Calorimetric measurement of ionexchange heats of homoionic heulandite and mordenite

The ionexchange heats of homoionic heulandite and mordenite were measured with a microcalorimeter. In the case of K, NH₄, Na, Mg and Ca, the selectivity of the zeolite is determined by the heat of hydration.We are very grateful to Dr. Ingemar Wadso from the Division of Thermochemistry of the University of Lund, Sweden, and to Dr. R. Ohlen from LKB, Sweden, for their advice, and to Ing. Valentina Zelenenko and Lic. Jose Sosa for providing homoionic samples.     

Solvent-free direct regioselective ring opening of epoxides with imidazoles

The reaction of different epoxides with commercially available imidazole at 60 °C leads to the formation of the corresponding 1-(β-hydroxyalkyl)imidazoles in a regioselective manner. When the reaction is applied to a chiral epoxide [(R)-styrene oxide], the expected chiral alcohol is isolated with the same enantiomeric excess. The use of benzimidazole as the heterocyclic component in the same process also allows the simple preparation of the corresponding 1-(β-hydroxyalkyl)benzimidazoles.     

Influence of inorganic mobile phase additives on the retention, efficiency and peak symmetry of protonated basic compounds in reversed-phase liquid chromatography

Inorganic eluent additives affect the retention of protonated basic analytes in reversed-phase HPLC. This influence is attributed to the disruption of the analyte solvation-desolvation equilibria in the mobile phase, also known as "chaotropic effect". With an increase of counteranion concentration analyte retention increases with concomitant decrease in the tailing factor. Different inorganic counteranions at equimolar concentrations affect protonated basic analyte retention and peak symmetry to varying degrees. The effect of the concentrations of four different inorganic mobile phase additives (KPF6, NaClO4, NaBF4, NaH2PO4) on the analyte retention, peak symmetry, and efficiency on a C8-bonded silica column has been studied. The analytes used in this study included phenols, toluene, benzyl amines, beta-blockers and ophthalmic drugs. The following trend in increase of basic analyte retention factor and decrease of tailing factor was found: PF6- > ClO4- approximately BF4- > H2PO4-. With the increase of the counteranion concentration greater analyte loading could be achieved and consequently an increase in the apparent efficiency was observed until the maximum plate number for the column was achieved. At the highest concentration of counteranions, the peak efficiency for most of the basic compounds studied was similar to that of the neutral markers. In contrast, the neutral markers, such as phenols, showed no significant changes in retention, efficiency or loading capacity as counteranion concentration was increased.     

Preparation of trout liver microsomes for iron speciation in P-450 enzymes by AE–FPLC with ICP–(ORS)MS detection

Cytochromes P-450 are members of a superfamily of hemoproteins involved in the oxidative metabolism of various physiological and xenobiotic compounds in eukaryotes and prokaryotes. The multiplicity of this group of enzymes has been widely studied by chromatographic techniques, mainly high-performance liquid chromatography (HPLC). Because these enzymes are membrane-bound proteins, sample preparation for chromatographic separation of P-450 enzymes requires a solubilization step. The sample-preparation procedures are critical, because detergents affect not only the efficiency of protein solubilization but also their further chromatographic resolution. Trout liver microsomes have been taken here as a model sample to investigate iron speciation in cytochrome P-450. Trouts were treated intraperitoneally with -naphthoflavone, a potent inducer of some P-450 enzymes, and a microsomal suspension containing 7.4±0.1 nmol mL^–1 P-450 enzymes was obtained by ultracentrifugation. Lubrol PX was selected as detergent for solubilization, resulting in about 90% solubilization recovery. The solubilized cytochromes P-450 were further separated by AE–FPLC, with UV detection, or coupled to ICP–MS with an octapole reaction system, ICP–(ORS)MS (monitoring Fe signals at masses 54, 56, and 57). A sampling procedure and chromatographic conditions are developed and were successfully applied to iron speciation in trout liver P-450 enzymes. ICP–(ORS)MS detection of P-450 enzymes is Fe-specific and so will give accurate information on the prosthetic group of the protein, which can constitute an advantageous alternative to classical methods for detection of these hemoproteins.     

Nitrile-functionalized pyridinium ionic liquids: synthesis, characterization, and their application in carbon-carbon coupling reactions

A series of relatively low-cost ionic liquids, based on the N-butyronitrile pyridinium cation [C(3)CNpy](+), designed to improve catalyst retention, have been prepared and evaluated in Suzuki and Stille coupling reactions. Depending on the nature of the anion, these salts react with palladium chloride to form [C(3)CNpy](2)[PdCl(4)] when the anion is Cl(-) and complexes of the formula [PdCl(2)(C(3)CNpy)(2)][anion](2) when the anion is PF(6)(-), BF(4)(-), or N(SO(2)CF(3))(2)(-). The solid-state structures of [C(3)CNpy]Cl and [C(3)CNpy](2)[PdCl(4)] have been established by single-crystal X-ray diffraction. The catalytic activity of these palladium complexes following immobilization in both N-butylpyridinium and nitrile-functionalized ionic liquids has been evaluated in Suzuki and Stille coupling reactions. All of the palladium complexes show good catalytic activity, but recycling and reuse is considerably superior in the nitrile-functionalized ionic liquid. Inductive coupled plasma spectroscopy reveals that the presence of the coordinating nitrile moiety in the ionic liquid leads to a significant decrease in palladium leaching relative to simple N-alkylpyridinium ionic liquids. Palladium nanoparticles have been identified as the active catalyst in the Stille reaction and were characterized using transmission electron microscopy.     

Single metal four-electron reduction by U(ii) and masked “U(ii)” compounds

The redox chemistry of uranium is dominated by single electron transfer reactions while single metal four-electron transfers remain unknown in f-element chemistry. Here we show that the oxo bridged diuranium(iii) complex [K(2.2.2-cryptand)]₂[{((Me₃Si)₂N)₃U}₂(μ-O)], 1, effects the two-electron reduction of diphenylacetylene and the four-electron reduction of azobenzene through a masked U(ii) intermediate affording a stable metallacyclopropene complex of uranium(iv), [K(2.2.2-cryptand)][U(η²-C₂Ph₂){N(SiMe₃)₂}₃], 3, and a bis(imido)uranium(vi) complex [K(2.2.2-cryptand)][U(NPh)₂{N(SiMe₃)₂}₃], 4, respectively. The same reactivity is observed for the previously reported U(ii) complex [K(2.2.2-cryptand)][U{N(SiMe₃)₂}₃], 2. Computational studies indicate that the four-electron reduction of azobenzene occurs at a single U(ii) centre via two consecutive two-electron transfers and involves the formation of a U(iv) hydrazide intermediate. The isolation of the cis-hydrazide intermediate [K(2.2.2-cryptand)][U(N₂Ph₂){N(SiMe₃)₂}₃], 5, corroborated the mechanism proposed for the formation of the U(vi) bis(imido) complex. The reduction of azobenzene by U(ii) provided the first example of a “clear-cut” single metal four-electron transfer in f-element chemistry.

Both a masked and the actual complex [U(ii){N(SiMe₃)₂}₃]⁺ effect the reduction of azobenzene to yield a U(vi) bis-imido species providing the first example of a “clear-cut” metal centred four-electron reduction in f-element chemistry.     

Flow analysis-vapor phase generation-Fourier transform infrared (FA-VPG-FTIR) spectrometric determination of nitrite

In this work, the coupling between flow analysis (FA)–vapor phase generation (VPG) and Fourier transform infrared spectrometry (FTIR) has been proposed as a novel and alternative strategy for the determination of nitrite. The analyte was transformed into the gaseous nitric oxide (NO) by on-line reaction with potassium iodide (KI) or ascorbic acid in acidic medium. The gaseous NO generated was transported by means of a N₂ gas carrier stream inside the IR gas cell and the corresponding FTIR spectrum was acquired in a continuous mode. The absorbance at 1876 cm⁻¹, corrected by a baseline established between 1879 and 1872 cm⁻¹ at a nominal resolution of 2 cm⁻¹, was selected as a measurement criterion. The effect of different spectroscopic and flow analysis experimental parameters, such as nominal resolution, number of scans, reducing agent and its concentration, acidic medium, reagents and sample flow rates, and the carrier gas flow rate on the analytical signal, and then in the figures of merit were initially evaluated by using a standard short path length (10 cm) IR gas cell. The optimization of the system was carried out by the univariate method. The main aims of this study were: (i) to investigate the on-line generation of gaseous nitric oxide in a continuous flow system, and (ii) the use of Fourier transform infrared spectrometry as an alternative and selective detector for the determination of nitrite. The proposed method was initially tested and applied for the determination of nitrite in samples with very high concentration of nitrite, such as frankfurters.     

Group contributions to the infinite dilution partial molar volumes of alkanes, alcohols, and glycols in polar organic solvents

Densities of binary mixtures of polar organic solvents with alcohols were measured at 25‡C. The solvents studied were N,N-dimethylformamide, dimethylsulfoxide, and formamide while alcohols were butanol, pentanol, hexanol, and 1,4-butanediol. Density measurements of hydrocarbons (from pentane to dodecane and some heptane isomers) + N,N-dimethylformamide were also performed. From these data the apparent molar volumes of alcohols and hydrocarbons as functions of concentration were calculated. The standard partial molar volumes were obtained by extrapolation to infinite dilution and are discussed in terms of group contributions.     

High-performance liquid chromatographic determination of cocaine and benzoylecgonine by direct injection of human blood plasma sample into an alkyl-diol-silica (ADS) precolumn

A column-switching high-performance liquid chromatographic method with UV detection for the determination of cocaine (COC) and benzoylecgonine (BZE) in human blood plasma samples is described. The method uses an alkyl-diol-silica ADS-C18 extraction precolumn. A 50- micro L plasma sample was introduced to the ADS precolumn in order to separate the analytes from proteins and endogenous compounds. The fraction containing COC and BZE was back-flushed and transferred to an Alltech mixed-mode C(18)/cation-exchange analytical column for final separation. The validation of the method revealed quantitative recoveries from 95.0 to 99.0% for COC at three different concentrations (0.5, 1.0 and 2.0 micro g mL(-1)), and from 96.0 to 99.0% for BZE at the same concentration levels with coefficients of variation <4.00% (n=5). The detection limit (signal to noise ratio (S/N)>3) was 0.03 micro g mL(-1) for all the compounds with an injection volume of 50 micro L. However, it was possible to enhance the sensitivity further by injecting larger plasma volumes, up to 200 micro L, at the same optimal conditions. The overlap of sample preparation, analysis and reconditioning of the extraction column, increase the overall sample throughput to 5 samples h(-1). The developed method has been applied to human blood plasma samples from subjects suspected of cocaine abuse.