Supramolecular systems-based extraction-separation techniques coupled to mass spectrometry

The combination of supramolecular chemistry and MS has not only been fruitful in the field of gas-phase fundamental studies of host-guest complexes and supramolecular assemblies. Mass spectrometric analysis has also benefited from the ability of supramolecular systems to behave as pseudophases in which solutes partition from the bulk solvent phase. Supramolecular systems-based extraction and concentration schemes and separation techniques have been widely used in different fields of analytical chemistry and are ideally suited for coupling with MS. This review describes the present status of the application of supramolecular chemistry in mass spectrometric analysis and includes topics such as the use of coacervative liquid-liquid extraction and hemimicelle/admicelle-based SPE of organic compounds prior to chromatography and electrophoresis. It also discusses the recent advances in enantioselective analysis using CD in electrophoresis- and chromatography-MS. The potential and analytical challenges of these approaches in environmental and bioanalytical chemistry, where one can expect significant developments in the future, are outlined.     

On the Stability of the Schiff Bases of Pyridoxal 5′-Phosphate with Polypeptides Containing L-Lysine

We determined the apparent equilibrium constant of formation, K_pH, of the Schiff bases of pyridoxal 5′-phosphate (PLP) and poly- and copolymers containing L -lysine, as a function of pH at 25° and a constant ionic strength of 0.1 M . The K_pH values obtained at acidic and neutral pH were larger that those reported for Schiff bases of PLP and hexylamine. We determined calorimetrically ΔH of formation of Schiff bases of PLP and poly(L -lysine) (?4.5′kcal/mol), and PLP and hexylamine (?3.4 kcal/mol) at pH 7.00. Semi-empirical theoretical calculations (INDO and AMI methods) of a model compound of Schiff base of PLP and polypeptide containing L -lysine show the capability of specific interactions between groups of PLP and the peptide skeleton.     

Determination of moxifloxacin in tablets and human urine by square-wave adsorptive voltammetry

This work presents an electroanalytical methodology developed for square-wave voltammetry based in the electrochemical reduction in hanging mercury drop electrode (HMDE), which is simple, fast, reliable and sensitive for determination of moxifloxacin (MOXI) in tablets and spiked urine human samples. The support electrolyte that provided a more defined and intense peak current for MOXI determination was the phosphate buffer 0.04 mol l^{− 1} pH 8.0. In the best-optimized conditions the drug presented an only peak of reduction at − 1.38 V vs. Ag/AgCl, using an E_acc. of − 0.30 V. An LOD of 0.44 and 3.20 ng ml^{− 1} and an LOQ of 1.46 and 10.60 ng ml^{− 1} were found for the pure standard of moxifloxacin and in the presence of matrix, respectively. A good recovery was obtained for assay spiked urine samples and a good quantification of MOXI was achieved in a commercial formulation. The methodology proposed was more sensitive than the spectrofluorimetric and spectrophotometric method with precision and accuracy equivalent.     

Complexes of copper(II) with sugar α-amino acids as ligands

Summary Complexes of Cu^II with 2-(benzylamino)-2-deoxy-d-glycero-d-talo heptonic acid (BnMa) and 2-(benzylamino)-2-deoxy-d-glycero-l-gluco heptonic acid (BnGa) were prepared and characterized by elemental analysis, thermal data, i.r., electronic and e.s.r. spectra, magnetic susceptibility measurements, and X-ray powder diffraction. The metal:ligand stoichiometry of these complexes is 12 and coordination around Cu^II seems to be octahedral, with the ligands bound through the N atom of the amino group and O atoms of the bridging carboxylate group.     

Twistor holomorphic Lagrangian surfaces in the complex projective and hyperbolic planes

We completely classify all the twistor holomorphic Lagrangian immersions in the complex projective plane ², i.e. those Lagrangian immersions such that their twistor lifts to the twistor space over ² are holomorphic. This classification provides a one-parameter family of examples of Lagrangian spheres in ².Research partially supported by a DGICYT grant No. PB91-0731.     

Effect of acetate on ferrihydrite crystallization

Mössbauer spectroscopy was used to follow the aging of ferrihydrite with different amounts of acetate, to achieve more crystalline products. Mössbauer spectra of fresh samples did not show any magnetic components. After two years aging, the solids presented crystalline fractions. Hematite formation was inhibited as acetate content increased in solids. For an acetate/iron molar ratio equal to 0.63 goethite was formed instead of hematite. X-ray diffraction confirmed these results. This work shows that synthetic samples can be used for elucidating the anti-hematitic effect of organic matter already detected in soils.     

The dilution of silica in a NiZnCo spinel ferrite matrix

Silica may dissolve up to about 0.05 wt% in an iron excess NiZnCo spinel matrix, affecting noticeably the magnetic properties at low and high values of the applied field. The initial permeability is reduced by about 50% with the addition of only 0.1 % SiO₂, while the coercivity almost triples, without noticeable changes in porosity or grain distribution. The vacancy and Fe²⁺ content of the sintered material also show a considerable change. The energy associated to the transformation Fe³⁺ Fe²⁺ for the samples without SiO₂ was found to be 0.41–0.42 eV, while for the samples with SiO₂ additions it decreased to 0.26 eV. The changes in magnetic properties are thought to be caused, more than because of the mentioned changes in ion distribution, by the stresses and defects created in the lattice due to the very small size of the Si⁴⁺ ion, which substitutes Fe³⁺ ions in tetrahedral sites. The transition Fe³⁺ Fe²⁺ seems to take place exclusively in the octahedral sites.     

Cohomology of the complement of a free divisor

We prove that if is a ``strongly quasihomogeneous" free divisor in the Stein manifold , and is its complement, then the de Rham cohomology of can be computed as the cohomology of the complex of meromorphic differential forms on with logarithmic poles along , with exterior derivative. The class of strongly quasihomogeneous free divisors, introduced here, includes free hyperplane arrangements and the discriminants of stable mappings in Mather's nice dimensions (and in particular the discriminants of Coxeter groups).