Photoinduced degradation by iron(III): removal of triphenyltin chloride from water

The photoredox process taking place in iron(III) aquacomplexes was used to cause the complete degradation of triphenyltin (TPT). TPT elimination was proved to come only from attack by hydroxyl radicals generated upon irradiation at 365 nm of Fe(H₂O)₅OH²⁺, the iron(III) species present under the experimental conditions ([Fe(III)] in the range (3–6) × 10^?4 mol l^?1). The first step is the formation of an adduct between hydroxyl radicals and the benzene ring. The main process is a stepwise dephenylation of the starting TPT. Hydroxylated phenyltin derivatives were also formed, but only as minor photoproducts. The process was shown to be efficient with artificial light as well as with solar light. Copyright © 2001 John Wiley & Sons, Ltd.     

Vector-Valued Tail Value-at-Risk and Capital Allocation

Enterprise risk management, actuarial science or finance are practice areas in which risk measures are important to evaluate for heterogeneous classes of homogeneous risks. We present new measures: bivariate lower and upper orthant Tail Value-at-Risk. They are based on bivariate lower and upper orthant Value-at-Risk, introduced in Cossette et al. (Insurance: Math Econ 50(2):247–256, 2012). Many properties and applications are derived. Notably, they are shown to be positive homogeneous, invariant under translation and subadditive in distribution. Capital allocation criteria are suggested. Moreover, results on the sum of random pairs are presented, allowing to use a more accurate model for dependent classes of homogeneous risks.     

Bulk hydrolysis and solid–liquid sorption of heavy metals in multi-component aqueous suspensions containing porous inorganic solids: Are these mechanisms competitive or cooperative?

Fundamental aspects of the removal of heavy metals from aqueous streams under conditions of competition among the various species have been studied between pH 3 and 9 on Spherosil XO75LS, ordered mesoporous MCM-41 and MCF silicas, as well as a MCF sample grafted with (3-aminopropyl)methoxydimethylsilane (AMPS-MCF). Cd(II), Co(II), Pb(II), or Sr(II) nitrate solutions were used to determine the percentage of metal uptake by each solid at 298K as a function of the pH of the equilibrium solution, at an initial metal concentration of 0.0001molL(-1) and the ionic strength being fixed with 0.01molL(-1) NaNO(3). Almost complete retention of the heavy metals on the four solid samples was observed, with the process beginning at pH values smaller than those marking the onset of "bulk" precipitation of a given metal in "free" solution. The heavy metal-uptake mechanism was regarded as hydrolysis-like phenomenon in metal-containing solid suspensions. Weak adsorption of metal species from slightly acidic and neutral solutions was a kind of nucleation step. Adding cadmium to an equimolar solution containing cobalt, lead, or strontium showed no significant effect on the retention of the main metal component. This indicated the great independence of the retention mechanisms.     

Synthesis of the trans-hydrindane core of dictyoxetane

A concise, stereoselective synthesis of the trans-hydrindane core of the marine natural product dictyoxetane is reported, starting from a Robinson annelation derived bicyclic enone. A phosphorane-mediated, pinacol-like rearrangement of a cis-diol, via a formal 1,2-hydride shift, is used to establish the requisite trans ring junction. (31)P NMR supports the formation of the intermediate phosphorane, generated in situ from the reaction of a diol with Ph(3)PCl(2).     

TVaR-based capital allocation for multivariate compound distributions with positive continuous claim amounts

In this paper, we consider a portfolio of n dependent risks X₁,…,X_n and we study the stochastic behavior of the aggregate claim amount S=X₁+?+X_n. Our objective is to determine the amount of economic capital needed for the whole portfolio and to compute the amount of capital to be allocated to each risk X₁,…,X_n. To do so, we use a top-down approach. For (X₁,…,X_n), we consider risk models based on multivariate compound distributions defined with a multivariate counting distribution. We use the TVaR to evaluate the total capital requirement of the portfolio based on the distribution of S, and we use the TVaR-based capital allocation method to quantify the contribution of each risk. To simplify the presentation, the claim amounts are assumed to be continuously distributed. For multivariate compound distributions with continuous claim amounts, we provide general formulas for the cumulative distribution function of S, for the TVaR of S and the contribution to each risk. We obtain closed-form expressions for those quantities for multivariate compound distributions with gamma and mixed Erlang claim amounts. Finally, we treat in detail the multivariate compound Poisson distribution case. Numerical examples are provided in order to examine the impact of the dependence relation on the TVaR of S, the contribution to each risk of the portfolio, and the benefit of the aggregation of several risks.     

Ultrafast breathinglike oscillation in the exciton density of ZnSe quantum wells

The spatial density profile of a low-density exciton ensemble in ZnSe quantum wells shows a breathinglike oscillation on a 30-ps time scale. This breathing results from the emission of the first acoustic phonon at the end of the quasiballistic transport phase of the excitons which reverses their direction of propagation. Since the scattering destroys the phase of the excitonic wave function, one can deduce simultaneously the coherence length and the coherence time of excitonic transport by evaluation of the oscillation measured from a single experiment. The breathing, which can be modeled by Monte Carlo simulations, is quenched for rising lattice temperature, i.e., increasing phonon absorption, and in samples with significant disorder. These results were obtained by time-resolved nanophotoluminescence with 5 ps and 250 nm temporal and spatial resolution, respectively.     

Structural and electrochemical characterization of mesoporous thin films of Nb2xV2 − 2xO5 upon lithium intercalation

Nb_2xV_2 ? 2xO₅ (0 ≤ x ≤ 1) powders were prepared by a synthetic route based on the inorganic polymerization of alkoxy-choride precursors and characterized by a combination of X-ray diffraction, ⁵¹V and ⁹³Nb NMR and Raman spectroscopy. Amorphous mesoporous thin films of similar compositions were successfully prepared by a modified Evaporation Induced Self Assembly method using polystyrene-b-polyethyleneoxide diblock copolymer as structuring agent. The electrochemical properties of the mesoporous films upon lithium insertion–deinsertion are investigated by cyclic voltammetry. This study highlights the advantages of such nanoarchitecture in terms of increased capacity to insert lithium.     

A Review of Manganese(III) (Oxyhydr)Oxides Use in Advanced Oxidation Processes

The key role of trivalent manganese (Mn(III)) species in promoting sulfate radical-based advanced oxidation processes (SR-AOPs) has recently attracted increasing attention. This review provides a comprehensive summary of Mn(III) (oxyhydr)oxide-based catalysts used to activate peroxymonosulfate (PMS) and peroxydisulfate (PDS) in water. The crystal structures of different Mn(III) (oxyhydr)oxides (such as α-Mn₂O₃, γ-MnOOH, and Mn₃O₄) are first introduced. Then the impact of the catalyst structure and composition on the activation mechanisms are discussed, as well as the effects of solution pH and inorganic ions. In the Mn(III) (oxyhydr)oxide activated SR-AOPs systems, the activation mechanisms of PMS and PDS are different. For example, both radical (such as sulfate and hydroxyl radical) and non-radical (singlet oxygen) were generated by Mn(III) (oxyhydr)oxide activated PMS. In comparison, the activation of PDS by α-Mn₂O₃ and γ-MnOOH preferred to form the singlet oxygen and catalyst surface activated complex to remove the organic pollutants. Finally, research gaps are discussed to suggest future directions in context of applying radical-based advanced oxidation in wastewater treatment processes.