Study of ion chromatographic behavior of inorganic and organic antimony species by using inductively coupled plasma mass spectrometric (ICP-MS) detection

An on-line method for the analysis of Sb(III), Sb(V) and trimethylstiboxide (TMSbO) is presented. The separation is performed using ion chromatography (IC) on a strong anion-exchange column with phthalic acid plus 2% acteone at pH 5 as mobile phase. The chromatographic system is coupled to an ICP-MS as detector. The influence of different complexing agents on the chromatographic behavior of the antimony species is studied. Rather stable complexes of Sb(III) seem to be formed with citrate and tartrate under the experimental conditions. TMSbO forms a dianionic species with citrate in contrast to the otherwise monoanionic complex. Received: 31 Juli 1997 / Revised: 8 December 1997 / Accepted: 11 December 1997     

钯-8-羟基喹啉-5-磺酸络合物电极反应和十二烷基硫酸钠的增敏机理

钯 8 羟基喹啉 5 磺酸形成的络合物的峰电流 (pH 8.6 ,- 0 .6 8V)具有吸附特性 ,为不可逆电极反应过程。其电子转移数 (n)、电子转移系数 (α)及饱和吸附量 (Γs)分别为 2、0 .4 6和 2 .2× 10 - 9mol cm2 ;钯 与8 羟基喹啉 5 磺酸的络合比为 1∶2 ;稳定常数 (K)为 8.73× 10 7。加入阴离子表面活性剂十二烷基硫酸钠未形成三元络合物 ,催化电流是由与十二烷基硫酸钠共吸附在电极表面上的超氧阴离子自由基氧化了络合物的电极反应中间体所产生的。     

Structure and dynamic stability of cyclodextrin inclusion complexes with 1,4-disubstituted bicyclo[2.2.2]octanes

The properties of inclusion complexes of 1,4-di-R-bicyclo[2.2.2]octaves (R = H (1), Me (2), Cl (3), Br (4), and OH (5)) with cyclodextrins have been studied by NMR, microcalorimetry, and force-field computations. The compounds2 and3 (but not the other compounds) give dynamically stable 1:2 guest-host complexes with -cyclodextrin. Microcalorimetry of5 in water indicates a moderately strong 1:1 complex with - but weak complexes with - or -cyclodextrin. The behaviour depends on the subtle interplay size, polarity, hydrophobicity and type of solvent.     

Direct vinylation of glucose derivatives with acetylene

Vinyl ethers, promising chiral carbohydrate synthons, have been synthesized by the addition of glucose acetals (1,2:5,6-di-O-isopropylidene-α-d-glucofuranose, methyl 4,6-O-benzylidene-α-d-glucopyranoside, 1,2-O-cyclohexylidene-α-d-glucofuranose, methyl α-d-glucopyranoside) to acetylene under atmospheric and elevated pressures in an autoclave in the presence of superbase catalytic systems (KOH-DMSO, t-BuOK-DMSO). The complete vinylation of 1,2:5,6-di-O-isopropylidene-α-d-glucofuranose and methyl α-d-glucopyranoside has been realized under elevated pressure of acetylene in the system KOH-THF as well.     

Formation of supported size-controlled nanoparticles of sulfated zirconia

Methods of the preparation of catalysts for alkane skeletal isomerization based on uniform nanoparticles of sulfated zirconia anchored to different supports were investigated. These catalysts were characterized by using the ICP, HRTEM and BET techniques. The activities of the catalysts in the reaction of n-butane isomerization were measured and compared with those of bulk catalysts.     

Adsorption thin-layer chromatography and viscometry of polystyrenes in solvent mixtures

The effect of the thermodynamic quality of solvent mixtures on the adsorption behavior of macromolecules under dynamic conditions was investigated. The chromatographic behavior of polystyrenes (PSs) in various mixed eluents was studied under conditions of adsorption and size-exclusion thin-layer chromatography as well as at the exclusion-adsorption transition point with silica gel KSKG adsorbent. The thermodynamic quality of the solvent mixtures used in the chromatographic experiments was determined viscometrically. The dependences of the intrinsic viscosity of PSs on solvent composition for solvent-non-solvent, two solvents, and theta-solvent-solvent mixtures were obtained. A correlation was found between Snyder's polarity indices for the solvent mixtures used in polymer chromatography under "critical conditions" and the intrinsic viscosity values of PSs in the same mixtures.     

Catalyzed Asymmetric Arylation Reactions

Addition and substitution reactions with carbon nucleophiles are fundamental processes in organic synthesis, and the development of general catalytic asymmetric variants thereof is still a major challenge today. In contrast to enantioselective alkyl transfer reactions, the corresponding arylations have not yet reached a high level of maturity. The existing protocols are either of no general applicability or are limited in terms of selectivity. This article summarizes established routes for catalytic asymmetric aryl transfer together with the latest developments in this area. The scope and limitations of this reaction are discussed.     

Preparation and redox properties of N,N,N-1,3,5-trialkylated flavin derivatives and their activity as redox catalysts

Eight different flavin derivatives have been synthesized and the electronic effects of substituents in various positions on the flavin redox chemistry were investigated. The redox potentials of the flavins, determined by cyclic voltammetry, correlated with their efficiency as catalysts in the H2O2 oxidation of methyl p-tolyl sulfide. Introduction of electron-withdrawing groups increased the stability of the reduced catalyst precursor.     

H-, C-NMR and ethylene polymerization studies of zirconocene/MAO catalysts: effect of the ligand structure on the formation of active intermediates and polymerization kinetics

Using ¹H- and ¹³C-NMR spectroscopies, cationic intermediates formed by activation of L₂ZrCl₂ with methylaluminoxane (MAO) in toluene were monitored at Al/Zr ratios from 50 to 1000 (L₂ are various cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands). The following catalysts were studied: (Cp-R)₂ZrCl₂ (R=Me, 1,2-Me₂, 1,2,3-Me₃, 1,2,4-Me₃, Me₄, Me₅, n-Bu, t-Bu), rac-ethanediyl(Ind)₂ZrCl₂, rac-Me₂Si(Ind)₂ZrCl₂, rac-Me₂Si(1-Ind-2-Me)₂ZrCl₂, rac-ethanediyl(1-Ind-4,5,6,7-H₄)₂ZrCl₂, (Ind-2-Me)₂ZrCl₂, Me₂C(Cp)(Flu)ZrCl₂, Me₂C(Cp-3-Me)(Flu)ZrCl₂ and Me₂Si(Flu)₂ZrCl₂. Correlations between spectroscopic and ethene polymerization data for catalysts (Cp-R)₂ZrCl₂/MAO (R=H, Me, 1,2-Me₂, 1,2,3-Me₃, 1,2,4-Me₃, Me₄, Me₅, n-Bu, t-Bu) and rac-Me₂Si(Ind)₂ZrCl₂ were established. The catalysts (Cp-R)₂ZrCl₂/AlMe₃/CPh₃⁺B(C₆F₅)₄⁻ (R=Me, 1,2-Me₂, 1,2,3-Me₃, 1,2,4-Me₃, Me₄, n-Bu, t-Bu) were also studied for comparison of spectroscopic and polymerization data with MAO-based systems. Complexes of type (Cp-R)₂ZrMe⁺←Me⁻-Al≡MAO (IV) with different [Me-MAO]⁻ counteranions have been identified in the (Cp-R)₂ZrCl₂/MAO (R=n-Bu, t-Bu) systems at low Al/Zr ratios (50-200). At Al/Zr ratios of 500-1000, the complex [L₂Zr(μ-Me)₂AlMe₂]⁺[Me-MAO]⁻ (III) dominates in all MAO-based reaction systems studied. Ethene polymerization activity strongly depends on the Al/Zr ratio (Al/Zr=200-1000) for the systems (Cp-R)₂ZrCl₂/MAO (R=H, Me, n-Bu, t-Bu), while it is virtually constant in the same range of Al/Zr ratios for the catalytic systems (Cp-R)₂ZrCl₂/MAO (R=1,2-Me₂, 1,2,3-Me₃, 1,2,4-Me₃, Me₄) and rac-Me₂Si(Ind)₂ZrCl₂/MAO. The data obtained are interpreted on assumption that complex III is the main precursor of the active centers of polymerization in MAO-based systems.     

Theoretical analysis of the porphyrin-porphyrin exciton interaction in circular dichroism spectra of dimeric tetraarylporphyrins

Chiral bis-porphyrins are currently the subject of intense interest as chiral receptors and as probes in the determination of structure and stereochemistry. To provide an improved framework for interpreting the circular dichroism (CD) spectra of bis-porphyrins, we have calculated the CD spectra of chiral bis-porphyrins from three classes: I, where porphyrins can adopt a relatively wide range of orientations relative to each other; II, porphyrins have a fixed relative orientation; III, porphyrins undergo pi-stacking. The calculations primarily utilized the classical polarizability theory of DeVoe, but were supplemented by the quantum mechanical matrix method. Class I was represented by three isomers of the diester of 5alpha-cholestane-3,17-diol with 5-(4'-carboxyphenyl)-10,15,20-triphenylporphin (2-alphabeta, 2-betaalpha, 2-betabeta). Careful analysis of the torsional degrees of freedom led to two to four minimum-energy conformers for each isomer, in each of which the phenyl-porphyrin bonds had torsional angles near 90 degrees. Libration about these bonds is relatively unrestricted over a range of +/-45 degrees. CD spectra in the Soret region were calculated as Boltzmann-weighted averages over the low-energy conformers for each isomer. Three models were used: the effective transition moment model, in which only one of the degenerate Soret components is considered, along the 5-15 direction; the circular oscillator model, in which both Soret components are given equal weight; and the hybrid model, in which the 10-20 oscillator is given half the weight of the 5-15 oscillator, to mimic the effect of extensive librational averaging about the 5-15 direction. All three models predict Soret exciton couplets with signs in agreement with experiment. Quantitatively, the best results are given by the hybrid and circular oscillator models. These results validate the widely used effective transition moment model for qualitative assignments of bis-porphyrin chirality and thus permit application of the exciton chirality model. However, for quantitative studies, the circular oscillator or hybrid models should be used. The simplified effective transition moment and hybrid models are justified by the librational averaging in the class I bis-porphyrins and should only be used with such systems. Two class II bis-porphyrins were also studied by DeVoe method calculations in the circular oscillator model, which yielded good agreement with experiment. Class III bis-porphyrins were represented by 2-alphaalpha, for which the calculations gave qualitative agreement. However, limitations in the conformational analysis with the close contacts and dynamic effects in these pi-stacked systems preclude quantitative results.