Micellar catalysis of the reaction of 2,4-dinitrofluorobenzene with phenoxide and thiophenoxide ions

The reactions of 2,4-dinitrofluorobenzene with phenoxide and thiophenoxide ion in water are strongly catalyzed by micelles of cetyltrimethylammonium bromide (CTABr) by factors of 230 and 1100 respectively. Nonionic micelles of Brij weakly catalyze the reaction with thiophenoxide ion. Spectral measurements show that phenoxide, and especially thiophenoxide, ions interact strongly with micelles of CTABr which also markedly change the acid dissociation of phenol under given buffer conditions.     

Multiresidue determination of pesticides in drinking and related waters by gas chromatography/mass spectrometry after solid-phase extraction: interlaboratory study

As part of a project funded by the European Commission (EC) for the development and evaluation of multiresidue methods for analysis of drinking and related waters, 15 European laboratories evaluated a method using styrene-divinylbenzene co-polymer solid-phase extraction followed by gas chromatography/mass spectrometry. The main aim of the study was to evaluate whether the method meets the requirements of EC Directive 98/83 in terms of accuracy, precision, and detection limit for 22 pesticides according to the following requirements: limit of detection, < or = 0.025 microg/L; accuracy, expressed as recovery between 75 and 125%; and precision, expressed as repeatability relative standard deviation of the method of < 12.5% and as reproducibility relative standard deviation of the method of < 25%. Analyses for unknown concentrations were performed with fortified commercial bottled and tap waters. All laboratories were able to achieve detection limits of 0.01 microg/L for all pesticides except dimethoate and desisopropylatrazine (0.02 microg/L). The criteria for repeatability were met for all compounds except trifluralin, dimethoate, and lindane in bottled water and chlorpyrifos, dimethoate, and lindane in tap water. The criteria for reproducibility were met for all compounds except trifluralin, dimethoate, and lindane in bottled water and pendimethalin, chlorpyrifos, dimethoate, terbutryn, and lindane in tap water. In terms of accuracy, the method meets the requirements for all pesticides in both matrixes, except for lindane in bottled water and lindane and chlorpyrifos in tap water.     

Thermal degradation of poly(2,6-dimethoxycarbonyl-1,6-heptadiene)

The thermal degradation under vacuum of poly(2,6-dimethoxycarbonyl-1,6-heptadiene), a polymer which contains cyclic structural units, has been investigated. The analysis of the degradation products has shown that depolymerisation (depropagation along the polymer chain with formation of diene monomer) occurs extensively, together with other degradation reactions. A mechanism is proposed to account for the degradation products which have been identified.     

Optimization of catalyst enantioselectivity and activity using achiral and meso ligands

The optimization of asymmetric catalysts for enantioselective synthesis has conventionally revolved around the synthesis and screening of enantiopure ligands. In contrast, we have optimized an asymmetric reaction by modification of a series of achiral ligands. Thus, employing (S)-3,3'-diphenyl BINOL [(S)-Ph(2)-BINOL] and a series of achiral diimine and diamine activators in the asymmetric addition of alkyl groups to benzaldehyde, we have observed enantiomeric excesses between 96% (R) and 75% (S) of 1-phenyl-1-propanol. Some of the ligands examined have low-energy chiral conformations that can contribute to the chiral environment of the catalyst. These include achiral diimine ligands with meso backbones that adopt chiral conformations, achiral diimine ligands with backbones that become axially chiral on coordination to metal centers, achiral diamine ligands that form stereocenters on coordination to metal centers, and achiral diamine ligands with pendant groups that have axially chiral conformations. Additionally, we have structurally characterized (Ph(2)-BINOLate)Zn(diimine) and (Ph(2)-BINOLate)Zn(diamine) complexes and studied their solution behavior.     

Multielement determination in river-water of Sepetiba Bay tributaries (Brazil) by total reflection X-ray fluorescence using synchrotron radiation

Summary Trace elements were determined in the surface waters of tributaries of the Sepetiba Bay, Brazil (Piraquê, Itá, S?o Francisco, Guarda, Guandu Mirim, Vala do Sangue and Engenho Novo rivers) by total reflection X-ray fluorescence using synchrotron radiation (SRTXRF). Eighteen trace elements could be determined in the dissolved and the suspended particulate phases: Al, Si, P, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sr and Pb. The elemental concentration values were compared to the values recommended by the Brazilian legislation.     

Synthesis, crystal structure, spectroscopic and electrochemical characterization of the dinuclear complex {tetra-μ-[(±)-2-(p-methoxyphenoxy)-propionato-O,O′]bis(aqua)dicopper(II)}

Structural, electrochemical and spectroscopic data of a new dinuclear copper(II) complex with (±)-2-(p-methoxyphenoxy)propionic acid are reported. The complex {tetra-μ-[(±)-2-(p-methoxyphenoxy)propionato-O,O′]-bis(aqua)dicopper(II)} crystallizes in the monoclinic system, space group P2₁/n with a = 14.149(1) ?, b = 7.495(1) ?, c = 19.827(1) ?, β = 90.62(1) and Z = 4. X-ray diffraction data show that the two copper(II) ions are held together through four carboxylate bridges, coordinated as equatorial ligands in square pyramidal geometry. The coordination sphere around each copper ion is completed by two water molecules as axial ligands. Thermogravimetric data are consistent with such results. The ligand has an “L” type shape due to the angle formed by the β-carbon of the propionic chain and the linked p-methoxyphenoxy group. This conformation contributes to the occurrence of a peculiar structure of the complex. The complex retains its dinuclear nature when dissolved in acetonitrile, but it decomposes into the corresponding mononuclear species if dissolved in ethanol, according to the EPR measurements. Further, cyclic voltammograms of the complex in acetonitrile show that the dinuclear species maintains the same structure, in agreement with the EPR data in this solvent. The voltammogram shows two irreversible reduction waves at E _pc = −0.73 and −1.04 V vs. Ag/AgCl assigned to the Cu(II)/Cu(I) and Cu(I)/Cu° redox couples, respectively, and two successive oxidation waves at E _pa =− 0.01 and +1.41 V vs. Ag/AgCl, assigned to the Cu°/Cu(I) and Cu(I)/Cu(II) redox couples, respectively, in addition to the oxidation waves of the carboxylate ligand.     

Thermal decomposition of 4,4′-diaminodiphenylsulphone

The thermal decomposition of 4,4′-diaminodiphenylsulphone (DDS) was studied by thermogravimetry, differential scanning calorimetry and thermal volatilisation analysis. Solid residues, high-boiling and gaseous products of degradation were collected at each step of thermal decomposition and analysed by infrared spectroscopy and gas chromatography/mass spectrometry.

On programmed heating at normal pressure, DDS starts to evaporate at 250°C. Thermal decomposition, which probably proceeds through homolytic scission of the S-C bond is simultaneously observed. The resulting sulphonyl radicals provoke polymerisation and cross-linking of the solid residue which undergoes a limited degradation at 350°C with elimination of heteroatoms N and S as volatile moieties. Above 400°C, the residue undergoes a complex charring process leading to an aromatic char typical of carbonised aromatic polymers.     

Determination of manganese and zinc in powdered chocolate samples by slurry sampling using sequential multi-element flame atomic absorption spectrometry

In the present work, a slurry sampling flame atomic absorption spectrometric method to determine directly manganese and zinc in powdered chocolate samples is proposed. The optimization step was performed using univariate methodology involving the following factors: nature and concentration of the acid solution, sonication time, and particle size. The established conditions led to the use of a sample mass of 150 mg, 2.0 mol L^− 1 nitric acid solution, sonication time of 15 min, and a slurry volume of 50 mL. This method allows the determination of manganese and zinc with detection limit of 52 and 61 ng g^− 1, respectively, and a precision expressed as relative standard deviation (RSD) of 2.6% and 3.2% (both, n = 10) for contents of manganese and zinc of 52.4 and 100.0 μg g^− 1, respectively. The proposed method was applied for determination of manganese and zinc in five powdered chocolate samples. In these, the manganese content varied from 42.8 to 52.7 and from 88.6 to 102.4 μg g^− 1 of zinc. The analytical results were compared with the results obtained by analysis of these samples after digestion using open vessel and acid bomb digestion procedures and determination using FS-FAAS. The statistical comparison by t-test (95% confidence level) showed no significant difference between these results.     

Quantitative separation of zinc traces from cadmium matrices by solid-phase extraction with polyurethane foam

A system for separation of zinc traces from large amounts of cadmium is proposed in this paper. It is based on the solid-phase extraction of the zinc in the form of thiocyanate complexes by the polyurethane foam. The following parameters were studied: effect of pH and of the thiocyanate concentration on the zinc extraction, shaking time required for quantitative extraction, amount of PU foam necessary for complete extraction, conditions for the separation of zinc from cadmium, influence of other cations and anions on the zinc sorption by PU foam, and required conditions for back extraction of zinc from the PU foam. The results show that zinc traces can be separated from large amounts of cadmium at pH 3.0±0.50, with the range of thiocyanate concentration from 0.15 to 0.20 mol l⁻¹, and the shaking time of 5 min. The back extraction of zinc can be done by shaking it with water for 10 min. Calcium, barium, strontium, magnesium, aluminum, nickel and iron(II) are efficiently separated. Iron(III), copper(II) and cobalt(II) are extracted simultaneously with zinc, but the iron reduction with ascorbic acid and the use of citrate to mask copper(II) and cobalt(II) increase the selectivity of the zinc extraction. The anions nitrate, chloride, sulfate, acetate, thiosulphate, tartarate, oxalate, fluoride, citrate, and carbonate do not affect the zinc extraction. Phosphate and EDTA must be absent. The method proposed was applied to determine zinc in cadmium salts using 4-(2-pyridylazo)-resorcinol (PAR) as a spectrophotometric reagent. The result achieved did not show significant difference in the accuracy and precision (95% confidence level) with those obtained by ICP–AES analysis.     

Energetics of hydroxybenzoic acids and of the corresponding carboxyphenoxyl radicals. Intramolecular hydrogen bonding in 2-hydroxybenzoic acid

The energetics of the phenolic O-H bond in the three hydroxybenzoic acid isomers and of the intramolecular hydrogen O-H- - -O-C bond in 2-hydroxybenzoic acid, 2-OHBA, were investigated by using a combination of experimental and theoretical methods. The standard molar enthalpies of formation of monoclinic 3- and 4-hydroxybenzoic acids, at 298.15 K, were determined as Delta(f)(3-OHBA, cr) = -593.9 +/- 2.0 kJ x mol(-1) and Delta(f)(4-OHBA, cr) = -597.2 +/- 1.4 kJ x mol(-1), by combustion calorimetry. Calvet drop-sublimation calorimetric measurements on monoclinic samples of 2-, 3-, and 4-OHBA, led to the following enthalpy of sublimation values at 298.15 K: Delta(sub)(2-OHBA) = 94.4 +/- 0.4 kJ x mol(-1), Delta(sub)(3-OHBA) = 118.3 +/- 1.1 kJ x mol(-1), and Delta(sub)(4-OHBA) = 117.0 +/- 0.5 kJ x mol(-1). From the obtained Delta(f)(cr) and Delta(sub) values and the previously reported enthalpy of formation of monoclinic 2-OHBA (-591.7 +/- 1.3 kJ x mol(-1)), it was possible to derive Delta(f)(2-OHBA, g) = -497.3 +/- 1.4 kJ x mol(-1), Delta(f)(3-OHBA, g) = -475.6 +/- 2.3 kJ x mol(-1), and Delta(f)(4-OHBA, cr) = -480.2 +/- 1.5 kJ x mol(-1). These values, together with the enthalpies of isodesmic and isogyric gas-phase reactions predicted by density functional theory (B3PW91/aug-cc-pVDZ, MPW1PW91/aug-cc-pVDZ, and MPW1PW91/aug-cc-pVTZ) and the CBS-QMPW1 methods, were used to derive the enthalpies of formation of the gaseous 2-, 3-, and 4-carboxyphenoxyl radicals as (2-HOOCC(6)H(4)O(*), g) = -322.5 +/- 3.0 kJ.mol(-1) Delta(f)(3-HOOCC(6)H(4)O(*), g) = -310.0 +/- 3.0 kJ x mol(-1), and Delta(f)(4-HOOCC(6)H(4)O(*), g) = -318.2 +/- 3.0 kJ x mol(-1). The O-H bond dissociation enthalpies in 2-OHBA, 3-OHBA, and 4-OHBA were 392.8 +/- 3.3, 383.6 +/- 3.8, and 380.0 +/- 3.4 kJ x mol(-1), respectively. Finally, by using the ortho-para method, it was found that the H- - -O intramolecular hydrogen bond in the 2-carboxyphenoxyl radical is 25.7 kJ x mol(-1), which is ca. 6-9 kJ x mol(-1) above the one estimated in its parent (2-OHBA), viz. 20.2 kJ x mol(-1) (theoretical) or 17.1 +/- 2.1 kJ x mol(-1) (experimental).