Synthesis of aggregation pheromone components of cerambycid species through α-hydroxylation of alkylketones

The synthesis of 3-hydroxy-2-hexanone and 2,3-hexanediol, two components of the aggregation pheromone of several cerambycid species, is disclosed in here. Starting from 2-hexanone, through an α-hydroxylation using (diacetoxyiodo)benzene, 3-hydroxy-2-hexanone is obtained in good yield. Further reduction of this compound, gives 2,3-hexanediol in excellent yield. A study of the α-hydroxylation reaction of several alkylketones using an hypervalent iodine reagent is also disclosed in here. The synthesis of optically active compounds (R)- and (S)-3-hydroxy-2-hexanone was achieved starting from 2-hexanone with nitrosobenzene and l- and d-proline respectively, in several reaction media.     

Probing defect species on real surfaces from the analysis of the spectral profile of admolecules

The analysis of changes in the vibrational spectrum of infrared active molecules adsorbed on a ionic surface containing point or extended defects can be an efficient method to determine the nature and density of surface defects. We study the infrared response of ammonia molecules deposited on a ionic surface of MgO containing charge vacancies and dipolar defects in various concentrations and distributions and show significant changes assigned to the defects signature. A Monte Carlo approach is used to randomly deposit the probe molecules on the surface displaying random or regularly arranged defects at low temperature.     

Synthesis of -5,6 Dihydro-1,4,2 Dioxazines from Hydroximates

Successive action of α-bromoesters and organometallics on hydroximates constitute a good way to obtain - 5,6 dihydro-1,4,2 dioxazines.     

Enzyme‐Responsive Silica Mesoporous Supports Capped with Azopyridinium Salts for Controlled Delivery Applications

The preparation of a new capped silica mesoporous material, Rh‐Azo‐S , for on‐command delivery applications in the presence of target enzymes is described. The material consists of nanometric mesoporous MCM‐41‐like supports loaded with Rhodamine B and capped with an azopyridine derivative. The material was designed to show “zero delivery” and to display a cargo release in the presence of reductases and esterases, which are usually present in the colon, mainly due to intestinal microflora. The opening and cargo release of Rh‐Azo‐S in vitro studies were assessed and seen to occur in the presence of these enzymes, whereas no delivery was noted in the presence of pepsine. Moreover, Rh‐Azo‐S nanoparticles were used to study controlled Rhodamine B dye delivery in intracellular media. HeLa cells were employed for testing the “non”‐toxicity of nanoparticles. Moreover, delivery of the dye in these cells, through internalization and enzyme‐mediated gate opening, was confirmed by confocal microscopy. Furthermore, the nanoparticles capped with the Azo group and loaded with a cytotoxic camptothecin ( CPT ) were also prepared (solid CPT‐Azo‐S ) and used as delivery nanodevices in HeLa cells. When this solid was employed, the cell viability decreased significantly due to internalization of the nanoparticles and delivery of the cytotoxic agent.     

New ion exchange membrane derived from sulfochlorated polyether sulfone for electrodialysis desalination of brackish water

The purpose of this work is to study the desalination of brackish water using a new ion exchange membrane, made from sulfochlorated polyethersulfone (Cl‐PES), and crosslinked using aminated polyethersulfone (NH2‐PES) as a crosslinking reagent. This membrane, named ClNH2 membrane, has been obtained by reaction between Cl‐PES with 1.3 SO₂Cl groups per monomer unit and 0.2 equivalent amount of NH2‐PES. ClNH2 membrane has been characterized in terms of contact angle, transport number, intrinsic conductivity, and water uptake (as a function of temperature). Electrodialysis performances of the newly synthetized membranes have been measured using an electrodialysis cell at a laboratory scale and compared to commercial membranes. All the experiments have been performed using synthetic brackish water solutions prepared from sodium chloride salts with different concentrations (varying from 0.5 to 5.0 g/L). The concentration of different water samples obtained has been found to be below the amount recommended by the World Health Organization (WHO) for drinking water.     

A Highly Sensitive and Selective Non-enzymatic Hydrogen Peroxide Sensor Based on Nanostructured Co3O4 Thin Films Using the Sol-gel Method

In this work we report an easy and efficient way to fabricate nanostructured cobalt oxide (Co₃O₄) thin films as a non-enzymatic sensor for H₂O₂ detection. Co₃O₄ thin films were grown on ITO glass substrates via the sol-gel method and characterized with several techniques including X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and optical absorbance. The Co₃O₄ thin films’ performance regarding hydrogen peroxide detection was studied in a 0.1 M NaOH solution using two techniques, cyclic voltammetry (CV) and amperometry. The films exhibited a high sensitivity of 1450 μA.mM⁻¹.cm⁻², a wide linear range from 0.05 μM to 1.1 mM, and a very low detection limit of 18 nM. Likewise, the Co₃O₄ thin films produced showed an exceptional stability and a high selectivity.     

Magnetic Coupling Constants of Self‐Assembled CuII [3×3] Grids: Alternative Spin Model from Theoretical Calculations

This paper reports a theoretical analysis of the electronic structure and magnetic properties of a ferromagnetic Cu^II [3×3] grid. A two‐step strategy, combining calculations on the whole grid and on binuclear fragments, has been employed to evaluate all the magnetic interactions in the grid. The calculations confirm an S=7/2 ground state, which is in accordance with the magnetisation versus field curve and the thermal dependence of the magnetic moment data. Only the first‐neighbour coupling terms present non‐negligible amplitudes, all of them in agreement with the structure and arrangement of the Cu 3d magnetic orbitals. The results indicate that the dominant interaction in the system is the antiferromagnetic coupling between the ring and the central Cu sites (J₃=J₄≈?31 cm^?1). In the ring two different interactions can be distinguished, J₁=4.6 cm^?1 and J₂=?0.1 cm^?1, in contrast to the single J model employed in the magnetic data fit. The calculated J values have been used to determine the energy level distribution of the Heisenberg magnetic states. The effective magnetic moment versus temperature plot resulting from this ab initio energy profile is in good agreement with the experimental curve and the fitting obtained with the simplified spin model, despite the differences between these two spin models. This study underlines the role that the theoretical evaluations of the coupling constants can play on the rationalisation of the magnetic properties of these complex polynuclear systems.     

Molecular Pom Poms from Self‐Assembling α,γ‐Cyclic Peptides

The hierarchical self‐assembly properties of a dimer‐forming cyclic peptide that bears a nicotinic acid moiety to form molecular pom‐pom‐like structures are described. This dimeric assembly self organizes into spherical structures that can encapsulate small organic molecules owing to its porosity and it can also facilitate metal deposition on its surface directed by the pyridine moiety.     

Experimental and Theoretical Studies on Arene‐Bridged Metal–Metal‐Bonded Dimolybdenum Complexes

The bis(hydride) dimolybdenum complex, [Mo₂(H)₂{HC(N‐2,6‐iPr₂C₆H₃)₂}₂(thf)₂], 2 , which possesses a quadruply bonded Mo₂^II core, undergoes light‐induced (365 nm) reductive elimination of H₂ and arene coordination in benzene and toluene solutions, with formation of the Mo^I₂ complexes [Mo₂{HC(N‐2,6‐iPr₂C₆H₃)₂}₂(arene)], 3?C₆H₆ and 3?C₆H₅Me , respectively. The analogous C₆H₅OMe, p‐C₆H₄Me₂, C₆H₅F, and p‐C₆H₄F₂ derivatives have also been prepared by thermal or photochemical methods, which nevertheless employ different Mo₂ complex precursors. X‐ray crystallography and solution NMR studies demonstrate that the molecule of the arene bridges the molybdenum atoms of the Mo^I₂ core, coordinating to each in an η² fashion. In solution, the arene rotates fast on the NMR timescale around the Mo₂‐arene axis. For the substituted aromatic hydrocarbons, the NMR data are consistent with the existence of a major rotamer in which the metal atoms are coordinated to the more electron‐rich C?C bonds.