Arsenite oxidation and arsenate determination by the molybdene blue method

Based on the similarity in properties of arsenate and phosphate, the colorimetric method using the molybdene blue complex was tested in order to determine low As(V) concentration in waters. The influence of complex formation time, daylight, temperature and competitive anions (silicate and sulphate) upon complex formation was determined. Optimal complex formation was reached in 1 h at 20±1 °C and was slightly favoured when developed in daylight. The formation rate declined with decreasing reaction temperature and no influence of any of the competitive anions tested (at concentrations usually found in natural waters of granitic areas) was noted. The detection limit of this method was 20 μg As(V) l⁻¹. This simple, fast and sensitive arsenic determination method is suitable for field analysis, especially for waters containing low levels of phosphate and organic matter. Through arsenate determination, this colorimetric method allowed the arsenite oxidation efficiency of five common industrial oxidants to be compared. H₂O₂ and MnO_2(s) were not considered as effective oxidants as a high excess was necessary to ensure As(III) oxidation. NaOCl and KMnO₄ were promising oxidants as they allowed complete arsenite oxidation with a small excess for NaOCl or even less than the electron stoichiometric ratio in the case of KMnO₄. FeCl₃ was the most effective oxidant among the reagents tested here.     

Complexes acetyleniques de titane(II). Reactivite vis-a-vis de l'hydrogene moleculaire: Une nouvelle approche du titanocene

¹³C NMR measurements were performed on [Re₃(μ-H)₃(CO)₁₀]^2? at various temperatures and field strengths. Selective decoupling allowed assignments of the carbonyl resonances. Spin-lattice relaxation time measurements indicated that two mechanisms, scalar coupling and chemical shielding anisotropy, contribute to the relaxation of carbon-13. Variable temperature experiments revealed that more than one mechanism is responsible for the fluxional behaviour.     

Synthesis of thienothiazocinoisoindolediones and thienothiazinoisoindolones from mercaptothiophenes and chloromethylphthalimide

2-Thienylthiomethylphthalimides 3a,b were synthesized by action of Chloromethylphthalimide on 2-or 3-mercaptothiophene. Reduction of 3a,b and Wittig reaction using carbethoxycarbonyltriphenyl-phosphorane gave the corresponding acetic acids 5a,b which cyclized under Friedel and Crafts conditions to lead the thienothiazocinoisoindolediones 6a,b. Thienothiazinoisoindolones 7a,b were obtained from hydroxyisoindolones derivatives 4a,b in acid conditions via an acyliminium ion.     

Anderson localization for multi-dimensional systems at large disorder or large energy

We prove that discrete Schrödinger operators on ^d with a random-potential have almost-surely only pure point spectrum and exponentially decaying eigenfunctions for large disorder or large energy. This is the first proof of localization for multi-dimensional Anderson models.Groupe de recherche 048 du CNRS     

Synthesis of new 4-(1-ethylthio-2,2,2-trifluoroethyl)-6-methylpyridazin-3(2H)-ones starting from S-ethyl 4-oxo-2-(pentafluoroethyl)pentanethiolate and hydrazines

The paper presents a one-pot conversion of γ-keto-α-pentafluoroethyl thioester into new pyridazin-3-ones and α,β-unsaturated lactams. The structures of all new compounds were ascribed using 1D (¹⁹F, ¹H, ¹³C) and 2D (¹H-¹⁵N) NMR data, and X-ray diffraction analysis. Two possible competitive reaction mechanisms for the synthesis of pyridazin-3-ones and lactams are presented.     

Two new 5-deoxyflavones from Albizia odoratissima

Two new 5-deoxyflavones, 7,8-dimethoxy-3',4'-methylenedioxyflavone (1) and 7,2',4'-trimethoxyflavone (2) together with a known flavone, 7,4'-dimethoxy-3'-hydroxyflavone (3) were isolated from the rootbark of Albizia odoratissima. The structures of these new compounds were elucidated by electrospray ionization mass spectrometry (ESI-MS) and 1D and 2D-NMR spectral studies including (1)H-(1)H correlation spectroscopy (COSY), heteronuclear single quantum coherence (HSQC), heteronuclear multiple bond connectivity (HMBC) and nuclear Overhauser enhancement spectroscopy (NOESY).     

Multicomponent coupling approach to (+/-)-frondosin B and a ring-expanded analogue

[reaction: see text] A recently discovered multicomponent coupling reaction is used to give direct access to a late intermediate in the synthesis of frondosin B. This intermediate can also be efficiently converted to a ring-expanded analogue of frondosin B by sustained heating of the reaction mixture. An unprecedented tandem 1,7-hydrogen shift, 8pi-electrocyclization is proposed to explain the formation of this ring-expanded species.     

Automatic sugar analysis in the beet industry. Part I: Parameter optimization of a reversed phase HPLC carbohydrate determination

An evaluation of the most commonly used HPLC system (reversed phase octadecyl sillica gel) was undertaken in order to determine the level of certain carbohydrates in molasses produced in the refining of sugar beet. Chromatographic parameters and purification operations prior to analysis are discussed in order to develop an analytical method permitting automation of sugar determination. A Zorbax ODS column (250 × 9.4 mm), water elution, and light scattering detection allow easy determination of glucose + fructose, sucrose, and raffinose in molasses using an internal standard (maltose).     

1,3,5-Trisubstituted hexahy drotriazines as mannich reagents. I. Preparation of secondary aminomethyl sulfide hydrochlorides

1,3,5-Trisubstituted hexahy drotriazines react with hydrogen chloride in the presence of anhydrous solvents to form useful intermediates for the introduction of the RNHCH₂- group into compounds which undergo the Mannich reaction. The effectiveness of the new aminomethyl-ating agent has been demonstrated by the preparation of secondary aminomethyl sulfide hydro-chlorides.