A convenient enantioselective synthesis of (S)-alpha-trifluoromethylisoserine

[reaction: see text] This report describes two straightforward synthetic methodologies to obtain alpha-CF3-isoserine, a new alpha,alpha-disubstituted beta-amino acid, from alpha-(trifluoromethyl)acrylic acid. The routes involve the synthesis of five-membered cyclic sulfates (using sulfuryl chloride) or sulfamidates (using the Burgess reagent) from the corresponding chiral diols, which are obtained by a catalytic asymmetric dihydroxylation (AD) reaction.     

Spectroscopic investigation of the adsorption and oxidation of thiourea on polycrystalline Au and Au(111) in acidic media

In the present paper, a systematic electrochemical investigation on thiourea (TU) electrooxidation was developed on polycrystalline and (111) single-crystal gold electrodes in 0.1 M perchloric acid. The combination of cyclic voltammetry with in situ Fourier transform infrared spectroscopy (FTIRS) and differential electrochemical mass spectrometry techniques have allowed the nature of the species formed during the electroadsorption and electrooxidation of TU to be established. FTIRS experiments were performed in D2O to clean up the region of the H2O bending around 1600 cm(-1). It was concluded that TU adsorbs tilted on the surface in the 0.05-0.40 VRHE potential range. A dual-path reaction mechanism was evidenced in the oxidation process. The first pathway takes place from adsorbed TU at E > 0.40 VRHE and implies the formation of [Au(I)-(TU)2]+, which is oxidized to NH2CN and S0 at E > 0.80 VRHE. In a following oxidation step at E > 1.20 V, N2, CO2, and HSO4-/SO4(2-) were produced. The second parallel reaction occurs from TU in solution at E > 0.50 VRHE to form (TU)2(2+). All these species were characterized from the spectroscopic experiments. Similar results were obtained for both surfaces.     

Heavy metal analysis of rainwaters: A comparison of TXRF and ASV analytical capabilities

The aim of this work consisted on the implementation of sufficiently accurate and sensitive analytical procedure for the analysis of metal concentration in rainwater. Different sample preparation procedures were tested to achieve the required concentration prior to direct total reflection X-ray fluorescence (TXRF) analysis. TXRF and anodic stripping voltammetry (ASV) were compared in regard to achieved detection limits, precision and accuracy.     

Molecular structures of edge-sharing square-planar dinuclear complexes with unsaturated bridges

The dinuclear complexes of transition metal ions of type [M(2)(mu,eta(1)-XY)(2)L(4)], where XY is an unsaturated ligand that can act as a four-electron or a two-electron donor through the X atom, appear in two molecular conformations depending on whether the coordination planes around the two metal atoms are coplanar or bent. In both structures the geometry of the X atom is planar, corresponding to an sp(2) hybridization. An ab initio theoretical study on 43 representative complexes, complemented with a structural database analysis, provides a rationale for the experimentally observed structures.     

Cluster beams from passivated nanocrystals

Stable, intense beams of large metal clusters (from 10² to 10³ Au or Ag atoms) can be produced by laser desorption of molecular films of passivated nanocrystals that have undergone fractionation by size and a separate structural characterization. The mass onset of the desorbed species corresponds directly to the dimensions of the nanocrystal core, indicating that only the surfactant shell is lost during desorption. Photofragmentation, photoionization, and photodetachment from beams of large metal clusters, generated in this way, have all been observed.     

Cationic copolymerization of tetrahydrofuran with propylene oxide. IV. Use of antimony pentachloride as catalyst

Propylene oxide and tetrahydrofuran were polymerized cationically by an in situ catalytic system composed of antimony pentachloride and 1,2-propanediol. The rates of polymerization were measured by vapor-phase chromatography in the temperature range from ?20°C to +20°C. The Arrhenius parameters pertaining to the reaction of each of the comonomers were evaluated and compared with data published earlier for other catalytic systems. The present catalyst system was incapable of initiating a homo-polymerization of tetrahydrofuran in the absence of propylene oxide, while the latter was readily homopolymerized. In a copolymerization system, the rates of consumption of both monomers were first-order in respect to the catalyst, but the reaction ceased when all of the propylene oxide had been consumed. The relative reactivity of the two monomers as characterized by the copolymerization parameters r₁ (PO) = 1.15 and r₂ (THF) = 0.70 suggests that in the copolymerization system, tetrahydrofuran is capable of a reaction with its own active center. This is discussed in terms of a possible mechanism involving the effects of penultimate units and extensive chain transfer. The latter is well evident from the molecular weights of resulting copolyethers, which do not exceed one thousand.     

Predictive models to describe VLE in ternary mixtures water + ethanol + congener for wine distillation

The modeling of liquid–vapor equilibrium in ternary mixtures that include substances found in alcoholic distillation processes of wine and musts is analyzed. In particular, vapor–liquid equilibrium in ternary mixtures containing water + ethanol + cogener has been modeled using parameters obtained from binary mixture data only. The congeners are substances that although present in very low concentrations, of the order of part per million, 10⁻⁶ to 10⁻⁴ mg/L, are important enological parameters [1] and [2]. In this work two predictive models, the PSRK equation of state and the UNIFAC liquid phase model and two semipredictive activity coefficient models: NRTL and UNIQUAC have been used. The results given by these different models have been compared with literature data and conclusions about the accuracy of the models studied are drawn, recommending the best models for correlating and predicting the phase equilibrium in this type of mixtures.     

Sorption of proton and heavy metal ions on a macroporous chelating resin with an iminodiacetate active group as a function of temperature

A macroporous resin containing iminodiacetic groups (Lewatit) was investigated for its sorption properties towards proton and nickel(II) and cadmium(II). Different compositions of the aqueous phase, and different temperatures were examined. The stoichiometry, the exchange coefficients and the intrinsic constants of the sorption equilibria were obtained from the experimental data by using the Gibbs-Donnan model for the ion exchange resin. The intrinsic constants were found to be independent of the composition of the solution, so that they were used for characterizing the sorption equilibria. While the first intrinsic protonation constant of the active groups in the resin was found to depend on the temperature, the second one was independent. The sorption equilibrium of nickel in the resin was different from that of cadmium, being ascribable respectively to the formation of the complexes NiL and Cd(HL)(2). inside the resin. Their intrinsic complexation constants were found to be 10(-1.84) and 10(-3.64) at 25 degrees C. Compared to those of another resin with the same active groups, but not macroporous, they are higher. The dependence of the intrinsic constant on the temperature was also different for the two metals, allowing to evaluate a DeltaH degrees of +30.9 and of +13.7 kJ mol(-1) respectively. When a comparison is possible, these values are near to those in aqueous solution for the complexation with ligands of similar structure. These results can be used to achieve metal ion separation based on temperature variations.     

Simultaneous determination of yohimbine and boldine by first-derivative synchronous spectrofluorimetry

A method for the simultaneous determination of yohimbine and boldine in mixtures by first-derivative synchronous spectrofluorimetry has been developed. The method is based on their native fluorescence in 0.1N sulphuric acid medium. The constant wavelength difference chosen to optimize the determination was =_em -_em=82 nm. Yohimbine was measured at _ex//_em= 285/367 nm, and boldine at _ex/_em=272/354 nm. The range of application is 10–500 g/l for yohimbine and 1–50 g/l for boldine. The method was applied to the determination of yohimbine and boldine in synthetic mixtures and pharmaceuticals, with errors generally 2%. Relative standard deviations were about 2%.Dedicated to Professor Fermin Capitán on his 72th birthday     

Evaluation of surface- and ground-water pollution due to herbicides in agricultural areas of Zamora and Salamanca (Spain)

The pollution of agricultural land due to herbicides was assessed in the Guare?a and Almar river basins, situated in the provinces of Zamora and Salamanca (Spain). A set of fifteen herbicides, including triazines, ureas, amides and others, was selected owing to their frequency of use, the amounts used, their toxicity and their persistence in the environment. Solid-phase extraction with polymeric cartridges, followed by HPLC with diode-array detection, were used to monitor the herbicides. This technique was chosen owing to the wide range of functionality and polarity of the analytes under study. The detection limits obtained were in the 0.004-0.025 microg/l range (lambda=220 nm). Surface and ground waters, taken from different locations in the basins, were analyzed over a 6-month period. The presence of six out of the fifteen herbicides monitored--chlortoluron, atrazine, terbutryn, alachlor, diflufenican and fluazifop-butyl--was detected in several samples at levels ranging from the detection limit to 1.2 microg/l. The relationship of these herbicides to the agricultural activities of the zone is discussed.