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.     

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.     

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.     

Compositional studies: antioxidant and antidiabetic activities of Capparis decidua (Forsk.) Edgew

Capparis decidua is one of the traditional remedies used for various medicinal treatments in Pakistan. This study presents the determination of proximate composition, amino acids, fatty acids, tocopherols, sterols, glucosinolate and phenolic content in extracts obtained from different aerial parts of C. decidua, as well as their antidiabetic and antioxidant activity. All examined extracts were prominently rich in phenolics and glucosinates, and they showed potent antidiabetic and antihemolytic activity. The present study could be helpful in developing medicinal preparations for the treatment of diabetes and related symptoms.     

Synthesis,characterization, and degradation of block polyesteramides containing poly(L-lactide) segments

Random multiblock polyesteramides (PEAs) having polyester (PE) content of 20–50 wt % have been prepared by low-temperature polycondensation using sebacoyl chloride, 1,6-diaminohexane, and telechelic oligomers of L-lactide with M_n = 600–1500. The PEAs were characterized by IR and ¹H-NMR spectroscopy, wide-angle X-ray diffraction, and thermal analysis. Only the polyamide segments are able to crystallize, and the crystallinity depends on the composition and architecture of the PEAs. From viscosity and IR measurements it was established that the chain degradation of PEA powders or films suspended in buffer solutions occurs by hydrolysis of the ester linkages. The degradation rate is influenced by pH, PE content, and, to a lesser extent, by crystallinity. © 1992 John Wiley & Sons, Inc.     

Catalytic Synergism in a C60IL10TEMPO2 Hybrid in the Efficient Oxidation of Alcohols

A novel fullerene [5:1]hexakisadduct bearing two 2,2,6,6‐tetramethylpiperidine 1‐oxyl (TEMPO) radicals and ten 1‐propyl‐3‐methylimidazolium bromide moieties has been synthesized and characterized. Such an C₆₀IL₁₀TEMPO₂ hybrid has been successfully employed as a catalyst in the selective oxidation of a wide series of alcohols and is highly active at just 0.1 mol% loading. Moreover, it can be easily recovered by adsorption onto a multi‐layered covalently‐linked SILP phase (mlc‐SILP) through a “release and catch” approach and reused for up to 12 cycles without loss in efficiency. Interestingly, a catalytic synergistic effect of TEMPO and imidazolium bromide moieties combined in the same hybrid has been clearly shown.