Extraction of gallium(III) and aluminium(III) with O,O-dialkyldithiophosphoric acids

The extraction of Ga³⁺ and Al³⁺ with the liquid cation-exchangers di-n-butyldithiophosphoric acid (DBTPA) and di-(2-ethylhexyl)dithiophosphoric acid (DETPA) in kerosene, in the presence and absence of alcohols and tri-n-butyl phosphate (TBP) has been studied. Both Ga³⁺ and Al³⁺ can be extracted in the form of a neutral complex, MA₃, but the distribution coefficient of Ga³⁺ is the higher by about two orders of magnitude, which can be the basis of the solvent extraction separation of gallium and aluminium. The differences can be explained by the interaction between the sulphur donor atoms of the extractants and the d¹⁰ electronic shell of Ga³⁺ as well as by the lower steric hindrance of ligands co-ordinated to Ga³⁺.     

Determination of aflatoxins in peanuts by matrix solid-phase dispersion and liquid chromatography

A new method based on matrix solid-phase dispersion (MSPD) extraction was studied to determine aflatoxin B1, B2, G1 and G2 from peanuts. Optimization of different parameters, such as type of solid supports for matrix dispersion and elution solvents were carried out. The method used 2 g of peanut sample, 2 g of C18 bonded silica as MSPD sorbent and acetonitrile as eluting solvent. Recoveries of each aflatoxin spiked to peanut samples at 2.5 ng/g (5 ng/g for aflatoxin G2) level were between 78 and 86% with relative standard deviations ranging from 4 to 7%. The limits of quantification ranged from 0.125 to 2.5 ng/g for the four studied aflatoxins using liquid chromatography (LC) with fluorescence detection. In addition, LC coupled to mass spectrometry with an electrospray interface was used for confirmation of aflatoxins present in real samples. Eleven peanut samples from different countries were analyzed by the proposed method and by using an enzyme-linked immunosorbent assay (ELISA). ELISA test is a good screening method for investigation of these mycotoxins in peanut samples.     

Optimization of a clean-up procedure for the determination of heterocyclic aromatic amines in urine by field-amplified sample injection-capillary electrophoresis-mass spectrometry

Heterocyclic amines (HAs), generated when proteinaceous food is cooked, are of special interest since they can be carcinogenic for humans. In this paper, the optimization of a clean-up procedure for the isolation and preconcentration of 15 heterocyclic amines in urine samples is described. The method proposed combines liquid extraction on a solid support of diatomaceous earth with solid-phase extraction in cartridges. Tests were performed on several cartridges containing graphitic carbon or mixed phases, i.e., combining reversed-phase and cation-exchange mechanism, and the best results were obtained with Oasis MCX. The optimized purification method was applied to the quantification of heterocyclic amines in hydrolyzed spiked human urine. The method was carried out by capillary electrophoresis (CE) coupled to mass spectrometry (MS) and applying field-amplified sample injection (FASI) as in-line preconcentration procedure. We obtained detection limits down to 0.3 ng/ml of urine and errors lower than 17%.     

Occurrence and analysis of estrogens and progestogens in river sediments by liquid chromatography-electrospray-mass spectrometry

In this study, an analytical procedure for the determination in sediment of the most abundant and/or physiological active estrogens (estradiol, estriol, estrone, ethynyl estradiol, and diethylstilbestrol) and progestogens (progesterone, norethindrone. and levonorgestrel) is described. The procedure includes ultrasonic extraction of the lyophilized sediment, clean-up with octadecylsilica cartridges, and analysis by liquid chromatography-diode array detection-mass spectrometry (LC-DAD-MS). MS detection is performed with an electrospray interface in the positive ion mode for determination of the progestogens and in the negative ion mode for determination of the estrogens. The method was applied to the determination of the target compounds in river sediments from the area of Catalonia. Estrogens and progestogens were found at concentrations usually in the low ng g(-1) range. Estriol and norethindrone were the compounds most frequently found whereas maximum concentrations in all sediment samples were obtained for ethynyl estradiol (22.8 ng g(-1)) and estrone (11.9 ng g(-1)). Detection limits were in the range of 0.04-1.00 ng g(-1). Preliminary conjectures with regards to the environmental behavior and impact of estrogens and progestogens in rivers are made. To the authors' knowledge, this is the first work reporting a detailed method for the analysis of estrogens and progestogens in river sediments and data on the environmental occurrence of both groups of compounds.     

Net analyte signal as a deconvolution-oriented resolution criterion in the optimisation of chromatographic techniques

The performance of two multivariate calibration measurements, multivariate selectivity (SEL(s)) and scalar net analyte signal (scalar NAS), as chromatographic objective functions (COFs), was investigated. Since both assessments are straightforwardly related to the quantification of analytes in the presence of interferents, they were expected to confer new features in the optimisation of compound resolution, not present in conventional assessments. These capabilities are especially interesting in situations of low resolution, where peak deconvolution becomes an attractive alternative. For comparison purposes, chromatographic resolution (R(s)) and peak purity (p(s)) were used as reference COFs. In order to correlate COFs with the probability of deconvolution error, an artificial peak crossing was used to generate 73 different peak arrangements, which were deconvolved using three different methods. SEL(s) exhibited the best correlation, which allowed predicting properly the risk of obtaining inaccurate deconvolutions. The optimisation of a poorly resolved mixture of 16 aromatic compounds by reversed-phase liquid chromatography with methanol-water and acetonitrile-water mobile phases was examined to investigate the differences in performance among the resolution criteria. In situations like these, SEL(s) tends to consider acceptable mobile phase compositions with partial coelution, which permits however the deconvolution with low errors. In contrast, p(s) selects compositions where the resolution of some compounds is sacrificed to enhance the separation of others. Scalar NAS was not so favourable as expected, since it depends on sampling frequency and peak widening. SEL(s) was not affected by these factors.     

The effect of pH on the reactions of catalytically important RhI complexes in aqueous solution: reaction of [RhCl(tppms)3] and trans-[RhCl(CO)(tppms)2] with hydrogen (TPPMS = mono-sulfonated triphenylphosphine).

Hydrolysis and hydrogenation of [RhCl(tppms)3] (1) and trans-[RhCl(CO)(tppms)2] (2) was studied in aqueous solutions in a wide pH range (2 < pH < 11) in the presence of excess TPPMS (3-diphenylphosphinyl-benzenesulfonic acid sodium salt). In acidic solutions hydrogenation of 1 yields a mixture of cis-mer- and cis-fac-[RhClH2(tppms)3] (3a,b) while in strongly basic solutions [RhH(H2O)(tppms)3] (4) is obtained, the midpoint of the equilibrium between these hydride species being at pH 8.2. The paper gives the first successful 1H and 31P NMR spectroscopic characterization of a water soluble rhodium(I)-monohydride (4) bearing only monodentate phosphine ligands. Hydrolysis of 2 is negligible below pH 9 and its hydrogenation results in formation of [Rh(CO)H(tppms)3] (5), which is an analogue to the well known and industrially used hydroformylation catalyst [Rh(CO)H(tppts)3] (6) (TPPTS = 3,3',3'-phosphinetriyltris(benzenesulfonic acid) trisodium salt). It was shown by pH-potentiometric measurements that formation of 5 is strongly pH dependent in the pH 5-9 range, this gives an explanation for the observed but previously unexplained pH dependence of several hydroformylation reactions. Conversely, the effect of pH on the rate of hydrogenation of maleic and fumaric acid catalyzed by 1 in the 2 < pH < 7 range can be adequately described by considering solely the changes in the ionization state of these substrates. All these results warrant the use of buffered (pH-controlled) solutions for aqueous organometallic catalysis.     

Pseudopotential calculations on Rb+2, Cs+2, RbH+, CsH+ and the mixed alkali dimer ions

Semi-empirical pseudopotentials are used in calculating the ground-state potentials curves for single valence-electron molecular ions. Very accurate results are obtained and a number of predictions given. The ionization energies of the neutral dimers are evaluated. A spectroscopic rule enables us to estimate the A ¹Σ⁺ state of KRb and RbCs.     

Magnetic and Mössbauer Studies of Magnetite-Loaded Polyvinyl Alcohol Hydrogels

Materials producing strain in a magnetic field are known as magnetoelastic or magnetostrictive materials. A new type of material that is able to produce giant strain in a nonhomogeneous magnetic field has been developed. In these magnetic-field-sensitive gels (ferrogels) fine colloidal particles having superparamagnetic behavior are incorporated into a highly swollen elastic polymer network. Magnetic properties of ferrogels have been investigated using electron microscopy, static magnetization measurements, and M?ssbauer spectroscopy. Analysis of the data yielded information on the superparamagnetic behavior of ferrogels and made it possible to estimate the size distribution of the magnetic cores of magnetite particles made by chemical precipitation and built into a chemically cross-linked polyvinyl alcohol matrix. The results are interpreted on the basis of a core-shell model. Copyright 2000 Academic Press.     

Improved coupled-column liquid chromatographic method for the determination of glyphosate and aminomethylphosphonic acid residues in environmental waters

An existing method for the determination of glyphosate and its main metabolite aminomethylphosphonic acid (AMPA) in water has been improved. It is based on precolumn derivatization with the fluorescent reagent 9-fluorenylmethylcloroformate (FMOC) followed by large-volume injection in a coupled-column LC system using fluorescence detection (LC-LC-FD). The derivatization step was slightly modified by changing parameters such as volume and/or concentration of sample and reagents to decrease the limits of quantification (LOQ) of glyphosate and AMPA to 0.1 microg/l. Additionally, the use of Amberlite IRA-900 for preconcentration of glyphosate, prior to the derivatization step, was investigated; the LOQ of glyphosate was lowered to 0.02 microg/l. Drinking, surface and ground water spiked with glyphosate and AMPA at 0.1-10 microg/l concentrations were analysed by the improved LC-LC-FD method. Recoveries were 87-106% with relative standard deviations lower than 8%. Drinking and ground water spiked with glyphosate at 0.02 and 0.1 microg/l were analysed after preconcentration on the anion-exchange resin with satisfactory recoveries (94-105%) and precision (better than 8%).     

Proton induced P-H and Mo-H bond activation at the phosphide bridged dimolybdenum complexes [Mo2Cp2(mu-H)(mu-PHR)(CO)4](R = Cy, 2,4,6-C6H2R'3; R'= H, Me, tBu)

The new hydride complexes [Mo2Cp2(mu-H)(mu-PHR)(CO)4] having bulky substituents (R = 2,4,6-C(6)H2tBu3= Mes*, R = 2,4,6-C6H2Me3= Mes) have been prepared in good yield by addition of Li[PHR] to the triply bonded [Mo2Cp2(CO)4] and further protonation of the resulting anionic phosphide complex [Mo2Cp2(mu-PHR)(CO)4]-. Protonation of the Mes* compound with either [H(OEt2)2][B{3,5-C6H3(CF3)2}4] or HBF4.OEt2 gives the cationic phosphinidene complex [Mo2Cp2(mu-H)(mu-PMes*)(CO)4]+ in high yield. In contrast, protonation of the analogous hydride compounds with Mes or Cy substituents on phosphorus give the corresponding unsaturated tetracarbonyls [Mo2Cp2(mu-PHR)(CO)4]+, which are unstable at room temperature and display a cis geometry. Decomposition of the latter give the electron-precise pentacarbonyls [Mo2Cp2(mu-PHR)(mu-CO)(CO)4]+, also displaying a cis arrangement of the metal fragments. In the presence of BF4- as external anion, fluoride abstraction competes with carbonylation to yield the neutral fluorophosphide hydrides [Mo2Cp2(mu-H)(mu-PFR)(CO)4]. Similar results were obtained in the protonation reactions of the hydride compounds having a Ph substituent on phosphorus. In that case, using HCl as protonation reagent gave the chloro-complex [Mo2ClCp2(mu-PHPh)(CO)4] in good yield. The structures and dynamic behaviour of the new compounds are analyzed on the basis of solution IR and 1H, 31P, 19F and 13C NMR data as well as the X-ray studies carried out on [Mo2Cp2(mu-H)(mu-PHMes)(CO)4](cis isomer), [Mo2Cp2(mu-H)(mu-PFMes)(CO)4](trans isomer), [Mo2Cp2(mu-PHCy)(mu-CO)(CO)4](BF4) and [Mo2ClCp2(mu-PHPh)(CO)4].