Activation of Hydrogen Peroxide by Ionic Liquids: Mechanistic Studies and Application in the Epoxidation of Olefins

Imidazolium‐based ionic liquids that contain perrhenate anions are very efficient reaction media for the epoxidation of olefins with H₂O₂ as an oxidant, thus affording cyclooctene in almost quantitative yields. The mechanism of this reaction does not follow the usual pathway through peroxo complexes, as is the case with long‐known molecular transition‐metal catalysts. By using in situ Raman, FTIR, and NMR spectroscopy and DFT calculations, we have shown that the formation of hydrogen bonds between the oxidant and perrhenate activates the oxidant, thereby leading to the transfer of an oxygen atom onto the olefin demonstrating the special features of an ionic liquid as a reaction environment. The influence of the imidazolium cation and the oxidant (aqueous H₂O₂, urea hydrogen peroxide, and tert‐butyl hydrogen peroxide) on the efficiency of the epoxidation of cis‐cyclooctene were examined. Other olefinic substrates were also used in this study and they exhibited good yields of the corresponding epoxides. This report shows the potential of using simple complexes or salts for the activation of hydrogen peroxide, owing to the interactions between the solvent medium and the active complex.     

Surface properties of some carotenoids spread in monolayers at the air/water interface. Experimental and computational approach

The surface pressure versus molecular area isotherms of some carotenoids: β,β-carotene-4-one (echinenone, ECH), β,β-carotene-4,4′-dione (canthaxanthin, CAN) and 4,4′-diapo-ω,ω-carotene-4,4′-dial (APO), spread at the air/water interface, are reported. A van der Waals type state equation is used to describe the high molecular area portions of the compression isotherms and interaction parameters within monolayers are derived. Quantum chemical semi-empirical SCF MO calculations (AM1 and PM3) are performed for the optimized geometries of molecules and dipole moments are calculated. Similar theoretical magnitudes are obtained by both methods. Surface properties, like collapse pressure, surface compressional modulus and interaction parameters are discussed in terms of dipole-dipole interactions, and correlations with the calculated quantities for the carotenoid molecules are analyzed. The orientation of the different carotenoid molecules in the monolayer is discussed.     

Optimal systems for equipment maintenance and replacement under Markovian deterioration

Deterioration of equipment is modeled as a multistate discrete time controlled Markov process. The states are classified according to the degree of deterioration. The problem of design of optimal systems for equipment maintenance and replacement is considered when the decision-maker may take, in each stage, one of many available maintenance actions, classified according to their “stochastic effectiveness”; no action and replacement are included as alternatives. It is assumed that the transition probabilities satisfy two conditions which effectively describe a trend for monotonically increasing expected deterioration and rate of deterioration. Under these assumptions it is proved in the paper that the optimal (cost minimizing) decision system in an infinite horizon is of the control limit rule type, rapidly obtained by policy improvement algorithms. A numerical example is presented for a specific practical application; detailed data are available from the authors on request.     

Uranium electrodeposition for alpha spectrometric source preparation

In this paper a simple method was used to design and set up an electrodeposition device for uranium source preparation for alpha spectrometry measurements. The aim of this work is to find the optimal parameters to be used to achieve uranium alpha sources with good spectral properties and maximum yield of the electrodeposition process. Samples with specific uranium activity were prepared from aqueous solution of uranyl nitrate hexahydrate (UO₂ (NO₃)₂·6H₂O). A series of preliminary experiments was conducted to establish the main parameters that have a significant influence on the deposition efficiency. Among these, the electrodeposition time was studied and the optimum time was found to be 1 h, in the case of our home-made deposition cell. It was also shown that a current of 1,500 mA, plating time of 60 min and pH range of 2–2.2 are the best conditions for deposition of uranium. The alpha spectrometry results show a good spectral resolution for the uranium sources obtained by the electrodeposition using the optimal parameters.     

Porous phosphate heterostructures containing CdS quantum dots: assembly, characterization and photoluminescence

The synthesis and characterization of cadmium sulphide (CdS) quantum dots, conjugated in a porous phosphate heterostructure functionalized with aminopropyl groups is described. The resulting material has fluorescence properties with maximum emission intensity at 575 nm. The fluorescent materials are not soluble in water and exhibit high stability in aqueous solution in the pH ranges from 2 to 9. Energy dispersive X-ray spectroscopy confirmed the qualitative elemental composition of the synthesized materials and X-ray photoelectron spectra showed a surface S/Cd atomic ratio of 1.09. SEM images show that the materials are amorphous, possessing porous with sizes of several tens nanometres, homogeneous and exhibit a layered morphology. The adsorption–desorption analysis by N₂ at 77 K showed the accessibility of the CdS quantum dots onto the pores of the structure. The CdS quantum dots were stabilized by mercaptopropionic acid and bounded to the host materials by amine groups.     

Characteristics of formvar films used to prevent alpha-detector contamination

Alpha spectrometry is an extremely useful and sensitive for detection of alpha-emitting nuclides. Contamination of the silicon detectors for low-level alpha spectrometry by recoil nuclides is a serious problem in the measurement of alpha emitters decaying to daughter nuclides with short half-lives. This unwanted contamination leads to decreased measurement sensitivity causing a degradation of the limit of detection. The simplest method to prevent this radioactive contamination of detector is to use a catcher film between the alpha source and the detector. In this work we describe the obtaining of the thin formvar films as stopper foils for recoil nuclei and we investigated the influence of these films on alpha spectrometry parameters, as energy shift (~30 keV) and resolution (~7%). No significant deterioration of the alpha spectrometry parameters was observed when using thin formvar films. Using the ASTAR web databases, which calculate stopping powers for alpha particles, the thickness of formvar films was estimated to be about 5.355 × 10⁻⁵ g/cm². The measurements were performed with an ORTEC SOLOIST alpha spectrometer with PIPS detector.     

Modification of Surface Charge Properties during Kaolinite to Halloysite-7Å Transformation

The surface charge properties of well and poorly ordered kaolinite and halloysite-7Å, representing three different stages of kaolinite to halloysite-7Å transformation identified in the kaolin deposit of São Vicente de Pereira (Portugal), were studied. Mineralogical (X-ray diffraction, Fourier transformation-infrared) and chemical data (analytic electron microscopy) showed that the gradual transformation from kaolinite to halloysite-7Å minerals was accompanied by an increase in hydration and a decrease in Si/Al ratio. In particular, the replacement of Si(IV) by Al(III) in the tetrahedral layer caused an electrical charge unbalance and a modification of surface charge properties during the kaolinite to halloysite transformation. Accordingly, the cation exchange capacity (CEC) gradually increases when passing from well-ordered kaolinite to halloysite-7Å, attesting the direct correspondence existing among the structural order of the samples, number of tetrahedral substitutions, and CEC. Electrophoretic experiments provided further evidences of the origin of surface charge properties and the variation encountered during kaolinite to halloysite-7Å transformation. The curves of ζ-potential versus pH show the same pH dependency for the three minerals, but a gradual increase of ζ-potential when passing from well ordered kaolinite to halloysite-7Å through the poorly ordered kaolinite. The results can unambiguously be attributed to the increase of permanent charge due to the higher degree of isomorphic substitution, more than to the increase of structural and ionizable water.     

Characterization of Portuguese geomaterials,the clay component of <Emphasis Type="Italic">rañas</Emphasis>, as potential liners for low and intermediate radioactive disposal sites

This paper describes the development of a separation method for americium from the effluents emanating from anion exchange column, used for the recovery of plutonium from analytical waste solutions. The waste contained uranium, sodium, calcium and iron as the major impurities as estimated by ICP-AES method. ~99% pure americium was obtained by three separation steps using solvent extraction and extraction chromatography techniques. In the first step, uranium was quantitatively separated by giving five contacts of equal volumes of 30% TBP in n-dodecane. Fe and Na were separated in the next step using 0.1 M TODGA + 0.5 M DHOA as the extractant. In the last step, Am was separated from the co-extracted Ca (about 76%) using CMPO loaded extraction chromatographic column. The overall recovery was >80% with decontamination factor (D.F.) from the impurities being >3000 while the purity of the product was 99%.     

Optical Characterization of CdS Quantum Dots Nanoparticles Dispersed in Clays

Synthesis, characterization, and the optical behavior of CdS quantum dots nanoparticles were studied confined in clays. An alternative synthesis approach in different natural clays K-10 bentonite, Na-montemorillonite, halloysite, and saponite was carried out. The composite materials were characterized by XRD and FTIR spectroscopy, energy dispersive, scanning, and transmission electron microscopy. After CdS-QDs formation, the synthesized materials became fluorescent with emission wavelengths (average and standard deviation of the maximum wavelength; full width of half maximum): K-10 bentonite-CdS (590 ± 5 nm; 183 nm); Na-montmorillonite-CdS (550 ± 3 nm; 219 nm); saponite-CdS (550 ± 5 nm; 219 nm), and halloysite-CdS (590 ± 8 nm; 185 nm). (Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of Dispersion Science and Technology to view the free supplemental file.)