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The design of modern devices that can fulfil the requirements for sustainability and renewable energy applications calls for both new materials and a better understanding of the mixing of existing materials. Among those, surely organic–inorganic hybrids are gaining increasing attention due to the wide possibility to tailor their properties by accurate structural design and materials choice. In this work, we'll describe the tight interplay between porous Si and two melanic polymers permeating the pores. Melanins are a class of biopolymers, known to cause pigmentation in many living species, that shows very interesting potential applications in a wide variety of fields. Given the complexity of the polymerization process beyond the formation and structure, the full understanding of the melanins' properties remains a challenging task. In this study, the use of a melanin/porous Si hybrid as a tool to characterize the polymer's properties within mesopores gives new insights into the conduction mechanisms of melanins. We demonstrate the dramatic effect induced on these mechanisms in a confined environment by the presence of a thick interface. In previous studies, we already showed that the interactions at the interface between porous Si and eumelanin play a key role in determining the final properties of composite materials. Here, thanks to a careful monitoring of the photoconductivity properties of porous Si filled with melanins obtained by ammonia-induced solid-state polymerization (AISSP) of 5,6-dihydroxyindole (DHI) or 1,8-dihydroxynaphthalene (DHN), we investigate the effect of wet, dry, and vacuum cycles of storage from the freshly prepared samples to months-old samples. A computational study on the mobility of water molecules within a melanin polymer is also presented to complete the understanding of the experimental data. Our results demonstrate that: (a) the hydration-dependent behavior of melanins is recovered in large pores (≈ 60 nm diameter) while is almost absent in thinner pores (≈ 20 nm diameter); (b) DHN-melanin materials can generate higher photocurrents and proved to be stable for several weeks and more sensitive to the wet/dry variations. [ABSTRACT FROM AUTHOR]

Two olive mill wastewaters (OMW) samples, OMWa and OMWb, containing different polyphenolic loads were used for decontaminating an unauthorized dump site in the Campania region, south Italy. In a bench-scale experiment, OMWa at pH 6.0 (OMWa pH6.0) and 4.7 (OMWa pH4.7), OMWb at pH 4.7 (OMWb pH4.7) and OMWa free of the polyphenolic moiety polyphenol-free OMWa (PF-OMWa) were added to the soil for a 96 h contact time. At 96 h, OMWa pH4.7 was more effective than OMWa pH6.0, with Cd, Cu, Pb and Zn removal percentages of 30.7–68.1. Cd and Pb levels were 6.0 and 915 mg kg −1, respectively, decreasing below the regulatory limits for industrial and commercial areas (15.0 and 1 × 10 3 mg kg −1, respectively). A threefold decrease in Zn levels was also observed from 13.5 × 10 3 to 4.3 × 10 3 mg kg −1. The metal removal efficiency of PF-OMWa dropped from 30.7 % to 15.6 % for Cd and from 37.9 % to 1.3 % for Pb. OMWb pH4.7 at 96 h was more efficient than OMWa pH4.7, with mean removal percentages of 32.5 versus 7.8, respectively. [ABSTRACT FROM AUTHOR]

Introduction: The reuse of wastewaters for agricultural purposes is a common practice in many countries and is increasingly recommended by organizations that promote sustainable development. Yet, it is restricted by the potential negative impact of these materials on soil and crops. The aim of this study was therefore to evaluate the environmental impact of walnut husk washing waters (WHWW) and their organic fractions, in order to conceive their agricultural exploitation. Discussion: Phytotoxicity tests and morphological investigations on representative plant species of horticultural interest indicated that WHWW and their organic fractions can elicit a concentration-dependent stimulating effect on the growth of radish, lettuce cv. cavolo Napoli with effects up to 165 %. An opposite inhibitory effect up to 70 % was observed on spinach and lettuce cv. Gentilina. Proapoptotic effects were observed by acridine orange/ethidium bromide assay in the species inhibited by WHWW treatment. High-performance liquid chromatography-mass spectrometry analysis of the WHWW revealed the presence of a main component which was extracted selectively in organic solvents and purified by preparative chromatography. Complete spectral analysis allowed identification as 4,8-dihydroxy-1-tetralone, commonly known as regiolone. Regiolone exhibited the same concentration-dependent activity on root elongation with a stimulation in the case of radish up to 135 % with respect to control. These results open perspectives in the exploitation of WHWW and the main phenolic constituent readily available by a straightforward isolation procedure as a natural fertilizer for specific crops. [ABSTRACT FROM AUTHOR]

Oxidative stress has been associated with Down syndrome (DS) and with its major phenotypic features, such as early ageing. In order to evaluate an in vivo pro-oxidant state, the following analytes were measured in a group of DS patients aged 2 months to 57 years: (a) leukocyte 8-hydroxy-2′-deoxyguanosine (8-OHdG); (b) blood glutathione; (c) plasma levels of: glyoxal (Glx) and methylglyoxal (MGlx); some antioxidants (uric acid, UA, ascorbic acid, AA and Vitamin E), and xanthine oxidase (XO) activity. A significant 1.5-fold increase in 8-OHdG levels was observed in 28 DS patients vs. 63 controls, with a sharper increase in DS patients aged up to 30 years. The GSSG:GSH×100 ratio was significantly higher in young DS patients (< 15 years), in contrast to DS patients aged ≥15 years that showed a significant decrease in the GSSG:GSH×100 ratio ratio vs. controls of the respective age groups. Plasma Glx levels were significantly higher in young DS patients, whereas no significant difference was detected in DS patients aged ≥15 years. Unlike Glx, the plasma levels of MGlx were found to be significantly lower in DS patients vs. controls. A significant increase was observed in plasma levels of UA in DS patients that could be related to an increased plasma XO activity in DS patients. The plasma concentrations of AA were also increased in young (< 15 years) DS patients, but not in older patients vs. controls in the same age range. The levels of Vitamin E in DS patients did not differ from the values determined in control donors. The evidence for a multiple pro-oxidant state in young DS patients supports the role of oxidative stress in DS phenotype, with relevant distinctions according to patients’ ages. [ABSTRACT FROM AUTHOR]

Werner syndrome is a genetic disease characterized by early ageing, excess cancer risk, high incidence of type II diabetes mellitus, early atherosclerosis, ocular cataracts, and osteoporosis. The protein encoded by the defective gene, WRN (WRNp) associates with three activities, that is, a RecQ DNA helicase, 3′-5′-exonuclease and ATPase activities. By highlighting the DNA helicase activity, a widespread consensus in WS-associated defect(s) has been established, pointing toward a deficiency in maintaining DNA integrity. However, a possible involvement of redox pathways in WS may be suggested by several lines of evidence that include: (i) the multiple functions and interactions of WRNp with oxidative stress-related activities and factors; (ii) the pleiotropic WS clinical phenotype encompassing a number of oxidative stress-related pathologies; (iii) redox-related toxicity mechanisms of several xenobiotics exerting excess toxicity in WS cells; (iv) recent in vivo and in vitro findings of redox abnormalities in WS patients and in WS cells. The working hypothesis is raised that a deficiency in WRNp, and the pleiotropic clinical phenotype in WS patients may provide the basis to envision an underlying in vivo prooxidant state, which causes oxidative damage to biomolecules, with multiple oxidative stress-related alterations, resulting in multi-faceted clinical consequences. [ABSTRACT FROM AUTHOR]

Silicon oxyfluoride materials are synthesized by the sol-gel method using triethoxyfluorosilane as precursor, bearing the Si—F bond. SiO(2−0.5 x) F x gel preparation requires peculiar experimental control of hydrolysis and condensation reactions. Maintenance of the Si—F bond during gelling, heating and aging was studied in the case of processes carried out under an argon atmosphere or in air. Fluorine contents in resulting samples were quantified by FT-IR and X-ray photoelectron spectroscopy (XPS); specific surface area and porosity of powdered samples were determined by N2 adsorption. The thermal stability of oxyfluoride gels was studied by thermogravimetric-mass spectrometric (TG-MS) coupled analyses during heat treatment, under He flow. Mass spectra recorded during principal weight losses indicate the release of variously fluorinated silicon species resulting from Si—F/Si—O exchange reactions. The evolution of these species was observed at different temperatures, depending on gelling conditions. In particular, degradation of ≡Si—F moieties was prominent for gels aged in air, whereas samples processed under an argon atmosphere preserve the ≡Si—F bond up to 300°C. [ABSTRACT FROM AUTHOR]

RhCl3·nH2O and [RhCl(C2H4)2]2 are used as precursors for the preparation of 1%Rh in sol-gel derived SiO2. The gelling process of Si(OEt)4 is carried out in the absence of solvent and under strong acid catalysis. The thermal behavior of Rh precursors, of SiO2 gel and Rh-SiO2 composites is independently studied by analysing organic species released at definite temperature intervals and concomitantly collecting infrared, XPS, TEM, XRD and porosity data. Results indicate that nanometric Rh particles may be obtained from [RhCl(C2H4)2]2, their dispersion being homogeneous, dense and stable up to 250°C, whereas RhCl3·nH2O affords less metallic dispersion with other crystalline Rh-species; in both cases, well-shaped Rh metal crystallites are obtained at 650°C. The different synthetic approaches used for the preparation of RhCl3- and [RhCl(C2H4)2]2-derived samples, are invoked to account for the features of Rh dispersion obtained by mild temperature treatment. Moreover, the particular procedures for sol-gel SiO2 synthesis are related to the high-temperature maintenance of great porosity and elevated specific surface area. [ABSTRACT FROM AUTHOR]

Eumelanins, the chief photoprotective pigments in man and mammals, owe their black color to an unusual broadband absorption spectrum whose origin is still a conundrum. Excitonic effects from the interplay of geometric order and disorder in 5,6-dihydroxyindole (DHI)-based oligomeric/polymeric structures play a central role, however the contributions of structural (scaffold-controlled) and redox (π-electron-controlled) disorder have remained uncharted. Herein, we report an integrated experimental-theoretical entry to eumelanin chromophore dynamics based on poly(vinyl alcohol)-controlled polymerization of a large set of 5,6-dihydroxyindoles and related dimers. The results a) uncover the impact of the structural scaffold on eumelanin optical properties, disproving the widespread assumption of a universal monotonic chromophore; b) delineate eumelanin chromophore buildup as a three-step dynamic process involving the rapid generation of oxidized oligomers, termed melanochromes (phase I), followed by a slow oxidant-independent band broadening (phase II) leading eventually to scattering (phase III); c) point to a slow reorganization-stabilization of melanochromes via intermolecular redox interactions as the main determinant of visible broadband absorption. [ABSTRACT FROM AUTHOR]

Starch suspension proves to be a useful matrix for the hydrolytic route to metal oxide nanoparticles, due to its size-stabilization effect, which works also at high temperatures. To understand the type of interaction between the organic part and the oxide particles, various parameters, such as viscosity, temperature, degree of polymerization, and organic/inorganic kinds of dispersant, are tested through x-ray diffraction (XRD), transmission electron microscopy (TEM), solid-state nuclear magnetic resonance (NMR), and thermogravimetric mass spectra (TG-MS) analyses of the obtained SnO2 nanopowders. Results highlight the unique role of starch compared with other hydrophilic dispersants that do not ensure effective size stabilization on curing up to 600 °C. The proof comes from the study of pyrolysis of the residual organic groups surrounding the particles. They are chelating carboxylic species that prevent the coalescence among metal oxide nanoparticles. [ABSTRACT FROM AUTHOR]