Structural Investigation and Molecular Modeling Studies of Strobilurin-Based Fungicides Active against the Rice Blast Pathogen Pyricularia oryzae

The increasing emergence of fungicide-resistant pathogens requires urgent solutions for crop disease management. Here, we describe a structural investigation of new fungicides obtained by combining strobilurin and succinate dehydrogenase inhibitor pharmacophores. We identified compounds endowed with very good activity against wild-type Pyricularia oryzae, combined in some cases with promising activity against strobilurin-resistant strains. The first three-dimensional model of P. oryzae cytochrome bc1 complex containing azoxystrobin as a ligand was developed. The model was validated with a set of commercially available strobilurins, and it well explains both the resistance mechanism to strobilurins mediated by the mutation G143A and the activity of metyltetraprole against strobilurin-resistant strains. The obtained results shed light on the key recognition determinants of strobilurin-like derivatives in the cytochrome bc1 active site and will guide the further rational design of new fungicides able to overcome resistance caused by G143A mutation in the rice blast pathogen.     

Electrochemical Behavior of Single CuO Nanoparticles: Implications for the Assessment of their Environmental Fate

The electrochemical behavior of copper oxide nanoparticles is investigated at both the single particle and at the ensemble level in neutral aqueous solutions through the electrode‐particle collision method and cyclic voltammetry, respectively. The influence of Cl^? and NO₃^? anions on the electrochemical processes occurring at the nanoparticles is further evaluated. The electroactivity of CuO nanoparticles is found to differ between the two types of experiments. At the single‐particle scale, the reduction of the CuO nanoparticles proceeds to a higher extent in the presence of chloride ion than of nitrate ion containing solutions. However, at the multiparticle scale the CuO reduction proceeds to the same extent regardless of the type of anions present in solution. The implications for assessing realistically the environmental fate and therefore the toxicity of metal‐based nanoparticles in general, and copper‐based nanoparticles in particular, are discussed.     

Oxidation of proteins: Basic principles and perspectives for blood proteomics

Protein oxidation mechanisms result in a wide array of modifications, from backbone cleavage or protein crosslinking to more subtle modifications such as side chain oxidations. Protein oxidation occurs as part of normal regulatory processes, as a defence mechanism against oxidative stress, or as a deleterious processes when antioxidant defences are overcome. Because blood is continually exposed to reactive oxygen and nitrogen species, blood proteomics should inherently adopt redox proteomic strategies. In this review, we recall the biochemical basis of protein oxidation, review the proteomic methodologies applied to analyse redox modifications, and highlight some physiological and in vitro responses to oxidative stress of various blood components.     

Intrinsic Fluorescence of the Active and the Inactive Functional Forms of Human Thymidylate Synthase

The observables associated with protein intrinsic fluorescence – spectra, time decays, anisotropies – offer opportunities to monitor in real time and non-invasively a protein‘s functional form and its interchange with other forms with different functions. We employed these observables to sketch the fluorometric profiles of two functional forms of human thymidylate synthase (hTS), a homodimeric enzyme crucial for cell proliferation and thus targeted by anticancer drugs. The protein takes an active and an inactive form. Stabilization of the latter by peptides that, unlike classical hTS inhibitors, bind it at the monomer/monomer interface offers an alternative inhibition mechanism that promises to avoid the onset of drug resistance in anticancer therapy. The fluorescence features depicted herein can be used as tools to identify and quantify each of the two protein forms in solution, thus making it possible to investigate the kinetic and thermodynamic aspects of the active/inactive conformational interchange. Two examples of fluorometrically monitored interconversion kinetics are provided.     

Partial replacement of sodium chloride with potassium chloride in marinated rabbit meat

This study was aimed at evaluating the consequences of sodium chloride reduction by potassium chloride up to 50% on technological, sensorial and microbiological traits of marinated rabbit meat. In total, 226 rabbit loin meat samples were obtained and subjected to vacuum tumbling using solutions with different NaCl/KCl ratios. Replacing of sodium chloride up to 30% by potassium chloride did not change microbiological traits (total aerobic mesophilic and lactic acid bacteria maximum cell loads), sensorial acceptability (perceived saltiness and overall liking) and technological traits (pH, colour, texture, cooking loss and yield). Otherwise, reduction in sodium chloride to 50% significantly decreased perceived saltiness (4.15 vs. 4.73; P < 0.05) and reduced microbial shelf life by 1 day when compared to control, even if there was still no effect on technological traits. In conclusion, it is feasible imparting an added value for processed rabbit meat products by reduction in sodium content that could increase market interest.     

Direct Ink Writing of a Preceramic Polymer and Fillers to Produce Hardystonite (Ca2ZnSi2O7) Bioceramic Scaffolds

The direct ink writing of an ink composed of a preceramic polymer and fillers was used to produce hardystonite (Ca₂ZnSi₂O₇) bioceramic scaffolds. Suitable formulations were developed for the extrusion of fine filaments (350 μm diameter) through a nozzle. The preceramic polymer was employed with the double purpose of contributing to the rheology of the ink by increasing its viscosity and of forming the hardystonite phase upon heat treatment by reacting with the fillers. A control of the rheology is essential when spanning features have to be produced, and therefore the main rheological characteristics of the inks were measured (flow curves, dynamic oscillation tests, viscosity recovery tests) and compared to models reported in the literature. Highly porous scaffolds (up to 80% total porosity) were produced and heat treated in air or in nitrogen atmosphere. The influence of the heat‐treatment atmosphere on the morphology, crystalline phase assemblage, and compressive strength of the scaffolds was investigated.     

Persistent organic pollutants in farmed European sea bass (Dicentrarchus labrax,Linnaeus, 1758) from Sicily (Italy)

Farmed European sea bass (Dicentrarchus labrax, Linnaeus, 1758) were collected during 2016 from one Sicilian fish farm that uses two different rearing systems – sea cage and concrete tank – for determination of polychlorinated biphenyls (PCB), organochlorine pesticides (OCP) and polycyclic aromatic hydrocarbons (PAH) residues by HRGC-MS/MS. Moreover, commercial feed was analysed. This study aimed to determine whether the different rearing systems affect the concentration of these compounds, and to assess the safety of cultured fish. PCBs represent the pollutants with the highest concentration; in particular, PCB138 and 153 have the highest concentration in almost all samples. Among OCPs, only 4,4′-DDE, 4,4′-DDD and 4,4′-DDT residues have been detected. Concerning PAHs, only fluorene and phenanthrene were detected, in both rearing systems. Although some residues of organic pollutants were found in the analysed samples, they were always below the MRLs, so the results suggest that farmed sea bass are safe for human consumption.     

Biosurfactants from Urban Wastes for Detergent Formulation: Surface Activity and Washing Performance

To promote biobased products for industry, six biosurfactants (BS) isolated from green and food urban residues aged under aerobic digestion for 0–60 days were investigated for their chemical composition, surface activity properties and detergent performance in fabric washing in comparison with commercial anionic and nonionic surfactants (CS). The BS exhibited a range of chemical composition and surface activity properties presumably related to their different biomass sources. Surface tension data for these substances correlated meaningfully with performance data in fabric washing. It was found that BS have similar performances as CS when used neat, but the 1:1 w/w BS–CS mixes are characterized by significant synergy. High sensitivity to water hardness and fabric yellowing were found to be the main deficiencies for the BS. However, both effects are minimized or are not critically evident when the BS are used together with CS and/or in common detergents formulations. The results indicate that when used above critical micellar concentration, no significant or critical performance differences are evident within the whole group of BS or between BS and CS. These facts encourage expectations for industrial production and real commercialization of BS as components of detergents formulations.     

Polycyclic aromatic hydrocarbon (PAH) content of soil and olives collected in areas contaminated with creosote released from old railway ties

Simple sample preparation procedures involving sonication and solid phase extraction (SPE), followed by reversed-phase high performance liquid chromatography (HPLC) and spectrofluorometric detection, were used to analyse polycyclic aromatic hydrocarbons (PAHs) in soil and olives collected in areas contaminated with creosote-treated railway ties. Very high PAH contents (with amounts ranging from 114.7 to 2157.2 and from 167.3 to 3121.8 microg kg(-1) dry weight for total light PAHs and total heavy PAHs, respectively) were found in soil sampled up to 1 m from the source of contamination. The PAH load decreased rapidly with the distance from the railway ties. High amounts of light PAHs, up to 6359.9 microg kg(-1), were also found in oil extracted from olives collected in a rural area where old railway ties were stored. No appreciable transfer of heavy PAHs and benzo[a]pyrene was observed in oil samples.