In the context of seed technology, the use of physical methods for increasing plant production offers advantages over conventional treatments based on chemical substances. The effects of physical invigoration treatments in seeds can be now addressed at multiple levels, ranging from morpho-structural aspects to changes in gene expression and protein or metabolite accumulation. Among the physical methods available, “magneto-priming” and irradiation with microwaves (MWs) or ionizing radiations (IRs) are the most promising pre-sowing seed treatments. “Magneto-priming” is based on the application of magnetic fields and described as an eco-friendly, cheap, non-invasive technique with proved beneficial effects on seed germination, vigor and crop yield. IRs, as γ-rays and X-rays, have been widely regarded as a powerful tool in agricultural sciences and food technology. Gamma-rays delivered at low dose have showed to enhance germination percentage and seedling establishment, acting as an actual ‘priming’ treatment. Different biological effects have been observed in seeds subjected to MWs and X-rays but knowledge about their impact as seed invigoration agent or stimulatory effects on germination need to be further extended. Ultraviolet (UV) radiations, namely UV-A and UV-C have shown to stimulate positive impacts on seed health, germination, and seedling vigor. For all mentioned physical treatments, extensive fundamental and applied research is still needed to define the optimal dose, exposition time, genotype- and environment-dependent irradiation conditions. Electron paramagnetic resonance has an enormous potential in seed technology not fully explored to monitor seed invigoration treatments and/or identifying the best suitable irradiation dose or time-point to stop the treatment. The present manuscript describes the use of physical methods for seed invigoration, while providing a critical discussion on the constraints and advantages. The future perspectives related to the use of these approaches to address the need of seed technologists, producers and trade markers will be also highlighted.
With tungsten and lamp: Ketones were prepared by the photocatalytic generation of acyl radicals from aldehydes and trapping them with equimolar amounts of electrophilic alkenes. Photocatalysis with tetrabutylammonium decatungstate is effective also at low temperatures (−20 to −50 °C), thus minimizing radical decarbonylation and allowing acylation by highly substituted aldehydes. EWG=electron‐withdrawing group.
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