Spectrofluorimetric Method for the Determination of Aluminum with Alizarin Red PS

 A simple and direct spectrofluorimetric method has been developed for the determination of aluminum using alizarin red PS (1,2,4-trihydroxy 9,10-anthraquinone-3-sulfonic acid). The method is based on the strong fluorescence (480/564 nm) of Al³⁺ and alizarin red. Experimental parameters such as pH, concentration of the ligand, ionic strength of the solution, reaction time and temperature were optimized in order to maximize the analytical signal. Interferences of several ions (anions and cations) were studied and evaluated. The linear range of the method extends from 3 to 100 μg L⁻¹. Limit of detection (3s_b) was 0.9 μg L⁻¹. The method was tested with a silicate certified reference material. Interferences were eliminated by a liquid extraction with cupferron. Author for correspondence. E-mail: aucelior@rdc.puc-rio.br Received September 10, 2002; accepted January 15, 2003 Published online May 5, 2003     

On the exact distribution of linear combinations of order statistics from dependent random variables

We study the exact distribution of linear combinations of order statistics of arbitrary (absolutely continuous) dependent random variables. In particular, we examine the case where the random variables have a joint elliptically contoured distribution and the case where the random variables are exchangeable. We investigate also the particular L-statistics that simply yield a set of order statistics, and study their joint distribution. We present the application of our results to genetic selection problems, design of cellular phone receivers, and visual acuity. We give illustrative examples based on the multivariate normal and multivariate Student t distributions.     

Working Methods Paper: Critical considerations with respect to the identification of tin species in the environment

Biogeochemical pathways of tin species in the environment are still controversial, e.g. with regard to methylation and transmethylation phenomena, owing to the fact that the identification of methylated tin-compounds is often difficult. The previous tentative identification of a mixed methylbutyltin compound in sediment and biological samples by GC/AAS after hydride generation gave an illustration of this problem. This compound was previously identified in sediments by other authors and also suspected to occur in a contaminated sediment sample from the Boyardville Marina, France. The retention time obtained by GC/AAS corresponded to the actual retention time of a mixed methylbutyltin calibrant. However, additional checks demonstrated that the compound detected was actually monophenyltin. This evidence was produced by a thorough analysis of a selected sediment sample by alternative techniques such as GC/AAS and GC/AES after pentylation, GC/FPD and GC/MS. The results presented highlight the need for a full identification of compounds to avoid mis-interpretation.     

Extraction techniques in speciation analysis of environmental samples

One of the main problems in speciation analysis is that the different species of metals are present in complex matrices at very low concentration levels. Thus it is almost always necessary to separate the analytes of concern from the matrix and to concentrate them up to detectable concentration levels. Special care should be paid during extraction in order to avoid any contamination of samples, losses and changes in speciation of analytes of concern. The most common extraction techniques for speciation analysis of Pb, Sn, Hg, Cr, As, Se and Sb in liquid and solid samples are presented and briefly discussed. Due to the large quantity of material to be covered, speciation of alkyl, aryl, and macromolecular compounds (porphyrines, thioneines, etc.) has not been taken into account.     

Synthesis and Characterization of Heterodinuclear IrCo, RuCo, IrNi, and RuNi Complexes Containing Pyrazolate and Pyrazolylborate Ligands

Treatment of the metallo ligands [ML(pz)(2)(Hpz)] (pz = pyrazolate; L = C(5)Me(5), M = Ir (1); L = mesitylene, M = Ru (3)) with [M'Cl{HB(3-i-Pr-4-Br-pz)(3)}] (M' = Co (4), Ni (5)) yields heterodinuclear complexes of formula [LM(&mgr;-pz)(2)(&mgr;-Cl)M'{HB(3-i-Pr-4-Br-pz)(3)}] (L = C(5)Me(5); M = Ir; M' = Co (6), Ni (7). L = mesitylene; M = Ru; M' = Co (8)). The related complex [Ru(eta(6)-p-cymene)(pz)(2)(Hpz)] (2) reacts with equimolar amounts of 4 or 5 to give mixtures of the corresponding bis(&mgr;-pyrazolato) &mgr;-chloro complexes [(eta(6)-p-cymene)Ru(&mgr;-pz)(2)(&mgr;-Cl)M'{HB(3-i-Pr-4-Br-pz)(3)}] (M' = Co (9), Ni (10)) and the triply pyrazolato-bridged complexes [(eta(6)-p-cymene)Ru(&mgr;-pz)(3)M'{HB(3-i-Pr-4-Br-pz)(3)}] (M' = Co (11), Ni (12)). Complex 1 reacts with 5 in the presence of KOH to give the IrNi complex [(eta(5)-C(5)Me(5))Ir(&mgr;-pz)(3)Ni{HB(3-i-Pr-4-Br-pz)(3)}] (13) whereas its reaction with 4 and KOH rendered the bis(&mgr;-pyrazolato) &mgr;-hydroxo complex [(eta(5)-C(5)Me(5))Ir(&mgr;-pz)(2)(&mgr;-OH)Co{HB(3-i-Pr-4-Br-pz)(3)}] (14). The molecular structure of the heterobridged IrCo complex (6) and those of the homobridged RuNi (12) and IrNi (13) complexes have been determined by X-ray analyses. Compound 6 crystallizes in the monoclinic space group P2(1)/n, with a = 10.146(5) ?, b = 18.435(4) ?, c = 22.187(13) ?, beta = 97.28(4) degrees, and Z = 4. Complex 12 is monoclinic, space group P2(1), with a = 10.1169(7) ?, b = 21.692(2) ?, c = 11.419(1) ?, beta = 112.179(7) degrees, and Z = 2. Compound 13 crystallizes in the monoclinic space group Cc, with a = 13.695(2) ?, b = 27.929(6) ?, c = 13.329(2) ?, beta = 94.11(4) degrees, and Z = 4. All the neutral complexes 6, 12, and 13 consist of linear M.M'.B backbones with two (6) or three (12, 13) pyrazolate ligands bridging the dimetallic M.M' units and three substituted 3-i-Pr-4-Br-pz groups joining M' to the boron atoms. The presence in the proximity of the first-row metal M' of the three space-demanding isopropyl substituents of the pyrazolate groups induces a significant trigonal distortion of the octahedral symmetry, yielding clearly different M'-N bond distances on both sides of the ideal octahedral coordination sphere of these metals.     

Anilinepropylsilica xerogel used as a selective Cu (II) adsorbent in aqueous solution

The metal ion adsorption properties of the microporous hybrid anilinepropylsilica xerogel were studied using divalent copper, zinc, and cadmium ions in aqueous solutions in concentrations ranging from 10(-4) up to 5x10(-3) moll(-1). At low concentrations the surface of the solid phase presents selectivity for Cu (II), even in competitive conditions. This preferential sorption ability for copper in relation to zinc and cadmium ions was interpreted by considering the xerogel morphology.     

Determination of site-site distance and site concentration within polymer beads: a combined swelling-electron paramagnetic resonance study

This work proposes a combined swelling-electron paramagnetic resonance (EPR) approach aiming at determining some unusual polymer solvation parameters relevant for chemical processes occurring inside beads. Batches of benzhydrylamine-resin (BHAR), a copolymer of styrene-1% divinylbenzene containing phenylmethylamine groups were, labeled with the paramagnetic amino acid 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amine-4-carboxylic acid (TOAC), and their swelling properties and EPR spectra were examined in DCM and DMF. By taking into account the BHARs labeling degrees, the corresponding swelling values, and some polymer structural characteristics, it was possible to calculate polymer swelling parameters, among them, the volume and the number of sites per bead, site-site distances and site concentration. The latter values ranged from 17 to 170 A and from 0.4 to 550 mM, respectively. EPR spectroscopy was applied to validate the multistep calculation strategy of these swelling parameters. Spin-spin interaction was detected in the labeled resins at site-site distances less than approximately 60 A or probe concentrations higher than approximately 1 x 10(-2) M, in close agreement with the values obtained for the spin probe free in solution. Complementarily, the yield of coupling reactions in different resins indicated that the greater the inter-site distance or the lower the site concentration, the faster the reaction. The results suggested that the model and the experimental measurements developed for the determination of solvation parameters represent a relevant step forward for the deeper understanding and improvement of polymer-related processes.     

Synthesis and molecular structure of [Re2(μ:η-C24H18N4)(CO)6] containing the rtct-tetrakis(2-pyridyl)cyclobutandiyl ligand, derived from the reaction of [Re2(CO)8(MeCN)2] and 1,2-bis(2-pyridyl)ethene

The reaction of the labile compound [Re₂(CO)₈(CH₃CN)₂] with trans-1,2-bis(2-pyridyl)ethene (C₁₂H₁₀N₂) at room temperature in tetrahydrofuran affords the compounds [Re₂(μ:η³-C₁₂H₁₀N₂)(CO)₈] (1) and the oxidative addition product [Re₂(μ-H)(μ:η³-C₁₂H₉N₂)(CO)₇] (2). When the reaction is carried out at temperatures of refluxing tetrahydrofuran, besides compounds 1 and 2, the oxidative addition product [Re₂(μ-H)(μ:η⁴-C₁₂H₉N₂)(CO)₆] (3), the insertion product [Re₂(μ:η⁴-C₁₂H₁₀N₂)(CO)₈] (4) and [Re₂(μ:η⁶-C₂₄H₁₈N₄)(CO)₆] (5) are obtained. Compound 5 contains the organic ligand rtct-tetrakis(2-pyridyl)cyclobutandiyl which is derived from a [2 + 2] cycloaddition of 1,2-bis(2-pyridyl)ethene mediated by its coordination to the bimetallic framework. The molecular structures of 1, 2, 4 and 5 were confirmed by X-ray crystallographic studies.     

Optimization of the reduction of Se(VI) to Se(IV) in a microwave oven

 Parameters for the reduction of Se(VI) to Se(IV) in HCl medium by heating in a microwave oven have been optimized. The reduction resulted to be quantitative applying 100% power, corresponding to 600 W heating for 2 min in 6 mol/L or for 3 min in 4 mol/L HCl. The behavior of selenomethionine and selenocystine under the optimized reduction conditions was studied in order to evaluate a possible interference of these selenium species in the determination of Se(VI). The final determination of Se(IV), and Se(VI) were done by hydride generation-atomic absorption spectrometry. The analytical merits of the method are reported. The method was applied to the selective determination of Se(IV), and Se(VI) in spiked river and lake water. Received: 6 December 1996/Revised: 1 April 1997/Accepted: 3 April 1997