Phenomena Affecting the Equilibrium of Al(III) and Zn(II) Extraction with Winsor II Microemulsions

The extraction of Al(III) and Zn(II) from an aqueous solution with two water-in-oil microemulsions, one containing di(2-ethylhexyl)phosphoric acid (DEHPA), was investigated to aid the understanding of the role of the extractant and the metal specific characteristics in the mechanism of microemulsion extraction. The extraction of Al with the DEHPA microemulsion increased by a factor of about 10 with respect to that in the conventional DEHPA system, whereas the extraction of Zn was lower than that in the single DEHPA system. Extraction with the DEHPA-free microemulsion was very low, showing that metal ion solubilization was not important in the mechanism of microemulsion extraction. It is proposed that the effect of the mixed microemulsion on the metal distribution coefficient is the result of the balance between a decrease in the complexation reaction yield due to the interaction between butanol and DEHPA, and the adsorption of the metal complex at the macro- and microinterfaces. The former leads to a decrease in Zn(II) extraction and the latter to Al(III) extraction synergism. Copyright 2000 Academic Press.     

Synthesis and characterization of three novel perfluoro-oligothiophenes ranging in length from the trimer to the pentamer

In this Article, we report on the synthesis and full characterization of three perfluorinated oligothiophenes, ranging in length from the trimer to the pentamer (PF-nT, with n = 3, 4, or 5). The differential pulse voltammetry (DPV) analysis of the compounds showed that they can be both oxidized and reduced (i.e., they display a dual or amphoteric electrochemical behavior), with the reduction peaks positively shifted relative to those of the corresponding unsubstituted oligothiophenes. The electrochemically determined energy gaps are in agreement with those measured from the UV-vis-NIR absorption spectra in solution. The conjugational properties have been investigated by means of FT-Raman spectroscopy, both as pure solids and as dilute solutes in CH(2)Cl(2), revealing that: (i) pi-conjugation does not still reach saturation with chain length for the longest oligomer, and (ii) conformational distortions from a nearly coplanar arrangement of the successive thiophene units upon solution are not too large. DFT and TDDFT quantum chemical calculations have been performed, at the B3LYP/6-31G level, to assess information about the optimized molecular structure, equilibrium atomic charges distribution, energies and topologies of the frontier molecular orbitals (MO) around the gap, vibrational normal modes associated with the most outstanding Raman scatterings, and vertical one-electron excitations that give rise to the main optical absorptions.     

Molecular photoionization cross sections in electron propagator theory: angular distributions beyond the dipole approximation

Corrections to dipole approximation results for angular distributions in photoionization of first-row hydrides have determined by using Dyson orbitals calculated with ab initio electron propagator theory and by considering the full multipole expansion for the incident photon representation. The relative importance of first-order corrections which consist of electric quadrupole and magnetic dipole terms and of higher-order terms has been estimated as a function of photon energy. Multipole corrections to the dipole approximation depend on photon energy and on the characteristics of the Dyson orbitals.     

己内酰胺的聚合——Ⅳ.一元羧酸对聚合过程所发生的作用

己内酰胺在苯甲酸和6-氨基己酸存在下的聚合反应,实验结果表明苯甲酸具有引发 单体聚合、酸解大分子链和酰化大分子的氨基的作用。反应的开始为催化引发单体生成大分子链而不是苯甲酸与单体的加成。随着大分子的增多,酸解和酰化也同时发生。在反应半小时后酸解的影响逐渐显著,到3—4小时以后,酸解影响超过缩聚使聚合物分子量下降羧基含量增加。到反应7—8小时后,聚合物生成量及分子量已达恒定而酰化仍继续进行。到反应达到平衡时,仍然有游离的苯甲酸,聚合物中仍有游离的氨基和羧基,说明酸解、酰化与缩聚都是可逆反应。 在不用苯甲酸的己内酰胺与水的聚合实验中,聚合物虽在常压通氮的情况下在250°,270°或300°加热6小时分子量仍能稳定在一定数值而不升高,即加热15小时(250°)变化也很小。氨基与羧基不再进行缩聚,可能系由于反应系统粘稠,水分子不易扩散除去,大分子不易移动接触,功能基又受本身分子链的空间阻碍,使反应不易继续进行,维持在一定平衡状态。     

Ternary complexes of cimetidine and phenobarbital with Cu(II) in methanolic solution

The formation constants of the binary complexes Cu(CM)²⁺ and Cu(CM) ₂ ²⁺ as well as those of the ternary complexes Cu(CM)L ⁺ and Cu(CM)₂ L ⁺ (CM=Cimetidine=N-Cyano-N-methyl-N[(5-methyl-1H-imidazol-4-yl)methyltioethyl]-guanidine; HL=Phenobarbital=5-ethyl-5-phenyl-barbituric acid) have been determined in 0.1 and 1.0 mol dm^–3 NaClO₄ methanol solutions at 25±0.2°C. The values of logX, log _stat.., and logK confirm the stability of the ternary complexes.

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Ternäre Komplexe von Cimetidin und Phenobarbital mit Cu(II) in methanolischer Lösung

Zusammenfassung Die Stabilitätskonstanten der binären Komplexe Cu(CM)²⁺ und Cu(CM) ₂ ²⁺ sowie die der ternären Komplexe Cu(CM)L ⁺ und Cu(CM)₂ L ⁺ (CM=Cimetidin=N-Cyan-N-methyl-N-[(5-methyl-1H-imidazol-4-yl)methylthioethyl]-guanidin; HL=Phenobarbitalum=5-Ethyl-5-phenyl-barbitursäure) wurden in 0.1 und 1.0M Lösungen von NaClO₄ in Methanol bei 25±0.2°C bestimmt. Die Werte von logX, log _stat. und logK bestätigen die Stabilität der ternären Komplexe.

     

Fast solid-phase extraction-gas chromatography-mass spectrometry procedure for oil fingerprinting. Application to the Prestige oil spill

A rapid and simple fractionation procedure using solid-phase extraction (SPE) cartridges was developed for an accurate determination of aliphatic and polycyclic aromatic hydrocarbons in petroleum residues and further application in chemical fingerprinting of oil spills by gas chromatography-mass spectrometry (GC-MS). Among the adsorbents evaluated, SiO2/C3-CN exhibited the best selectivity, providing, by elution with n-hexane (4 ml) and n-hexane-CH2Cl2 (1:1) (5 ml), two well-resolved aliphatic and aromatic hydrocarbon fractions, with recoveries of 97 +/- 7.2 and 99.7 +/- 13.9%, respectively. The SPE fractionation procedure was compared with the conventional silica-alumina adsorption chromatography showing similar results but practical advantages in terms of reproducibility, analysis time, solvent reduction and cost. Moreover, is particularly suitable for routine analysis with a high sample throughput. The developed methodology was tested in the characterization of fuel-oil samples collected along the Spanish north-west coast, after the Prestige oil spill accident.     

Kinetic analysis of liquid-phase depolymerization of trioxane from programmed temperature data

A sequential kinetic discrimination of potential kinetic models for non-isothermal linear programmed temperature data on the depolymerization of trioxane in a homogeneous liquid phase has been discussed.The influence of the initial concentration on the kinetic curves has been used as an experimental confirmation of the first-order influence of the concentration on the model.Kinetic analysis at constant temperature and conversion permits separation of the effects of concentration and temperature on the kinetic analysis at different levels of the variables.It is provided via non-isothermal kinetic data on the depolymerization of trioxane that nonisothermal experiment's allow a systematic approach to the kinetic behaviour in a wide range of the variables temperature and concentration, leading to maximum knowledge of the reaction model through minimum experimental effort.

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Zusammenfassung Eine sequentielle kinetische Unterscheidung potentieller kinetischer Modelle für die nicht-isotherme, linear temperaturprogrammierte Depolymerisation von Trioxan in homogener flüssiger Phase wird diskutiert. Der Einfluß der Ausgangskonzentration auf die kinetischen Kurven wurde als experimentelle Bestätigung dafür angesehen, daß die Konzentration auf das Modell nach erster Ordnung einwirkt. Die kinetische Analyse bei konstanter Temperatur und Konversion ermöglicht eine Trennung des Einflusses der Konzentration und Temperatur auf die kinetische Analyse bei unterschiedlichen Werten dieser Variablen. In der vorliegenden Arbeit wurde anhand von nichtisothermen kinetischen Daten für die Depolymerisation von Trioxan gezeigt, daß nicht-isotherme Experimente eine systematische Näherung an das kinetische Verhalten in einem weiten Bereich der Variablen Temperatur und Konzentration erlauben und zu einen Maximum an Erkenntnissen über das Reaktionsmodell bei einem Minimum an experimentellen Aufwand führen.

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Influence of the distal his in imparting imidazolate character to the proximal his in heme peroxidase: (1)h NMR spectroscopic study of cyanide-inhibited his42-->ala horseradish peroxidase

The functional higher oxidation states of heme peroxidases have been proposed to be stabilized by the significant imidazolate character of the proximal His. This is induced by a "push-pull" combination effect produced by the proximal Asp that abstracts ("pulls") the axial His ring N(delta)H, along with the distal protonated His that contributes ("pushes") a strong hydrogen bond to the distal ligand. The molecular and electronic structure of the distal His mutant of cyanide-inhibited horseradish peroxidase, H42A-HRPCN, has been investigated by NMR. This complex is a valid model for the active site hydrogen-bonding network of HRP compound II. The (1)H and (15)N NMR spectral parameters characterize the relative roles of the distal His42 and proximal Asp247 in imparting imidazolate character to the axial His. 1D/2D spectra reveal a heme pocket molecular structure that is highly conserved in the mutant, except for residues in the immediate proximity of the mutation. This conserved structure, together with the observed dipolar shifts of numerous active site residue protons, allowed a quantitative determination of the orientation and anisotropies of the paramagnetic susceptibility tensor, both of which are only minimally perturbed relative to wild-type HRPCN. The quantitated dipolar shifts allowed the factoring of the hyperfine shifts to reveal that the significant changes in hyperfine shifts for the axial His and ligated (15)N-cyanide result primarily from changes in contact shifts that reflect an approximately one-third reduction in the axial His imidazolate character upon abolishing the distal hydrogen-bond to the ligated cyanide. Significant changes in side chain orientation were found for the distal Arg38, whose terminus reorients to partially fill the void left by the substituted His42 side chain. It is concluded that 1D/2D NMR can quantitate both molecular and electronic structural changes in cyanide-inhibited heme peroxidase and that, while both residues contribute, the proximal Asp247 is more important than the distal His42 in imparting imidazole character to the axial His 170.