Reduction of nitrobenzene derivatives using sodium borohydride and transition metal sulfides

Reported here is the reduction of aromatic nitro compounds using sodium borohydride and transition metal sulfides as catalysts. The reaction conditions were optimized using the reduction of nitrobenzene as a model reaction. The catalysts studied were iron sulfide (Fe₃S₄), copper sulfide (CuS), zinc sulfide (ZnS), cobalt sulfide (Co₃S₄), and nickel sulfide (NiS). The reduction was monitored using gas chromatography. Quantitative conversions were achieved using Co₃S₄ and NiS, representing a ten-fold increase in reactivity compared to the non-catalyzed reaction. Fe₃S₄ and ZnS had no apparent effect on the reduction of nitrobenzene while the reduction using CuS showed a marginal increase. The reduction method was applied to several aryl-nitro derivatives containing either electron-withdrawing or electron-donating groups. Halogen containing aryl-nitro compounds were reduced without dehalogenation. The reduction had no effect on other functional groups such as carboxylic acids, esters, amides, or alkenes, indicating that the reduction is highly chemoselective.     

Lipid-Based Nanostructures for the Delivery of Natural Antimicrobials

Encapsulation can be a suitable strategy to protect natural antimicrobial substances against some harsh conditions of processing and storage and to provide efficient formulations for antimicrobial delivery. Lipid-based nanostructures, including liposomes, solid lipid nanoparticles (SLNs), and nanostructured lipid nanocarriers (NLCs), are valuable systems for the delivery and controlled release of natural antimicrobial substances. These nanostructures have been used as carriers for bacteriocins and other antimicrobial peptides, antimicrobial enzymes, essential oils, and antimicrobial phytochemicals. Most studies are conducted with liposomes, although the potential of SLNs and NLCs as antimicrobial nanocarriers is not yet fully established. Some studies reveal that lipid-based formulations can be used for co-encapsulation of natural antimicrobials, improving their potential to control microbial pathogens.     

Synthesis of New Brassinosteroid 24-Norcholane Type Analogs Conjugated in C-3 with Benzoate Groups

The metabolism of brassinosteroid leads to structural modifications in the ring skeleton or the side alkyl chain. The esterification and glycosylation at C-3 are the most common metabolic pathways, and it has been suggested that conjugate brassinosteroids are less active or inactive. In this way, plants regulate the content of active brassinosteroids. In this work, the synthesis of brassinosteroid 24-norcholane type analogs conjugated at C-3 with benzoate groups, carrying electron donor and electron attractant substituents on the aromatic ring, is described. Additionally, their growth-promoting activities were evaluated using the Rice Lamina Inclination Test (RLIT) and compared with that exhibited by brassinolide (used as positive control) and non-conjugated analogs. The results indicate that at the lowest tested concentrations (10⁻⁸–10⁻⁷ M), all analogs conjugated at C-3 exhibit similar or higher activities than brassinolide, and the diasteroisomers with S configuration at C-22 are the more active ones. Increasing concentration (10⁻⁶ M) reduces the biological activities of analogs as compared to brassinolide.     

Growth and Atomic-Scale Characterization of Ultrathin Silica and Germania Films: The Crucial Role of the Metal Support

The present review reports on the preparation and atomic-scale characterization of the thinnest possible films of the glass-forming materials silica and germania. To this end state-of-the-art surface science techniques, in particular scanning probe microscopy, and density functional theory calculations have been employed. The investigated films range from monolayer to bilayer coverage where both, the crystalline and the amorphous films, contain characteristic XO₄ (X=Si,Ge) building blocks. A side-by-side comparison of silica and germania monolayer, zigzag phase and bilayer films supported on Mo(112), Ru(0001), Pt(111), and Au(111) leads to a more general comprehension of the network structure of glass former materials. This allows us to understand the crucial role of the metal support for the pathway from crystalline to amorphous ultrathin film growth.     

Palladium nanoparticles on modified cellulose as a novel catalyst for low temperature gas reactions

Cellulose - Palladium was incorporated into carboxymethylated cellulose fibers as a support, thereby becoming an efficient and stable catalyst for low temperature gas phase reaction. Thus, NO was...     

Nickel‐Catalyzed Mizoroki–Heck Reaction of Aryl Sulfonates and Chlorides with Electronically Unbiased Terminal Olefins: High Selectivity for Branched Products

Achieving high selectivity in the Heck reaction of electronically unbiased alkenes has been a longstanding challenge. Using a nickel‐catalyzed cationic Heck reaction, we were able to achieve excellent selectivity for branched products (≥19:1 in all cases) over a wide range of aryl electrophiles and aliphatic olefins. A bidentate ligand with a suitable bite angle and steric profile was key to obtaining high branched/linear selectivity, whereas the appropriate base suppressed alkene isomerization of the product. Although aryl triflates are traditionally used to access the cationic Heck pathway, we have shown that, by using triethylsilyl trifluoromethanesulfonate, we can effect a counterion exchange of the catalytic nickel complex, such that cheaper and more stable aryl chlorides, mesylates, tosylates, and sulfamates can be used to yield the same branched products with high selectivity.     

Study of medieval enamelling on gilded objects combining SEM-EDAX and PIXE

A set of fragments of metallic artefacts from the medieval period excavated from Ciudad Real in Spain has been studied. The objects are gilded copper buckles with a champlevé enamelling decoration. The composition of predominantly blue-coloured enamels has been analysed using three non-destructive techniques, SEM-EDAX (scanning electron microscopy coupled with energy-dispersive X-ray analysis), X-ray fluorescence (XRF) and PIXE (particle-induced X-ray emission). Analyses show that Co is responsible for the blue colour. The results of the two techniques are compared, as well as the main components which constitute the enamel. Analyses suggest that Cu is responsible for red colour.     

Thermomechanical treatment of two Ecuadorian zeolite-rich tuffs and their potential usage as supplementary cementitious materials

Two Ecuadorian zeolite-rich tuffs, coded as Zeo1 (Mordenite) and Zeo2 (Clinoptilolite–Heulandite–Mordenite), were treated and used as supplementary cementitious materials (SCM) so as to study the effect of the thermal and mechanical treatments on pozzolanic reaction in mortars. The treatment was carried out by means of thermomechanical process according to a central composite-blocked cube-star experimental design. In this experimental design as independent factors the milling time (48, 60, 90, 120 and 132 min) and the heating temperatures (559, 600, 700, 800 and 841 °C) were used but keeping a constant heating time (5 h), and zeolite-rich tuffs as experimental blocks. The proportion of SCM was kept constant i.e. 15 %. On the other hand, the compressive strength, fixed lime, normalized water in hydrates and mg Ca(OH)₂ per mg Cement at 7, 28 and 45 days, as well as hydration products related to dehydration degree of the zeolitic tuffs (DOD) were used as dependent factors. In addition, Quantitative and High-temperature chamber XRD, TG-DSC, particle size distribution and SEM-EDS were also carried out. The most significant factor was calcination leading to increase in the compressive strength compared to control, but just up to 800 °C because of recrystallization. As a conclusion, a meaningful loss of crystal structure of zeolites was not observed; but instead, the treatment could only lead to removing the water in cages and voids, thus improving the reaction with Ca(OH)₂, producing more hydrates. In addition, lime was not only fixed by pozzolanic reaction, but also by carbonation.     

A relativistic quark-diquark model for the nucleon

We developed a constituent quark-diquark model for the nucleon and its resonances using a harmonic oscillator potential for the interaction. The effects due to relativistic kinetic energy correction are studied. Finally, charge form factor of the model is calculated and compared with experimental data.      

Super-exponential inflation from a dynamical foliation of a 5D vacuum state

We introduce super-exponential inflation (ω<−1) from a 5D Riemann-flat canonical metric on which we make a dynamical foliation. The resulting metric describes a super accelerated expansion for the early universe well known as super-exponential inflation that, for very large times, tends to an asymptotic de Sitter (vacuum dominated) expansion. The scalar field fluctuations are analyzed. The important result here obtained is that the spectral index for energy density fluctuations is not scale invariant, and for cosmological scales becomes ns(k<k_?)?1. However, for astrophysical scales this spectrum changes to negative values ns(k>k_?)<0.