Development of a new sequential injection in-line cloud point extraction system for flame atomic absorption spectrometric determination of manganese in food samples

A preconcentration method for manganese determination by sequential injection cloud point extraction with subsequent detection by flame atomic absorption spectrometry (FAAS) has been developed. The enrichment of Mn was performed after a preliminary on-line cloud point extraction and entrapment of manganese-containing surfactant aggregated within a minicolumn packed with cotton. The laboratory-made reagent 4-(5′-bromo-2′-thiazolylazo)orcinol (Br-TAO) and the surfactant Triton X-114 were used for cloud point extraction. The manganese ions were eluted with sulphuric acid solution and directly introduced into the FAAS. Chemical and flow variables affecting the preconcentration were studied. Using a sample volume of 2.80 mL the limit of detection and enrichment factor were calculated to be 0.5 μg L⁻¹ and 14, respectively. The sample frequency is 48 h⁻¹, considering a total run cycle of 75 s. The accuracy of the proposed method has been demonstrated by the analysis of the certified reference biological materials rice flour and tomato leaves. The method has been applied to determination of manganese in food samples.     

Cascade dicopper architectures of a dibenzodioxatetraazamacrocycle

The dibenzodioxatetraazamacrocycle [26]pbz₂N₄O₂ was characterised by single crystal X-ray diffraction and the protonation constants of this compound and the stability constants of its copper(II) and lead(II) complexes were determined by potentiometry in water at 298.2 K in 0.10 mol dm⁻³ in KNO₃. Mono- and dinuclear complexes were found for both metal ions, the dinuclear complexes being the main species in the 5–7.5 pH range for copper(II) and 7.5–8.5 for lead(II). As expected the values of the stability constants for the copper(II) complexes are lower than those for related macrocycles containing only nitrogen atoms. The presence of mono- and dinuclear copper complexes was also confirmed by electrospray ionization mass spectrometry. These results suggest that the symmetric macrocyclic cavity of [26]pbz₂N₄O₂ has enough space for the coordination of two metal ions. Additionally, NMR spectroscopy showed that the dinuclear complex of lead(II) has high symmetry. The equilibrium constants of the dinuclear copper(II) complexes and dicarboxylate anions (oxalate, malonate and succinate) were also determined in 0.10 mol dm⁻³ aqueous KNO₃ solution. Only species containing one anion, Cu₂H_hLA^(2+h), were found, strongly suggesting that the anion bridges the two copper(II) ions. The binding constants of the cascade species formed by [Cu₂[26]pbz₂N₄O₂(H₂O)_x]⁴⁺ with dicarboxylate anions decrease with the increase in length of the alkyl chain of the anion, a fact which was attributed to a higher conformational energy necessary for the rearrangement of the macrocycle to accommodate the larger anions bridging the two copper(II) centres. The variation of the magnetic susceptibility with temperature of [Cu₂(H₂[26]pbz₂N₄O₂)(oxa)₃] · 4H₂O and [Cu₂([26]pbz₂N₄O₂)(suc)Cl₂] were measured and the two complexes showed different behaviour.     

A versatile parameter for comparing the capacities of soils for sorption and retention of heavy metals dumped individually or together: results for cadmium, copper and lead in twenty soil horizons

Heavy metals can be immobilized by soils and their distribution among the particulate soil components depends on the identity and amount of the metal, the properties of the soil, and other environmental factors. Cd, Cu and Pb are among the most potentially toxic heavy metals, are present--often together--in numerous polluting spills and in agrochemicals. We evaluated the individual and competitive sorption and retention of Cd, Cu and Pb on 20 soil horizons. As is usual, the isotherms constructed were so irregular, especially the retention isotherms, that it was not possible to classify and compare them in terms of the conventional isotherm shapes. Nor could they be compared using Langmuir or Freundlich parameters, since not all could be fitted with either of these equations. They were therefore characterized and compared in terms of several varieties of distribution coefficient, including a novel adimensional parameter K(r) which on the basis of correlation and principal components analyses was judged to be the most coherent and generally applicable to all experimental conditions (sorption and desorption starting from single- or multi-metal solutions). K(r) proved to be mainly determined by soil pH, effective cation exchange capacity, and Mn oxides content.     

Structure and magnetic properties of Ca2Fe1−xMnxAlO5+δ

Ca₂Fe_1−xMn_xAlO₅ (0?x?1) compounds were prepared by a self-combustion method under air (x=0, 0.1, 0.2 and 0.3) and nitrogen (x=0.5, 0.7 and 1.0). The samples prepared under nitrogen were successfully oxidized after short annealing under air. Both X-ray powder diffraction (XRD) Rietveld analysis and electron diffraction revealed that all compounds adopt the brownmillerite-type structure. All samples present an overall antiferromagnetic behaviour and data from magnetic measurements and Mössbauer spectroscopy allowed to conclude that the transition temperature decreases as Mn content increases for x?0.3 and increases in the case of the x?0.5 compounds. Except for x=1, chemical disorder due to the occupancy of both octahedral and tetrahedral sites by different metals as well as the competition between different moments’ orientation induce a complex magnetic behaviour characterized by magnetic frustration and canted antiferromagnetism. Mössbauer spectroscopy and chemical titrations also allowed to conclude about the preferential oxidation of Mn³⁺ over Fe³⁺, obtained by thermal treatment under air of the x=0.5 and 0.7 compositions.     

Use of effective core potential calculations for the conformational and vibrational study of platinum(II) anticancer drugs. cis-Diamminedichloroplatinum(II) as a case study

In the light of the recognized anticancer properties of cisplatin-type inorganic systems, the exact knowledge of their conformational preferences is of the utmost importance for understanding their biological activity. The present study reports the use of theoretical (quantum mechanical) calculations for achieving this goal. An alternative calculation method to the use of the AE basis sets, both accurate and computationally feasible, was presently tested for the conformational and vibrational study of cis-diamminedichloroplatinum(II). Effective core potentials (ECPs) were used, within the HF methodology and, within the B3LYP and mPW1PW DFT protocols. The DFT methods (particularly mPW1PW) were found to be the best choice for describing cDDP (as compared to the HF methodology).     

Organo-Laponites as novel mesoporous supports for manganese(III) salen catalysts

A Mn(III) salen complex was immobilized onto the Laponite surface using three different methodologies: method A, direct immobilization of the complex on the parent Laponite; method B, covalent anchoring through cyanuric chloride (CC); and method C, covalent anchoring through CC into a 3-aminopropyl)triethoxysilane (APTES) modified Laponite. All of the materials were characterized by FTIR, XPS, thermogravimetry, XRD, and nitrogen isotherms at 77 K, to gather information on the modifications introduced by the organo spacers within the Laponite surface, as well as on the anchored complex integrity; the Mn based materials were screened in the heterogeneous epoxidation of styrene. The results have shown that the immobilization of the manganese(III) salen complex by methods B and C have occurred at the edges of the clay particles through the spacers (APTES and CC) that have been anchored onto the Si-OH groups, whereas in method A, the complex is distributed throughout the clay surface, including the interlayer region. Therefore, the manganese loadings on the Laponites were as follows: materials prepared by method A > method B > method C. All of the heterogeneous catalysts showed high styrene epoxide selectivity, with that prepared by method A showing comparable styrene epoxide selectivity as the homogeneous phase reaction. The styrene epoxide yields decrease in the following order: materials prepared by method A > method B > method C (1st cycles), which parallel the respective support catalytic activity and decreasing of manganese content. The heterogeneous catalysts prepared using methods B and C could be reused at least for four times, with the former exhibiting the most stable catalytic activity, but that prepared by method A showed a significant decrease after two catalytic cycles.     

Eikonal representation in the momentum-transfer space

By means of empirical fits to the differential cross section data on pp and elastic scattering, above 10 GeV (center-of-mass energy), we determine the eikonal in the momentum-transfer space (q ²- space). We make use of a numerical method and a novel semi-analytical method, through which the uncertainties from the fit parameters can be propagated up to the eikonal in the q ²- space. A systematic study of the effect of the experimental information at large values of the momentum transfer is developed and discussed in detail. We present statistical evidence that the imaginary part of the eikonal changes sign in the q ²- space and that the position of the zero decreases as the energy increases; after the position of the zero, the eikonal presents a minimum and then goes to zero through negative values. We discuss the applicability of our results in the phenomenological context, outlining some connections with nonperturbative QCD. A short review and a critical discussion on the main results concerning “model-independent” analyses are also presented. Received: 19 August 2004, Revised: 12 November 2004, Published online: 14 January 2005 PACS: 13.85.Dz, 13.85.-t     

Highly excited states decay in p-terphenyl crystals. Magnetic field effect investigation

The magnetic field effect on the fluorescence of p-terphenyl crystals was investigated. It is shown that in aromatic crystals an important decay channel of highly excited states is autoionization followed by a triplet exciton creation by collision of the emitted electron.     

Polymers and g|φ|4 theory in four dimensions

We investigate the approach to the critical point and the scaling limit of a variety of models on a four-dimensional lattice, including g|φ|₄⁴ theory and the self-avoiding random walk. Our results, both theoretical and numerical, provide strong evidence for the triviality of the scaling limit and for logarithmic corrections to mean field scaling laws, as predicted by the perturbative renormalization group. We relate logarithmic corrections to scaling to the triviality of the scaling limit. Our numerical analysis is based on a novel, high-precision Monte Carlo technique.     

High accuracy A.D.I. methods for fourth order parabolic equations with variable coefficients

High accuracy alternating direction implicit (A.D.I.) methods are derived for solving fourth order parabolic equations with variable coefficients in one, two, and three space dimensions. Splittings are discussed and numerical results are presented.