Theoretical study of Diels-Alder reactions between cyclopentadiene and 2-aryl-4,6-dinitrobenzotriazole 1-oxides

This work deals with the theoretical study of Diels-Alder inverse and normal electron demand reactions. Based on various calculation methods such as SCF/6-31G and DFT/B3LYP with the standard basis set 6-31G, we discuss the possibility of reactions between cyclopentadiene with a series of 2-aryl-4,6-dinitrobenzotriazole 1-oxides from a thermodynamic perspective.     

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.     

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.     

Functionalization of Pasteurized Milk Using Rosemary,Thyme, and Ammoides Aqueous Extracts for Better Microbial Quality and an Improved Antioxidant Activity

This study aimed to evaluate the effects of thyme (Thymus vulgaris L.), rosemary (Rosmarinus officinalis L.), and ammoides (Ammoidespusilla L.) aqueous extracts supplementation on the quality of heat-treated (55, 65, and 75 °C) raw milk (sample lots: A, B, and C) and cold-stored pasteurized milk (lot D). The three herbs have shown rich polyphenol contents (32.65–104.23 mgGAE/g), relevant antioxidant capacity, and high caffeic and rosmarinic acids and catechin contents. A significant reduction in psychrotrophic and total viable bacteria counts (PC and TVC) was attained following milk extract supplementation in both experiments. Monitoring PC and TVC counts in sample lots (A, B, and C) has revealed a significant improvement in extracts’ effectiveness in reducing the TVC count with the increment of temperature. The highest reductions of PC and TVC counts were achieved, respectively, in samples treated with thyme and rosemary in (lots: A, B, and C) and in samples treated with ammoides and thyme in (lot D). Thyme extract showed the highest milk serum DPPH scavenging activity (74.84% at 0.1 mg/mL) and induced a significant Listeria monocytogenes growth inhibition (>1 Log cycle). The sensory evaluation of supplemented milk has shown good consumer acceptability of ammoides-supplemented milk, quite similar to the control sample.     

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.     

Using Bezier curves for the calculation of retention indices of polycyclic aromatic hydrocarbons in the so-called Lee's scale in temperature-programmed gas chromatography with mass spectrometry detection

The retention indices of some polycyclic aromatic hydrocarbons (PAHs) separated by temperature-programmed gas chromatography are computed by smoothing reference data with Bezier curves of orders 6 are more consistent with the scheme of this retention parameter, and they present standard deviations systematically smaller than those associated with classical retention indices. The Bezier curve possesses the property of local control, (i.e., their graphs are modified only in the neighbourhood of the displaced point). The values thus obtained were compared with the corresponding ones calculated in a classical way. Detailed statistical analysis is presented to describe the retention indices of PAHs expressed in the so-called Lee's scale as a function of retention temperatures (in degrees C). As a training set, experimental retention data of PAHs obtained on a PE-5 phase is used for correlation. As prediction sets, literature experimental retention indices expressed in the so-called Lee's scale obtained on a DB-5 slightly polar stationary phase are applied for comparison. The method developed is successfully used for estimating and predicting the capillary gas chromatography retention index of PAHs.     

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.