Hydrogen production by photoreforming of formic acid in aqueous copper/TiO2 suspensions under UV-simulated solar radiation at room temperature

A new photocatalytic system consisting of two subsystems – Cu⁰/Cl⁻/H⁺/UV_ssr and Cu^II/H⁺/TiO₂/formic acid/UV_ssr – is proposed as a tool to produce hydrogen by reforming an organic species. Formic acid is used as hole scavenger during the experimental runs. An experimental campaign is carried out to demonstrate that the systems can generate hydrogen and to assess how the generation rate depends upon experimental conditions such as copper and TiO₂ loads, chloride and proton ions, and formic acid concentrations. A strong dependence of the Cu⁰/Cl⁻/H⁺/UV_ssr subsystem reactivity upon copper load, chloride concentration and pH is observed. The investigation on the complete system, starting from zero-valent copper, indicates that the addition of TiO₂ and formic acid to the Cu⁰/Cl⁻/H⁺/UV_ssr subsystem does not result into any gain in terms of hydrogen produced and, renders the system totally unreactive under some conditions. On the other hand, when a complete system, starting from cupric ions, is adopted, hydrogen production is observed also for prolonged reaction times with a surplus of hydrogen production with respect to that generated by the Cu⁰/Cl⁻/H⁺/UV_ssr subsystem with the same Cu⁰ starting load and in absence of TiO₂ and sacrificial agent.     

Ni/La2O3 catalysts for dry reforming of methane: Effect of La2O3 synthesis conditions on the structural properties and catalytic performances

10 wt%Ni/La₂O₃ catalysts for dry reforming of methane (DRM) were synthesized by wetness impregnation of lanthana supports prepared using sol-gel citric method with and without NH₃ addition (Ni–La CA-NH₃ and Ni–La CA, respectively). The support preparation conditions affect the nature, phase composition, and distribution of Ni phases (LaNiO₃, NiO and La₃Ni₂O₆). The gradient temperature DRM tests (400–800 °C) reveal higher catalytic activity of Ni–La CA (at 650 °C, X(CO₂) = 65.7%, X(CH₄) = 54.6%, H₂/CO = 0.71). The Ni–La CA-NH₃ shows higher stability (at 650 °C and 24 h, X(CO₂): 73.7% => 76.4%, X(CH₄): 64.7% => 64.6%, H₂/CO: 0.77 => 0.72). For both catalysts, La₂O₂CO₃ phase is formed after long run tests at 650 °C 24 h, with the greater TGA weight loss and stronger deactivation being observed for Ni–La CA. The H₂-reduced Ni La CA-NH₃ features ultrasmall (1–2 nm) Ni NPs strongly interacting with the support. Catalyst nature affects the amount of carbon coke formed.     

Production of biodiesel at small-scale (10 L) for local power generation

The transesterification reaction of two different types of raw materials, a refined cooking oil and a used cooking sample, was performed at small scale (10 L) at the constant temperature of 65 °C. The effects of several reaction parameters, such as KOH wt% with respect to the oil weight, methanol/oil molar ratio and reaction time, were investigated. Biodiesel yields as good as 97.5 and 93.2% were achieved for the refined and the cooking oils, respectively, in the following conditions: 1.2 wt% of KOH as catalyst, a methanol/oil molar ratio of 6:1 and reaction time of 60 min.The properties of the biodiesel obtained starting from the used cooking oil are as good as those of the biodiesels obeying the European standards. The resulting product was used in a diesel electricity generator engine, which operated in real conditions. The results showed that biodiesel combustion leads to higher concentration of CO and to a lower emission of NO_x as compared to a petrodiesel-fueled engine. An optimization of the operating parameters of the engine would guarantee lower CO emissions in conformity with the regulation.     

Evaluation of the Antioxidant Properties of the Brazilian Cerrado Fruit Annona crassiflora (Araticum)

Annona crassiflora, known commonly as araticum, is an exotic tropical fruit consumed mainly by native people of the Brazilian Cerrado (2nd biggest biome of Brazil). In this study, pulp, seed, and peel of slight ripe and overripe fruits were extracted using ethanol and water. The extracts showed high content of total phenols and were screening for their potential as antioxidants using the in vitro model 1,1‐ dipheniyl‐2‐picryl hydrazyl (DPPH). The ethanol extracts of peel and seeds showed IC50 of 48.82 μg/mL and 31.14 μg/mL, respectively, for the slightly ripe fruits. As the ethanolic fractions of araticum showed the highest antioxidant activity, they were selected for testing of its effect on lipid peroxidation. The ethanolic extracts of slightly ripe fruits showed IC₅₀ of 4.44 μg/mL, 1.72 μg/mL, and 8.62 μg/mL for the peel, seed, and pulp, respectively. This is the 1st report on the antioxidant properties of the extracts of araticum. Owing to these properties, the studies can be further extending to exploit them for their possible application as natural antioxidant for cosmetic, supplements, and functional ingredients for food products.     

Enzymatic synthesis of sugar esters and their potential as surface-active stabilizers of coconut milk emulsions

Sugar esters are compounds with surfactant properties (biosurfactants), i.e., capable of reducing the surface tension and promote the emulsification of immiscible liquids. On the other hand, as with all emulsions, coconut milk is not physically stable and is prone to phase separation. Therefore, the aim of this work was to evaluate the synthesis of fructose, sucrose and lactose esters from the corresponding sugars using Candida antarctica type B lipase immobilized in two different supports, namely acrylic resin and chitosan, and evaluate its application in the stabilization of coconut milk emulsions. The enzyme immobilized on chitosan showed the highest yield of lactose ester production (84.1%). Additionally, the production of fructose ester was found to be higher for the enzyme immobilized on the acrylic resin support (74.3%) as compared with the one immobilized on chitosan (70.1%). The same trend was observed for the sucrose ester, although with lower percentage yields. Sugar esters were then added to samples of fresh coconut milk and characterized according to their surface tension, emulsification index and particle size distribution. Although the microscopic analysis showed similar results for all sugar esters, results indicated lactose ester as the best biosurfactant, with a surface tension of 38.0 N/m and an emulsification index of 54.1%, when used in a ratio of 1:10 (biosurfactant:coconut milk, v/v) for 48 h experiments.     

Assessing the antiproliferative effect of biogenic silver chloride nanoparticles on glioblastoma cell lines by quantitative image‐based analysis

Glioblastoma is the most life‐threatening tumour of the central nervous system. Temozolomide (TMZ) is the first‐choice oral drug for the treatment of glioblastoma, although it shows low efficacy. Silver nanoparticles (AgNPs) have been shown to exhibit biocidal activity in a variety of microorganisms, including some pathogenic microorganisms. Herein, the antiproliferative effect of AgCl‐NPs on glioblastoma cell lines (GBM02 and GBM11) and on astrocytes was evaluated through automated quantitative image‐based analysis (HCA) of the cells. The cells were treated with 0.1‐5.0 μg/ml AgCl‐NPs or with 9.7‐48.5 μg/ml TMZ. Cells that received combined treatment were also analysed. At a maximum tested concentration of AgCl‐NPs, GBM02 and GBM11, the growth decreased by 93% and 40%, respectively, following 72 h of treatment. TMZ treatment decreased the proliferation of GBM02 and GBM11 cells by 58% and 34%, respectively. Combinations of AgCl‐NPs and TMZ showed intermediate antiproliferative effects; the lowest concentrations caused an inhibition similar to that obtained with TMZ, and the highest concentrations caused inhibition similar to that obtained with AgCl‐NPs alone. No significant changes in astrocyte proliferation were observed. The authors’ findings showed that HCA is a fast and reliable approach that can be used to evaluate the antiproliferative effect of the nanoparticles at the single‐cell level and that AgCl‐NPs are promising agents for glioblastoma treatment.     

Production of fungal lipases using wheat bran and soybean bran and incorporation of sugarcane bagasse as a co-substrate in solid-state fermentation

Fungal strains were screened for lipase producing activities and 10 strains were classified as good producers. Aspergillus sp., Fusarium sp., and Penicillium sp. exhibited the highest activities when fermented in wheat bran (WB) and soybean bran (SB). No fungal growth was observed using sugarcane bagasse (CB). An experimental design was applied to incorporate CB into the fermentation process for lipase production by Aspergillus sp. and Penicillium sp., and to evaluate the best moisture content for the substrate. Strains studied achieved maximum lipase activities with 25% CB combined with 75% WB or SB at 40% moisture content. The highest lipase activities were observed for WB and SB, and for SB combined with CB using Aspergillus sp. Fermentation of 96 h was the optimum period for enzyme production.     

Removal of fulvic acid from aqueous media by adsorption onto modified vermiculite

Clay minerals are low cost materials that can be structurally modified and exploited for removal of natural organic matter from freshwaters. The present study shows that vermiculites modified by ion exchange with hexadecyltrimethylammonium or intercalation with poly(hydroxy iron) cations are potential adsorbents for removal of fulvic acid, whereas the adsorption on the raw clay mineral is negligible. The efficiency of the modified vermiculite was evaluated by measuring adsorption isotherms by the batch technique using initial fulvic acid concentrations between 2.5 and 50.0 mg L^− 1, with one hour of contact time. At least 94% of the fulvic acid initially present in a 20 mg L^− 1 solution was sorbed onto either the intercalated poly(hydroxy iron) cations or the organically modified vermiculite. Up to an initial concentration of 5.0 mg L^− 1 the adsorption is irreversible, and no quantifiable fulvic acid was measured in the desorption experiments. For initial fulvic acid concentrations between 10.0 and 50.0 mg L^− 1, desorption was between 2.3% and 4.9% for Fe(III) intercalated vermiculite, and between 1.4% and 9.2% for the organoclay. The adsorption percentages on intercalated poly(hydroxy iron) cations increased upon lowering pH and increasing the ionic strength, indicating the occurrence of strong binding mechanisms such as ligand exchange. Adsorption percentage of fulvic acid onto the organoclay also increased with lowering of pH, but in this case the adsorption percentages showed a small decrease at high ionic strength, suggesting that electrostatic attraction plays an important role in the adsorption process.     

The impact of related variety on the creative employment growth

Cultural and creative industries (CCIs) have recently become highly relevant with regard to creative economy research, as they are considered drivers of regional and urban innovation policies and economic growth. CCIs are a priority sector on the European agenda and represent an excellent opportunity to exit the current economic crisis. In the literature, the most discussed aspect of CCIs is their value creation ability, which is due to a high degree of diversity/variety, and their impact on innovation within the wider economy, which results from the activation of cross-fertilisation processes between different sectors. Evolutionary economic geography (EEG), adopting the recently established approach based on related variety, also emphasises the issues of diversity/variety as determinants of local and urban development and innovation. This interesting and complex theoretical framework has produced a considerable number of empirical studies, none of which has been specifically applied to the creative sector. With the present study, we intended to contribute to the debate on creative economy research and EEG by investigating the impact of variety in CCIs in Italy, following the related-variety approach and using a long-term employment perspective (1991–2011). The results indicated that related variety has an important effect on the growth of creative industries, characterised by high internal connections between different creative activities. Our outcomes also led us to reassess the view held by some, namely, that creative industries can actually make a strong impact on economic growth in the wider economy; this did not appear to emerge in the Italian context, according to the methodologies we used.     

Endometriosis Susceptibility to Dapsone-Hydroxylamine-Induced Alterations Can Be Prevented by Licorice Intake: In Vivo and In Vitro Study

Endometriosis, an estrogen-dependent chronic gynecological disease, is characterized by a systemic inflammation that affects circulating red blood cells (RBC), by reducing anti-oxidant defenses. The aim of this study was to investigate the potential beneficial effects of licorice intake to protect RBCs from dapsone hydroxylamine (DDS-NHOH), a harmful metabolite of dapsone, commonly used in the treatment of many diseases. A control group (CG, n = 12) and a patient group (PG, n = 18) were treated with licorice extract (25 mg/day), for a week. Blood samples before (T₀) and after (T₁) treatment were analyzed for: i) band 3 tyrosine phosphorylation and high molecular weight aggregates; and ii) glutathionylation and carbonic anhydrase activity, in the presence or absence of adjunctive oxidative stress induced by DDS-NHOH. Results were correlated with plasma glycyrrhetinic acid (GA) concentrations, measured by HPLC–MS. Results showed that licorice intake decreased the level of DDS-NHOH-related oxidative alterations in RBCs, and the reduction was directly correlated with plasma GA concentration. In conclusion, in PG, the inability to counteract oxidative stress is a serious concern in the evaluation of therapeutic approaches. GA, by protecting RBC from oxidative assault, as in dapsone therapy, might be considered as a new potential tool for preventing further switching into severe endometriosis.