Characterization of polyoxometalate/polymer photo-composites: A toolbox for the photodegradation of organic pollutants

Different inorganic/organic photocomposites based on polyoxometalate (POM) nanoparticles have been developed for photocatalytic applications. Currently, polyoxometalate nanoparticles have been successfully in-situ embedded into an acrylate polymer network by photopolymerization upon mild visible light irradiation at 405 nm. The proposed POM/polymer photocomposites have been characterized using complementary techniques for a better understanding of their photocatalytic activity. Interestingly, the obtained photocomposites exhibit high rigidity, excellent thermal stability, a non-negligible porosity and new functionalities such as light reactivity and redox properties. Moreover, developed composites showed efficient catalytic activity for the color removal of aqueous solutions of erythrosine and rose Bengal under Light Emitting Diodes LED@375 nm irradiation reaching 80 and 90% as a final color removal, respectively.     

Transformations de N-acylaziridines catalysées par des supports à base de silice et d’alumine : une élucidation mécanistique

The silica gel, neutral alumina and acid activated clays transform the N-acyl-2,2-dimethylaziridines 1 into a mixture of N-methallylamides 2, oxazolines 3 and amidoalcohols 4. The reaction of N-benzoyl-2,2-dimethylaziridine with benzylcyanid anion leads to a mixture of amidopyrroline 5 and iminopyrrolidine 6. The product 5 was converted into its tautomer 6 by chromatogaphy on silica gel. Ionic mechanisms were then proposed to explain the formation of products 2–6 resulting from the regioselective ring opening on the more substituted C2 carbon side.     

Experimental and theoretical investigations of the molecular structure,the spectroscopic properties and TD-DFT analysis of a new semiconductor hybrid based iron(III)

In this work, a new hybrid material (C₅H₆N₂Cl)₂[FeCl₄].Cl abbreviated (CAP)₂[FeCl₄].Cl was prepared using room temperature slow evaporation technique. The X-ray diffraction analysis revealed that the compound is crystallized in the centrosymmetric space group P2₁/c of the monoclinic system. The crystallographic network consists of an Fe(III) ion located on an inversion center and coordinated by four chlorine, isolated Cl^– and two (CAP)⁺ protonated cations linked by N–H...Cl and C–H...Cl hydrogen bonds to form a zero-dimensional network. Hirshfeld surface analysis was used to analyze intermolecular interactions present in the crystal structure. The vibrational properties were inspected by means of Infra-Red absorption and Raman diffusion spectroscopy techniques. In addition, theoretical calculations based on the DFT/B3LYP/LanL2DZ method and the time-dependent density functional theory (TD–DFT) were performed in order to gain more information and help in the examination of over-all properties of the title compound. Good and interesting experimental findings were presented and good consistency was found with the calculated results.     

Line broadening,shifting and mixing parameters for the ν1 + ν3 band of OCS perturbed by N2 and O2

In this paper, we report measured Rosenkranz N₂- and O₂-broadening, induced pressure-shift and mixing coefficients for OCS in the ν₁ + ν₃ band, using a multi-pressure fitting technique applied to the measured shapes of the lines, including the interference effects caused by the line overlaps. These measurements were made by analysing six laboratory absorption spectra recorded at 0.004 cm^?1 resolution using the Fourier transform spectrometer Bruker IFS125HR located at the Laboratoire Interuniversitaire des Systèmes Atmosphériques, in Créteil. The spectra have been recorded in the 1850–3000 cm^?1 wave number range at 295 K, using a multipass absorption cell with an optical path of 3.249 m. The total sample pressures ranged from 5.97 to 83.28 Torr with OCS volume mixing ratios between 0.001 and 0.013 in nitrogen or oxygen. We have been able to determine the N₂- and O₂-pressure-broadening coefficients of 81 ν₁ + ν₃ transitions with rotational quantum number J up to 50. The measured N₂- and O₂-broadening coefficients range from 0.0815 ± 0.0698 to 0.1169 ± 0.1027 cm^?1 atm^?1 at 295 K, respectively. Most of the measured pressure shifts are positive. The reported N₂- and O₂-induced pressure-shift coefficients vary from about ?0.0103 ± 0.0092 to 0.0097 ± 0.0092 cm^?1 atm^?1, respectively. We have examined the dependence of the measured broadening parameters on the quantum number m (m = ?J for the P branch and m = J + 1 for the R branch) and also developed an empirical expression to describe the broadening coefficients in terms of |m|. On average, this empirical expression reproduces the measured broadening coefficients to within 2%. Using a semi-classical Robert and Bonamy formalism, the theoretical broadening coefficients have been calculated at room temperature and compared with the experimental results. The theoretical results of the broadening coefficients are in very good overall agreement with the experimental data (2%).     

Theoretical study of the SrLi+ molecular ion: structural,electronic and dipolar properties

ABSTRACT

The structural and electronic properties of (SrLi)⁺ molecular ion have been determined by the use of ab initio approaches. Potential energy curves (PECs) with their spectroscopic constants (R_e, D_e, ω_e, T_e, B_e and ω_eχ_e) have been calculated. Also, the vibrational properties and the electric dipole moments, either permanent (PDM) or transition (TDM) ones, have been investigated and analysed. Large Gaussian basis sets, the full valence configuration interaction (FCI) and the formalism of non-empirical pseudo-potential including the two approaches, effective core potential (ECP) and core polarisation potential (CPP), are analysed. Therefore, (SrLi)⁺ is considered as a two effective electrons system. Numerous excited states of symmetries ^1,3Σ⁺, ^1,3Π and ^1,3Δ dissociating below the ionic limit Sr²⁺Li^? have been investigated. This study shows interesting behaviours around the avoided crossing related to charge transfer involving important processes in physics and astrophysics such as dynamics, pre-dissociation and inelastic transitions.     

Sur l'acylation et l'alkylation de l'amino-4 pyrazolo [3,4-d] pyrimidine

New derivatives of 4-amino [3,4-d] pyrazolo pyrimidine have been prepared. Mono, di- and tri-substitution products are characterised by unequivocal synthesis. Several compounds are being tested for possible carcinostatic activity.     

New hybrid polyoxometalate/polymer composites for photodegradation of eosin dye

New polyoxometalate (POM)/polymer hybrid composites were prepared by photopolymerization under mild conditions for suitable photocatalytic processes. Polyoxometalates were incorporated in special photosensitive resins, which were photopolymerized under visible light to obtain new materials with photocatalytic activity for dye removal. The synthesized composites were characterized by real‐time FT‐IR, and the photocatalytic ability was investigated on Eosin‐Y removal using photolysis under near UV irradiation. Interestingly, the polyoxometalates keep their photocatalytic properties, while incorporated into the polymeric matrix since very high conversion rates of Eosin‐Y were achieved. Indeed, degradation efficiencies of about 98% and 93% were registered when using H₃PMo₁₂O₄₀/polymer and 94% for SiMo₁₂O₄₀(IPh₂)₄/polymer composites, respectively. These first results reported in this article show that the new synthesized POM/polymer composites could be considered as promising materials for green and more suitable organic dye removal from aqueous solutions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1538–1549     

Large Scale Experiment on Transport of Trichloroethylene in a Controlled Aquifer

Pollution by dense non-aqueous phase liquids (DNAPLs) represents a major threat to groundwater resources. In a real case of site contamination, the efficiency of remediation techniques is often limited by a lack of knowledge of both the extent of the pollution and the behavior of the different phases of the pollutant in the subsurface. An experiment simulating pollution of an aquifer by a chlorinated solvent (Trichloroethylene: TCE) was conducted on a large controlled experimental site called SCERES. The experiment consisted of an injection of 8.9 liters of TCE under controlled conditions at 35cm below the soil surface with an appropriate set up. The goal was to study the behavior of the three phases of the pollutant (trapped TCE phase forming the impregnation body, vapors in the vadose zone, and dissolved traces in the aquifer) in order to better comprehend the mechanisms which govern the propagation and the transfer of this type of pollution underground. The SCERES experimental data indicate that mass transfer from the saturated zone to the vadose zone is important, affecting the repartition of the vapor plume and causing a significant decrease of dissolved TCE concentrations in the groundwater. Furthermore, vertical leaching of TCE vapors due to rainfall strongly influences the degree of groundwater pollution and its lateral extent. The transient mass balance of the experiment is very satisfactory and shows that the main part of the spilled quantity is lost to the atmosphere.