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.     

Variable coordination geometries at the diiron(II) active site of ribonucleotide reductase R2

The R2 subunit of Escherichia coli ribonucleotide reductase contains a dinuclear iron center that generates a catalytically essential stable tyrosyl radical by one electron oxidation of a nearby tyrosine residue. After acquisition of Fe(II) ions by the apo protein, the resulting diiron(II) center reacts with O(2) to initiate formation of the radical. Knowledge of the structure of the reactant diiron(II) form of R2 is a prerequisite for a detailed understanding of the O(2) activation mechanism. Whereas kinetic and spectroscopic studies of the reaction have generally been conducted at pH 7.6 with reactant produced by the addition of Fe(II) ions to the apo protein, the available crystal structures of diferrous R2 have been obtained by chemical or photoreduction of the oxidized diiron(III) protein at pH 5-6. To address this discrepancy, we have generated the diiron(II) states of wildtype R2 (R2-wt), R2-D84E, and R2-D84E/W48F by infusion of Fe(II) ions into crystals of the apo proteins at neutral pH. The structures of diferrous R2-wt and R2-D48E determined from these crystals reveal diiron(II) centers with active site geometries that differ significantly from those observed in either chemically or photoreduced crystals. Structures of R2-wt and R2-D48E/W48F determined at both neutral and low pH are very similar, suggesting that the differences are not due solely to pH effects. The structures of these "ferrous soaked" forms are more consistent with circular dichroism (CD) and magnetic circular dichroism (MCD) spectroscopic data and provide alternate starting points for consideration of possible O(2) activation mechanisms.     

Optimization of a GFAAS method for determination of total inorganic arsenic in drinking water

The new 10 μg l⁻¹ arsenic standard in drinking water has been a spur to the search for reliable routine analytical methods with a limit of detection at the μg l⁻¹ level. These methods also need to be easy to handle due to the routine analyses that are required in drinking water monitoring. Graphite furnace atomic absorption spectrometry (GFAAS) meets these requirements, but the limit of detection is generally too high except for methods using a pre-concentration or separation step. The use of a high-intensity boosted discharge hollow-cathode lamp decreases the baseline noise level and therefore allows a lower limit of detection. The temperature program, chemical matrix modifier and thermal stabilizer additives were optimized for total inorganic arsenic determination with GFAAS, without preliminary treatment. The optimal furnace program was validated with a proprietary software. The limit of detection was 0.26 μg As l⁻¹ for a sample volume of 16 μl corresponding to 4.2 pg As. This attractive technique is rapid as 20 samples can be analysed per hour. This method was validated with arsenic reference solutions. Its applicability was verified with artificial and natural groundwaters. Recoveries from 91 to 105% with relative standard deviation <5% can be easily achieved. The effect of interfering anions and cations commonly found in groundwater was studied. Only phosphates and silicates (respectively at 4 and 20 mg l⁻¹) lead to significant interferences in the determination of total inorganic arsenic at 4 μg l⁻¹.     

Konfigurative Zusammenhänge in der Muscarinreihe; Chiralität des epi-, allo- und epiallo-Muscarins,des Muscarons und allo-Muscarons. Zur biogenese des muscarins 37. Mitteilung über muscarin und verwandte stoffe

The chirality of all stereoisomeric muscarines has been determined. (–)-Muscarine chloride was converted to (+)-normuscarine, which in turn was oxidized to (+)-normuscarone. Epimerisation by acid catalysis of the latter gave a mixture of the C(2)-epimers, namely (+)-normuscarone and (–)-allo-normuscarone. From these were prepared by reduction with LiAlH₄ optically active stereoisomeric noralcohols. The natural stereoisomeric muscarines so far isolated are: (+)-(2S, 3R, 5S)-muscarine, (–)-(2S, 3R, 5R)-allo-muscarine and (+)-(2S, 3S, 5S)-epi-muscarine. Identical chirality appears only at C(2). This fact has to be taken into consideration for further speculations about the biogenesis of muscarines. Optically active muscarone and normuscarone exhibit a strong Cotton effect at 300 nm, which is interpreted in terms of absolute configuration by analogy to optically active substituted cyclopentanones. Optically active allo-normuscarone exhibits a very weak Cotton effect only, presumably because of predominant pseudo-rotation. The relative stability of the stereoisomeric norketones has been determined. Normuscarone (cis-2,5) is by 0,39 kcal/mol more stable than allo-normuscarone (trans-2,5).     

Préparation et Étude Physico-chimique de Quelques Copolyamides Aromatiques Séquencés. I. Synthèse des Copolycondensats Séquencés

A two-stage low-temperature solution polycondensation process is described for the synthesis of two kinds of block copolyamides: poly(p-biphenylene terephtalamide-co-adipamide) and poly(2,5-dimethyl trans-piperazine terephthalamide-co-adipamide). The reactivity of oligomeric end groups in various solvents is examined. This study ascertains the influence of the nature of the solvent on the extent of polycondensation. End groups seem to be more reactive in a medium in which the polyamide is soluble; this property is used for the synthesis of block copolycondensates.     

Characterization of Block Structures in Copolycondensates: A Review

Various kinds of copolymers, differing in composition and in arrangement of monomeric units in the macromolecule, can be obtained from the copolymerization of two monomers. In a given composition, monomeric units may assemble in a random way, alternatively, or tend to give sequences of the same unit:     

Influence of high magnetic fields on the superconducting transition of one-dimensional Nb and MoGe nanowires

The effects of a strong magnetic field on superconducting Nb and MoGe nanowires with diameter approximately 10 nm have been studied. We have found that the Langer-Ambegaokar-McCumber-Halperin (LAMH) theory of thermally activated phase slips is applicable in a wide range of magnetic fields and describes well the temperature dependence of the wire resistance, over 11 orders of magnitude. The field dependence of the critical temperature, T(c), extracted from the LAMH fits is in good quantitative agreement with the theory of pair-breaking perturbations that takes into account both spin and orbital contributions. The extracted spin-orbit scattering time agrees with an estimate tau(s.o.) approximately tau(variant Planck's over 2pic/Ze(2))(4), where tau is the elastic scattering time and Z is the atomic number.     

Dynamic arsenic removal on a MnO2-loaded resin

Previous batch studies on a polystyrene matrix loaded with manganese dioxide, synthesized from an anionic commercial resin in chloride form, have proven the efficiency of this sorbent in As(V) and As(III) removal. This solid is now tested with column experiments to predict its behavior in a treatment process. An artificial water, with a composition in major ions similar to that of granitic water, often contaminated with arsenic, was prepared. This artificial water was used to simulate arsenic removal processes under near-natural conditions and with a stable composition. Furthermore, the hydride generation AAS analytical method was optimized to measure low arsenic concentrations (1 to 20 microg/L).     

(Benzo[4, 5]cyclohepta[l, 2-b]thiophen-4-ylidene)acetic Acids: Novel Non-ulcerogenic Antiinflammatory Agents

Compound (Z)- 8a has been found to display interesting antiinflammatory activity. In order to prepare derivatives with a wide variety of substituents in the aromatic part of the molecule, a new synthesis of the key intermediates 9a-g was developed starting from thiophene-3-carboxylic acid ( 11 ) and substituted benzyl bromides. The conversion of 9a-g to 10a-g follows a known procedure. Ketones 10a-g , on reaction with alkyl (dialkoxy-phosphoryl)acetate, followed by isomer separation and alkaline ester hydrolysis, yielded the desired derivatives (Z)- 8a-g and (E)- 8a-g . The biologically most interesting compound (Z)- 8a is currently undergoing clinical trials.