Liquid chromatography and characterization of ether-functionalized imidazolium ionic liquids on mixed-mode reversed-phase/cation exchange stationary phase

A new series [C_nO_mmim]Cl of imidazolium cation-based ionic liquids (ILs), with an ether functional group on the alkyl side-chain, has been prepared. The possibility of analyzing the ionic liquids by high performance liquid chromatography (HPLC) was investigated on mixed-mode reversed/cation exchange stationary phase with the aqueous-acetonitrile mobile phase. Elution parameters, such as retention factor, selectivity and column efficiency, were studied as functions of mobile phase composition and pH. The ILs were characterized by elemental analysis, and infrared, UV and ¹H, ¹³C NMR spectroscopy.     

Desirability-based optimization and its sensitivity analysis for the perindopril and its impurities analysis in a microemulsion LC system

In the current paper the application of multiobjective optimization (MOOP) technique, via Derringer's desirability function, to a microemulsion liquid chromatographic (MELC) method is described. Chromatographic separation of perindopril tert-butylamine and its four impurities was selected as the case study. Central composite design (CCD) with fractional factorial design, ± 0.5 α star design and four replications in central point was applied for a response surface study, in order to examine in depth the effects of the most important factors. As factors that influence the system mostly (i) content of ethyl acetate and (ii) butyl acetate in composite internal phase, (iii) content of sodium dodecyl sulfate (surfactant) and (iv) n-butanol (co-surfactant), as well as (v) pH of the mobile phase were selected. Retention factor of (a) perindoprilat and (b) impurity Y 31 and (c) resolution factor for impurities Y 32 and 33 were chosen for simultaneous optimization. By adjustment of the importance coefficients and weights, according to defined objectives, the optimal mobile phase composition was predicted to be: 0.24% w/v butyl acetate, 0.3% w/v ethyl acetate, 2% w/v SDS, 7.75% w/v n-butanol and pH of the mobile phase 3.7. The sensitivity analysis of desirability function for these optimal conditions was conducted for the first time in LC separations, by applying a sensitivity procedure. The performed sensitivity analysis confirmed that the higher overall desirability does not necessarily mean a better solution. The accuracy of prediction might be affected if the optimal levels of input variables, achieved from several design points, end up with equal settings and different corresponding overall desirability. In our study this was not the issue, which confirmed the adequacy of predicted optimum.     

Mono-Phosphazenyl Phosphines (R2N)3P=N–P(NR2)2 – Strong P-Bases,P-Donors,and P-Nucleophiles for the Construction of Chelates

We present a convenient three-step synthesis of amino substituted phosphazenyl phosphines of the general formula (R₂N)₃P=N–P(NR₂)₂ [NR₂ = N(CH₂)₄, N(CH₂)₅, N(CH₂)₆]. These easily accessible mixed valent compounds display a surprisingly high proton affinity and basicity in the same range as the corresponding Schwesinger diphosphazene (Me₂N)₃P=N–P=NEt(NMe₂)₂ (Et-P₂) and Verkade's proazaphosphatrane superbases. Within the central [P^III–N=P^V] scaffold, the phosphine P^III and not the phosphazene N^III atom is the center of highest proton affinity, basicity and donor strength. As P-bases, the title compounds display calculated proton affinities between 265.8 (NR₂ = NMe₂) and 274.7 kcal · mol^–1 [NR₂ = N(CH₂)₄] and pK_BH⁺ values between 26.4 (NR₂ = NMe₂) and 31.5 [NR₂ = N(CH₂)₄] on the acetonitrile scale. As P-nucleophiles, they are key intermediates in the synthesis of hyperbasic bis(diphosphazene) proton sponges, chiral bis(diphosphazene) proton pincers, bisphosphazides, and superbasic P₂-bisylides. Their Staudinger reactions as nucleophile towards 1,8-diazidonaphthalene leading to 1,8-naphthalene-bisphosphazides is described in detail. The donor strength of the title compounds towards fragments [Se] and [Ni(CO)₃] is in the same range as that of N-heterocyclic carbenes.     

Decaborane thiols as building blocks for self-assembled monolayers on metal surfaces

Three nido-decaborane thiol cluster compounds, [1-(HS)-nido-B(10)H(13)] 1, [2-(HS)-nido-B(10)H(13)] 2, and [1,2-(HS)(2)-nido-B(10)H(12)] 3 have been characterized using NMR spectroscopy, single-crystal X-ray diffraction analysis, and quantum-chemical calculations. In the solid state, 1, 2, and 3 feature weak intermolecular hydrogen bonding between the sulfur atom and the relatively positive bridging hydrogen atoms on the open face of an adjacent cluster. Density functional theory (DFT) calculations show that the value of the interaction energy is approximately proportional to the number of hydrogen atoms involved in the interaction and that these values are consistent with a related bridging-hydrogen atom interaction calculated for a B(18)H(22)·C(6)H(6) solvate. Self-assembled monolayers (SAMs) of 1, 2, and 3 on gold and silver surfaces have been prepared and characterized using X-ray photoelectron spectroscopy. The variations in the measured sulfur binding energies, as thiolates on the surface, correlate with the (CC2) calculated atomic charge for the relevant boron vertices and for the associated sulfur substituents for the parent B(10)H(13)(SH) compounds. The calculated charges also correlate with the measured and DFT-calculated thiol (1)H chemical shifts. Wetting-angle measurements indicate that the hydrophilic open face of the cluster is directed upward from the substrate surface, allowing the bridging hydrogen atoms to exhibit a similar reactivity to that of the bulk compound. Thus, [PtMe(2)(PMe(2)Ph)(2)] reacts with the exposed and acidic B-H-B bridging hydrogen atoms of a SAM of 1 on a gold substrate, affording the addition of the metal moiety to the cluster. The XPS-derived stoichiometry is very similar to that for a SAM produced directly from the adsorption of [1-(HS)-7,7-(PMe(2)Ph)(2)-nido-7-PtB(10)H(11)] 4. The use of reactive boron hydride SAMs as templates on which further chemistry may be carried out is unprecedented, and the principle may be extended to other binary boron hydride clusters.     

Sample-induced internal pH gradients in microcolumn liquid chromatography of proteins

Summary The technique of an internal pH gradient induced by the sample is applied to the separation of proteins by liquid chromatography. Compatibility of the method with microcolumns is demonstrated and examples of separations on different types of sorbents are given.     

The axial dependence of the cathode current density in the longitudinal hollow cathode discharge

In the present paper the axial dependence of the cathode current distribution in the longitudinal hollow cathode discharge is investigated. On the basis of experimental results the model of the longitudinal hollow cathode discharge is developed and axial distribution of the cathode current is discussed.This work has been done in the frame of the Association for Education, Research and Application in Plasma-Chemical Processes and has been partially financially supported by Nos. 202/93/0659 and 202/95/1222 grants of Grant Agency of the Czech Republic. The main results have been presented as a poster on 10th Symposium on Elementary Processes and Chemical Reaction in Low Temperature Plasma, Stará Lesná (Slovakia), 1994.     

Kinetics of the manganese(III)-oxalate reaction in acidic sulphate media

The kinetics of the reaction of manganese(III) with oxalic acid (OA) has been studied in H₂SO₄ solutions. Under the experimental conditions of 6 × 10^–3 <>₀ < 0.4=" mol=">^–3 and [H₂SO₄]₀ 0.2 mol dm^–3 the observed pseudo-first order rate constant k _obs follows the expression

Characterization of fatty acid and triacylglycerol composition in animal fats using silver-ion and non-aqueous reversed-phase high-performance liquid chromatography/mass spectrometry and gas chromatography/flame ionization detection

Fatty acid (FA) and triacylglycerol (TG) composition of natural oils and fats intake in the diet has a strong influence on the human health and chronic diseases. In this work, non-aqueous reversed-phase (NARP) and silver-ion high-performance liquid chromatography with atmospheric pressure chemical ionization mass spectrometry detection and gas chromatography with flame-ionization detection (GC/FID) and mass spectrometry detection are used for the characterization of FA and TG composition in complex samples of animal fats from fallow deer, red deer, sheep, moufflon, wild boar, cock, duck and rabbit. The FA composition of samples is determined based on the GC/FID analysis of FA methyl esters. In total, 81 FAs of different acyl chain length, double bond (DB) number, branched/linear, cis-/trans- and DB positional isomers are identified. TGs in animal fats contain mainly monounsaturated and saturated FAs. High amounts of branched and trans-FAs are observed in the samples of ruminants. In NARP mode, individual TG species are separated including the separation of trans- and branched TGs. Silver-ion mode provides the separation of TG regioisomers, which enables the determination of their ratios. Great differences in the preference of unsaturated and saturated FAs in the sn-2 position on the glycerol skeleton are observed among individual animal fats. Unsaturated FAs are preferentially occupied in the sn-2 position in all animal samples except for wild boar with the strong preference of saturated FAs in the sn-2 position.     

Efficiency assessment of wastewater treatment plant based on SPMD sampling

The efficiency of treatment processes forboth municipal and industrial wastewater (treatment plant-Ostrava, Czech Republic) focused on persistent organic pollutants (POPs) was assessed. Semipermeable membrane devices (SPMDs) as a sampling system were applied. Exposed SPMDs were analyzed both for chemical contaminants of POPs and toxicity response. The chemical analyses of PAHs were made by HPLC-FLD, PCDD/Fs and PCBs were analysed by GC/MS/MS on GCQ or PolarisQ (Thermoquest). Ecotoxicity data on chlorococcal alga Desmodesmus subspicatus (Scenedesmus subspicatus) and luminescent bacteria Vibrio fischeri are presented here. All toxicity data as effective volume Vtox are expressed. The results show good treatment ability of the treatment plant and proved used system as an appropriate tool for efficiency assessment of treatment and/or decontamination processes.