X‐ray induced degradation of surface bound azido groups during XPS analysis

Mesoporous silica SBA‐15 was synthesized and silanized with azidopropyl triethoxysilane in order to design a clickable material. Fourier transform infrared analysis permitted to prove the attachment of the azidopropylene groups to SBA‐15 resulting in the reactive and functional material N₃‐SBA‐15. X‐ray photoelectron spectroscopy was used to determine the surface composition of SBA‐15. However, we unexpectedly found that the surface bound azido groups undergo X‐ray induced decomposition during the X‐ray photoelectron spectroscopy analysis resulting in the formation of nitrenes. These are very reactive groups able to intercalate C―C and C―H bonds of the propylene chains as judged from the N1s peak shape. Possible mechanisms of intercalation are suggested. C1s and N1s peaks were recorded at different exposure time. N/C, N⁺/N and N⁺/C undergo exponential decay. N⁺/N reaches the value of zero in less than 80 min of exposure to the X‐ray source. The N⁺/C decay plot was fitted with first‐order kinetics, and the decomposition kinetic constant (k_dec) was found to equal to 516.4 s^?1. This is a fast X‐ray induced degradation which must be considered with care when examining clickable materials with surface bound alkyl azido groups. Copyright © 2016 John Wiley & Sons, Ltd.     

Solvent free synthesis of 1,3-diaryl-2-propenones catalyzed by commercial acid-clays under ultrasound irradiation

This paper presents a novel solvent free method of synthesis of trans-chalcones. The method was based on ultrasound irradiation of the reagents (aryl methyl ketones and aryl aldehydes) in presence of commercial acid-montmorillonites as catalysts. The trans-chalcones were synthesized in high yields (85–95%) and excellent selectivity in a short reaction time.     

A DFT study of the hydration of monophosphate complexes of iron (III),

A systematic theoretical DFT study of the bonding between the cation Fe³⁺ and the anion was carried out. The role of water ligands is presented. Several isomers with tetrahedral, bipyramidal and octahedral environments around the iron ion were investigated. 5-fold coordination of the Fe³⁺ cation is found when 5 and 6 water molecules are included. Calculated infrared spectra are also presented.     

Towards gas chromatography-mass spectrometry coupling protocols for both identifying and quantification essential oils of Thymus capitatus Hoff et Link

Essential oil of Thymus capitatus Hoff et Link is analysed by using four techniques: GC/pyrolyse/MS, GC/FID, electronic impact GC/MS (quadripole), and GC/MS (ion trap). Both major and trace components are analysed. The GC/pyrolyse/MS coupling provides reference to the exact mass compositions without any need of the previously purified references, neither for major or trace components. The comparison between this reference analysis and GC/FID shows that the FID response coefficients may vary by a mean 7% from one component to another. As it was expected, quadripole or ion trap response coefficients vary to a much greater extent (a mean 25%), although the two MS techniques response coefficients are first order consistent. We conclude that GC/MS coupling could be used not only as it is usual for reliable identifications, but also for a complete quantitative routine analysis of essential oils. Expected precision could be very similar to GC/FID precision provided correcting species by species the MS analysis by a mean value of the response coefficient measured for the MS 70 eV electronic impact ionisation technologies. The GC/pyrolyse/MS coupling is proposed as a relevant tool for analysing reference samples containing trace natural species that could not be purified.     

Sequential photo-addition of glycine methyl-ester to [60]fullerene

While direct photo-addition of glycine-methyl-esters (GME) to [60]fullerene (C₆₀) can yield a complex product mixture, only a fulleropyrrolidine (FP) mono-adduct has been characterized and the mechanism remains to be ascertained. We show here that visible light irradiation of a mixture of C₆₀ and GME in the presence of oxygen is a direct route to synthesize sequentially higher FP poly-adducts through an unprecedented cyclization–deamination mechanism. Each step of this mechanism leads to a FP adduct involving the correlated addition of two GME radicals and the departure of an ammonia molecule.     

First-row transition metal atoms adsorption on rutile TiO2(110) surface

We performed periodic DFT calculations for adsorption of metal atoms on a perfect rutile TiO₂(110) surface (at low coverage, ???=?1/3) to investigate the interaction of an individual metal atom with TiO₂ and to compare it with a study previously done on MgO(100). We considered partial period of Mendeleev??s table from K to Zn. The overall evolution of the adsorption energies shows two maxima as for MgO(100). Two main differences, however, exist: the adsorption energy is much stronger and the first maximum is enhanced relative to the second one. This is attributed to the reducibility of the surface titanium cation. When the adsorbed metal is electropositive, it is oxidized under adsorption transferring electrons to titanium cations. We present the effect of introducing a Hubbard term to the gradient-corrected approximation band-structure Hamiltonian (GGA?+?U). The introduction of a reasonable Hubbard correction preserves the trends and allows localizing the electron of the reduction on Ti atoms in the near surface region. Finally, our results conclude that for heavier M atoms of the period, insertion is energetically favored relative to adsorption.     

Solubility of some phenolic compounds in aqueous alkali metal nitrate solutions from (293.15 to 318.15) K

This paper is continuation of the study concerning the solubility-temperature dependence data for some phenolic compounds (PhC), contained in olive mill wastewater (OMWW), in two nitrate salts (KNO₃ and NaNO₃) aqueous solutions. The solubilities of PhC were determined in the temperature ranging from (293.15 to 318.15) K. It has been observed that the solubility, in aqueous nitrate solutions, increases with increasing temperature. Results showed that alkali metal nitrate has a salting-out effect on the solubility of PhC. The effect of the anion of the electrolyte on the solubility of PhC is observed by comparing these results with values reported in the previous papers for the effect of LiCl, NaCl and KCl. For each cation, the solubilites of the phenolic compounds are higher with nitrate anion than with chloride anion. Results were interpreted in terms of the salt hydration shells and the ability of the solute to form hydrogen-bond with water. The solubility data were accurately correlated by a semi empirical equation. The standard molar Gibbs free energies of transfer of PhC (Δ_trG^°) from pure water to aqueous solutions of the nitrate salts have been calculated from the solubility data. The decrease in solubility is correlated to the positive Δ_trG^° value which is mainly of enthalpic origin.     

Chemical Composition and <em>in Vitro</em> Evaluation of the Antioxidant and Antimicrobial Activities of <em>Eucalyptus gillii </em>Essential Oil and Extracts<em></em>

In this study, essential oil and various extracts (hexane, petroleum ether, acetone, ethanol, methanol and water) of Eucalyptus gilii were screened for their chemical composition, antimicrobial and antioxidant activities. The essential oil chemical composition was analyzed by gas chromatography-mass spectrometry (GC-MS) and gas chromatography-flame ionization detection (GC-FID), respectively. Thirty four compounds were identified, corresponding to 99.5% of the total essential oil. Tannins [104.9-251.3 g catechin equivalent (CE)/Kg dry mass], flavonoids [3.3-34.3 g quercetin equivalent (QE)/Kg dry mass], phenolics [4.7-216.6 g gallic acid equivalent (GAE)/Kg dry mass] and anthocyannins [1.2-45.3 mg cyanidin-3-glucoside equivalent (C3GE)/Kg dry mass] of various extracts were investigated. Free radical scavenging capacity of all samples was determinedt. In the 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay, the IC₅₀ of essential oil was 163.5 ± 10.7 mg/L and in the 2,2'-azinobis-3-ethylbenzothiazoline-6-sulphonate (ABTS) assay, it was 94.7 ± 7.1 mg/L. Among the various extracts, the water extract showed the best result (IC₅₀ = 11.4 ± 0.6 mg/L) in the DPPH assay which was comparable to vitamin C (IC₅₀ = 4.4 ± 0.2 mg/L). The antimicrobial activities were evaluated against different bacterial and fungal strains. Gram positive bacteria were found to be more sensitive to the essential oil and extracts than Gram negative ones. Anthocyanins seem to have a major effect on the growth of Bacillus subtilis (R² = 0.79). A significant antifungal activity was observed against the yeast and fungi. Correlations between chemical composition and antioxidant activities were studied and R² values were about 0.96 for the effect of phenolics on the DPPH assay.     

Optoelectronic and conductivity of ᴫ‐conjugated polymers based on phenylenevinylene, 1,3,4‐thiadiazole and thiophene: Suitable candidates for n‐type organic semiconductors

New poly‐phenylenevinylenes PPVs containing 1,3,4‐thiadiazole as candidates for organic semiconductors have been theoretically studied at density functional theory (DFT) and time‐dependent DFT levels. This study has been conducted in order to investigate the geometrical and electronic properties as well as the conductivity of a series of PPV–thiophene–1,3,4–thiadiazole–thiophene (H–PhTAT–H) containing –CHO, –CH₂–P(=O)(OCH₃)₂, and phenyl–CHO (PhCHO) terminal groups. The impact of terminal groups on the optical bandgaps, electron affinity, LUMO energy, and intramolecular reorganization energy was studied for different oligomers and for a limit polymer. The incorporation of terminal groups did not affect the chain length evolution and the vertical transition energy E_vert value for a polymer limit compared with the unsubstituted oligomer (H–PhTAT–H). All studied properties showed that CHO–PhTAT–PhCHO and H–PhTAT–H oligomers can be considered as n‐type semiconductors.