Electric Field Enhanced Ammoxidation of Aldehydes Using Supported Fe Clusters Under Ambient Oxygen Pressure

Heterogeneous catalytic ammoxidation provides an eco-friendly route for the cyanide-free synthesis of nitrile compounds, which are important precursors for synthetic chemistry and pharmaceutical applications. However, in general such a process requires high pressures of molecular oxygen at elevated temperatures to accelerate the oxygen reduction and imine dehydrogenation steps, which is highly risky in practical applications. Here, we report an electric field enhanced ammoxidation system using a supported Fe clusters catalyst (Fe/NC), which enables efficient synthesis of nitriles from the corresponding aldehydes under ambient air pressure at room temperature (RT). A synergistic effect between the external electric field and the Fe/NC catalyst promotes the ammonia activation and the dehydrogenation of the generated imine intermediates and avoids the unwanted backwards reaction to aldehydes. This electric field enhanced ammoxidation system presents high efficiency and selectivity for the conversion of a series of aldehydes under mild conditions with high durability, rendering it an attractive process for the green synthesis of nitriles with fragile functional groups.     

Covalent-ionic nature of the potential energy surface of the Li-CO2 complex

Unrestricted Hartree-Fock calculations with large basis sets, including d-functions, and the estimation of the correlation energy, show that the potential energy surface for the Li-CO₂ complex is built from the crossing of two states, each of them corresponding to a different electron arrangement. One has a strong ionic character and the other is of van der Waals type. Each portion of the energy surface presents a minimum, which is stable in respect to the dissociation limit.     

Thermal lens spectrometric determination of hexavalent chromium

The applicability of thermal lens spectrometry (TLS) for quantification and routine determination of hexavalent chromium was investigated by using a collinear dual beam thermal lens spectrometer. In aqueous solutions the LOD of 0.1 μg l⁻¹ was obtained for Cr(VI) by using 160 mW laser power. The performance of the technique was verified by the determination of hexavalent chromium in standard reference water samples (NIST SRM 1643a and NIST SRM 1643c) and comparing the results for Cr(VI) in CCA (Cr, Cu, As)-treated timber extracts to concentrations obtained by atomic absorption spectrometry (AAS). Good agreement between the TLS results and reported values for Cr(VI) in SRMs as well as AAS results for Cr(VI) in CCA-treated timbers confirmed that TLS is a reliable and accurate analytical technique applicable for the determination of Cr(VI) in aqueous solutions at concentration levels 0.5–100 μg l⁻¹.     

Ionization of Ozone/Chlorofluorocarbon Mixtures in Atmospheric Gases: Formation and Dissociation of [CHX2O3]+ Complexes (X=Cl,F)

Complexes that undergo extensive molecular reorganization upon unimolecular metastable dissociation are obtained after ionization of atmospheric gases containing ozone and chlorofluorocarbons [Eq. (1)]. These unusual processes, which require fission of all bonds initially present in the CHX₂ unit (X=Cl, F) and combination of C with one of the O atoms of ozone, were demonstrated and their mechanism rationalized by the joint application of mass spectrometric and theoretical methods.     

Essential oil extraction,chemical analysis and anti-Candida activity of Foeniculum vulgare Miller – new approaches

A comprehensive study on essential oil samples of Foeniculum vulgare Miller from Tarquinia (Italy) is reported. A 24-h systematic steam distillation was performed on different harvested samples applying different extraction times. The GC-MS analysis of the residue outcome showed o-cymene, α-phellandrene, α-pinene and estragole as the major constituents. The predominance and continued presence of o-cymene makes this fennel oil a rather unique chemotype. An evident correlation between the antifungal activity and phenological stage is demonstrated. The most active fractions were particularly rich in estragole, as well as a significant amount of fenchone that possibly exerts some additive effect in the expression of overall antifungal potency. Pre-fruiting material produced oil particularly rich in o-cymene. With reference to the duration of the extraction, the maximum amount of oil was released within the first 3 h, whereas the reproductive phase material needed at least 6 h for the extraction.     

Fullerene Derivatives Embedded in Hybrid Sol-Gel Glasses: Nonlinear Optical Properties and Optical Limiting Performances

Hybrid organic-inorganic materials are investigated as suitable materials for inclusion of fullerene derivatives and for fabrication of laser protection devices. A specific synthesis has been developed in order to optimize non-linear optical performances of fullerene derivatives. 3-glicydoxypropyltrymethoxysilane has been used as an inorganic and organic network former to obtain the host material. The sol-gel synthesis consists of the hydrolysis and condensation in acidic conditions of the inorganic network. Epoxy polymerization has been achieved by using zirconium or BF₃ alkoxides precursors. Bulk and multilayer materials doped with a fullerene derivative have been fabricated. They show good optical requirements: high fullerenes concentration, high microstructural homogeneity, high laser damage threshold and high optical limiting efficiency. Optical limiting (OL) mechanisms have been investigated. The most effective in the sol-gel materials is the reverse saturable absorption (RSA) one. However, different mechanisms, like non-linear (NL) scattering and NL refraction contribute to a different extent. Open- and closed-aperture OL and z-scan measurements on sol-gel samples show the contribution of NL scattering and NL refraction at 690 nm. Laser damage threshold has been characterized as a function of the structure of the samples and of the optical configurations (f/66 and f/5).     

A Jocic-type approach for a practical and scalable synthesis of pyrrolonaphthoxazepine (PNOX)-based potent proapoptotic agents

We developed a Jocic-type protocol for the construction of the pyrrolonaphthoxazepine (PNOX) core. After an initial investigation based on the isolation of a trichloromethyl carbinol derivative, we shifted our attention towards a multicomponent single-step protocol. Screening of a variety of bases and solvents led to the identification of the optimum conditions for the preparation of the key α-aryloxy carboxylic acids to undergo intramolecular cyclization. The novel chemical route significantly improved overall yields for the preparation of PNOX-based compounds and was successfully extended to the preparation of 1,4-benzoxazinone-based templates.     

Generalized immediate exchange models and their symmetries

We reconsider the discrete dual of the immediate exchange model and define a more general class of models where mass is split, exchanged and merged. We relate the splitting process to the symmetric inclusion process via thermalization and from that obtain symmetries and self-duality for it and its generalization. We show that analogous properties hold for models where the splitting is related to the symmetric exclusion process or to independent random walkers.