In situ growth of well-dispersed CdS nanocrystals in semiconducting polymers

A straight synthetic route to fabricate hybrid nanocomposite films of well-dispersed CdS nanocrystals (NCs) in poly[2-methoxy-5-(2''-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) is reported. A soluble cadmium complex [Cd(SBz)₂]₂·MI, obtained by incorporating a Lewis base (1-methylimidazole, MI) on the cadmium bis(benzyl)thiol, is used as starting reagent in an in situ thermolytic process. CdS NCs with spherical shape nucleate and grow well below 200°C in a relatively short time (30 min). Photoluminescence spectroscopy measurements performed on CdS/MEH-PPV nanocomposites show that CdS photoluminescence peaks are totally quenched inside MEH-PPV, if compared to CdS/PMMA nanocomposites, as expected due to overlapping of the polymer absorption and CdS emission spectra. The CdS NCs are well-dispersed in size and homogeneously distributed within MEH-PPV matrix as proved by transmission electron microscopy. Nanocomposites with different precursor/polymer weight ratios were prepared in the range from 1:4 to 4:1. Highly dense materials, without NCs clustering, were obtained for a weight/weight ratio of 2:3 between precursor and polymer, making these nanocomposites particularly suitable for optoelectronic and solar energy conversion applications.     

Direct Regio‐, Diastereo‐, and Enantioselective Vinylogous Michael Addition of Prochiral 3‐Alkylideneoxindoles to Nitroolefins

3‐Alkylidene‐2‐oxindoles represent a simple, yet enabling subfamily of indole alkaloids, and their ability to react as electron‐poor acceptors has largely been investigated. In contrast, their utility as pronucleophilic synthons remains elusive. In this context, the present article describes the successful execution of the direct, organocatalytic asymmetric Michael addition of prochiral 3‐alkylideneoxindoles to nitroolefins. A variety of γ‐substituted alkylideneoxindoles carrying two stereocenters at both the γ‐ and δ‐carbon sites was assembled with excellent stereoselectivity and without olefin isomerization or stereochemical ablation.     

Obesity and Male Reproduction: Do Sirtuins Play a Role?

Obesity is a major current public health problem of global significance. A progressive sperm quality decline, and a decline in male fertility, have been reported in recent decades. Several studies have reported a strict relationship between obesity and male reproductive dysfunction. Among the many mechanisms by which obesity impairs male gonadal function, sirtuins (SIRTs) have an emerging role. SIRTs are highly conserved nicotinamide adenine dinucleotide (NAD+)-dependent deacetylases that play a role in gene regulation, metabolism, aging, and cancer. SIRTs regulate the energy balance, the lipid balance, glucose metabolism, and adipogenesis, but current evidence also indicates a role for SIRTs in male reproduction. However, the majority of the studies have been conducted in animal models and very few have been conducted with humans. This review shows that SIRTs play an important role among the molecular mechanisms by which obesity interferes with male fertility. This highlights the need to deepen this relationship. It will be of particular interest to evaluate whether synthetic and/or natural compounds capable of modifying the activity of SIRTs may also be useful for the treatment of obesity and its effects on gonadal function. Although few studies have explored the role of SIRT activators in obesity-induced male infertility, some molecules, such as resveratrol, appear to be effective in modulating SIRT activity, as well as counteracting the negative effects of obesity on male fertility. The search for strategies to improve male reproductive function in overweight/obese patients is a challenge and understanding the role of SIRTs and their activators may open new interesting scenarios in the coming years.     

Myo-Inositol Limits Kainic Acid-Induced Epileptogenesis in Rats

Epilepsy is a severe neurological disease characterized by spontaneous recurrent seizures (SRS). A complex pathophysiological process referred to as epileptogenesis transforms a normal brain into an epileptic one. Prevention of epileptogenesis is a subject of intensive research. Currently, there are no clinically approved drugs that can act as preventive medication. Our previous studies have revealed highly promising antiepileptogenic properties of a compound–myo-inositol (MI) and the present research broadens previous results and demonstrates the long-term disease-modifying effect of this drug, as well as the amelioration of cognitive comorbidities. For the first time, we show that long-term treatment with MI: (i) decreases the frequency and duration of electrographic SRS in the hippocampus; (ii) has an ameliorating effect on spatial learning and memory deficit associated with epileptogenesis, and (iii) attenuates cell loss in the hippocampus. MI treatment also alters the expression of the glial fibrillary acidic protein, LRRC8A subunit of volume-regulated anion channels, and protein tyrosine phosphatase receptor type R, all expected to counteract the epileptogenesis. All these effects are still present even 4 weeks after MI treatment ceased. This suggests that MI may exert multiple actions on various epileptogenesis-associated changes in the brain and, therefore, could be considered as a candidate target for prevention of epileptogenesis.     

Alumina/Silicon Carbide Laminated Composites by Spark Plasma Sintering

Ceramic laminates composed of alumina/silicon carbide composite layers were produced by spark plasma sintering (SPS). Monolithic composite disks containing up to 30 vol% of silicon carbide were fabricated by stacking together and cosintering by SPS green layers prepared by tape casting water-based suspensions. An engineered laminate with a specific layer combination that is able to promote the stable growth of surface defects before final failure was also designed and produced. Fully dense materials with an optimum adhesion between the constituting layers and a homogeneous distribution of the two phases were obtained after SPS. Monolithic composites showed an increasing strength with SiC load, and biaxial strength values as high as 700 MPa were observed for a SiC content of 30 vol%. The engineered laminate showed a peculiar crack propagation that is responsible for the high strength value of about 600 MPa and for the evident insensitivity to surface defects.     

Photocatalytic Inactivation of Legionella Pneumophila and an Aerobic Bacteria Consortium in Water over TiO2/SiO2 Fibres in a Continuous Reactor

A continuous photoreactor, working in a total recycle mode and irradiated by a low-pressure Hg lamp, has been used to study the bactericidal effect of a photocatalyst, formed by TiO₂ embedded in SiO₂ fibres, on Legionella pneumophila and a consortium of common gram-negative aerobic bacteria: (Escherichia coli, Klebsiella sp., Pseudomona sp. and Proteus sp.) in water. The kinetic modeling of the inactivation process, carried out with the measured values of viable bacteria concentration at the outlet of photoreactor, evidenced that for each pass inside the photoreactor the ratio between the outlet and inlet cell concentrations was of order of 0.01 for the inactivation of L. pneumophila. For the other aerobic bacteria, which are usually taken as reference in photocatalytic bacteria inactivation studies, this ratio was of order of 0.3 for the first hour of illumination, while upon prolonged irradiation (up to 9 h) this ratio increased to 0.7. Several factors inducing this latter decrease of efficiency are possible, as e.g. competition for photocatalytic attack between microorganisms and organic compounds released by damaged bacteria or photoinduced alteration of a small fraction of still viable bacteria making them less interactive with the photocatalyst. The inactivation mechanism normally proposed for common bacteria involves an initial attack of the photogenerated radicals to the outer membrane; the consequent membrane dispersion allows the radicals to damage the cytoplasmic membrane. The higher lethality of the photocatalytic method observed towards Legionella: (in comparison to the other aerobic bacteria) is explained considering that the radicals attack the Legionella secretion system, which is adapted for high virulence and would become activated for and through adhesion to the TiO₂ surface. This attack would then be able to inactivate L. pneumophila without dispersing the outer membrane. Apart from this, the water flow through the catalyst fibres can facilitate the bacteria transport towards the anatase surface, and additionally the generated shear stress may help adhesion, at least for some bacteria as E. coli, contributing further to improve the photokilling efficiency; both factors may contribute to the efficiency of this photoreactor configuration.     

Effect of sonolysis on waste activated sludge solubilisation and anaerobic biodegradability

Activated sludge processes are key technologies in wastewater treatment. These biological processes produce huge amounts of waste activated sludge (WAS) or otherwise biosolids. Mechanical, thermal, and/or chemical WAS conditioning techniques have been proposed to reduce the sludge burden. Among the WAS treatments, the pre-treatment with ultrasound (US) is one of the most innovative processes. In many anaerobic digestion processes for the treatment of the sludge produced in wastewater treatment plants, the hydrolysis of the organic matter has been identified as the rate limiting step.This study is focused on the effect of US pre-treatment of WAS to the anaerobic digestion. Particle size reduction, Chemical Oxygen Demand (COD) solubilization and biodegradability by anaerobic digestion were monitored in order to find the optimal dose in US pre-treatment.The results show the better sonolysis conditions (US density, sonication time, specific energy) which can significantly improve the COD solubilisation and the anaerobic biodegradability.     

Nonglycosidic Agonists of Invariant NKT Cells for Use as Vaccine Adjuvants

Based on the crystal structures of human α‐GalCer–CD1d and iNKT–α‐GalCer–CD1d complexes, nonglycosidic analogues of α‐GalCer were synthesized. They activate iNKT cells resulting in dendritic cell maturation and the priming of antigen‐specific T and B cells. Therefore, they are attractive adjuvants in vaccination strategies for cancer and infectious diseases.

     

Azacrown Ethers with Naphthyl Branches. Fluorescence Properties,Protonation and Metal Coordination

Starting from 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane, we have prepared two compounds by replacing the amine hydrogens with naphthyl or 3,5-bis(2′-oxymethylnaphthyl)benzyl units. The absorption and emission spectra of compounds 2 (N,N′-bis(2-naphthylmethyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane) and 3 (N,N′-bis[3,5-bis(2′-oxymethylnaphthyl)benzyl]-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane) have been studied in CH₃CN:CH₂Cl₂ 1:1 (v/v) solution. For comparison purposes, the spectroscopic properties of N-methyl(2-methylnaphthalene)ethylamine (1) have also been investigated. For each compound, the absorption spectra are qualitatively very similar to that of naphthalene, with molar absorption coefficients as expected for the presence of one (1), two (2), and four (3) naphthyl chromophoric groups. The fluorescence spectra, however, are quite different from that of naphthalene. The naphthalene-type fluorescence (λ_max = 337 nm) is strongly quenched, particularly for compounds 1 and 2 which also exhibit a broad emission band in the visible region (λ_max ≈ 480 nm) assigned to a low lying charge-transfer excited state. In the case of compound 3, a quenched naphthalene-type band is accompanied by weak exciplex and excimer emissions. Upon titration with CF₃SO₃H, the charge transfer bands of 1 and 2 and the exciplex emission of 3 disappear and the naphthalene-type bands regain intensity. Titration plots show that in compounds 2 and 3 the protonation of the two nitrogens occurs stoichiometrically in two distinct steps. Titration with Zn²⁺ gives rise to 2.Zn²⁺ and 3.Zn²⁺ complexes. This article is dedicated to Professor Dedier Astruc.     

Guanidinoneomycin B recognition of an HIV-1 RNA helix

Aminoglycoside antibiotics are small-molecule drugs that bind RNA. The affinity and specificity of aminoglycoside binding to RNA can be increased through chemical modification, such as guanidinylation. Here, we report the binding of guanidinoneomycin B (GNB) to an RNA helix from the HIV-1 frameshift site. The binding of GNB increases the melting temperature (T(m)) of the frameshift-site RNA by at least 10 degrees C, to a point at which a melting transition is not even observed in 2 M urea. A structure of the complex was obtained by using multidimensional heteronuclear NMR spectroscopic methods. We also used a novel paramagnetic-probe assay to identify the site of GNB binding to the surface of the RNA. GNB makes major-groove contacts to two sets of Watson-Crick bases and is in van der Waals contact with a highly structured ACAA tetraloop. Rings I and II of GNB fit into the major groove and form the binding interface with the RNA, whereas rings III and IV are exposed to the solvent and disordered. The binding of GNB causes a broadening of the major groove across the binding site.