Development of a capillary electrophoretic method for determination of ketorolac enantiomers in human plasma using cationic β-cyclodextrin derivative as a chiral selector

A novel approach for the separation of ketorolac enantiomers by capillary electrophoresis is presented. A cationic β-cyclodextrin derivative based on imidazole was synthesized and used as a chiral selector in the background electrolyte. The influence of pH and ionic strength of background electrolyte, as well as cationic β-cyclodextrin derivative concentration on the resolution of ketorolac enantiomers, was investigated. The highest value of the resolution for ketorolac enantiomers was 1.46 when the background electrolyte consisted of 25 mM NaH₂PO₄ (pH 6.4) with 1 mM 1-butyl-3-β-cyclodextrinimidazolium tosylate. Additionally, the possibilities of cationic derivatives for the separation of ketoprofen enantiomers were shown (peak resolution 1.06). The two-step preconcentration mode was developed to reduce the limit of detection of individual enantiomers. The proposed approach was successfully applied to determine ketorolac enantiomers in tablet “Ketorol express” and human plasma. The calibration range of ketorolac enantiomers for plasma samples was 0.25–2.50 μg/ml with coefficients of determination ≥ 0.99. The relative standard deviation both of the peak area and migration time was less than 15%, as well as the accuracy ranged from 90.1% to 110.2% for both analytes. The limits of detection were 44 and 55 ng/ml for R- and S-ketorolac. The quantity of ketorolac in plasma was verified with high-performance liquid chromatography.     

Structure and real composition of undoped and Cr- and Ni-doped Sr<Subscript>0.61</Subscript>Ba<Subscript>0.39</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> single crystals

Strontium barium niobate crystals with congruent melting composition Sr_0.61Ba_0.39Nb₂O₆ (SBN-61), both nominally pure and doped with Cr³⁺ и Ni³⁺ ions, have been investigated by neutron diffraction. Different strontium and barium contents as well as their different distribution over the Sr1, of Sr2 and Ba2 crystallographic sites of SBN-61 structure, caused by introduction of dopants, have been revealed. Coordination polyhedra of cations have been established based on the analysis of cation–anion internuclear distances together with the calculation of bond-valence sums for cations, which are equal to their formal charge. It was found that the Nb1 and Nb2 atoms are located in distorted octahedra with quadfurcated (the Nb1O₆ polyhedron) or bifurcated (the Nb2O₆ polyhedron) vertices, and the Sr1 atoms are located in a cuboctahedron with bifurcated vertices in the base plane. Different polyhedra have been revealed for the Sr2 and Ba2 atoms: Sr2 atoms are coordinated by 15 oxygen atoms to form a highly distorted five-capped pentagonal prism, whereas Ba2 atoms are located in a highly distorted three-capped trigonal prism with a coordination number 9. Comparison of interatomic and internuclear distances, determined by X-ray and neutron diffraction analyses, respectively, allowed to reveal a highly pronounced shift of electron density in Nb1 and Sr2 polyhedra, responsible for the covalent bond and properties of crystals. Location of Cr³⁺ и Ni³⁺ dopant ions in the SBN-61 structure as well as their formal charges has been discussed.     

The adsorption of gases on the surface of solid solutions and binary compounds of the GaSb-ZnTe system

The adsorption of ammonia, carbon monoxide, and oxygen on solid solution and binary compound films of the GaSb-ZnTe system was studied. The mechanism of adsorption and rules governing adsorption processes depending on adsorption conditions and system composition were determined by analyzing adsorption isobars, equilibrium and kinetic isotherms, the thermodynamic and kinetic characteristics of adsorption, and the electronic nature of adsorbate molecules. The behavior of (GaSb)_x(ZnTe)_1?x solid solutions was similar to that of binary compounds (GaSb and ZnTe) and had special features characteristic of multicomponent systems. The latter manifested themselves by the presence of extrema in adsorption characteristic-composition diagrams. The use of such diagrams allowed us to identify system components most active with respect to NH₃, CO, and O₂ and use them to create high-sensitivity and selectivity sensors.     

Semiclathrates of the Ge-P-Te system: synthesis and crystal structures

Novel compounds [Ge_46?xP_x]Te_y (13.9≤x≤15.6, 5.92≤y≤7.75) with clathrate‐like structures have been prepared and structurally characterized. They crystallize in the space group Fm$\bar 3Novel compounds [Ge(46-x) P(x) ]Te(y) (13.9≤x≤15.6, 5.92≤y≤7.75) with clathrate-like structures have been prepared and structurally characterized. They crystallize in the space group Fm ?3 with the unit cell parameter changing from 20.544(2) to 20.698(2) ? (Z=8) on going from x=13.9 to x=15.6. Their crystal structure is composed of a covalently bonded Ge-P framework that hosts tellurium atoms in the guest positions and can be viewed as a peculiar variant of the type?I clathrate superstructure. In contrast to the conventional type I clathrates, [Ge(46-x) P(x) ]Te(y) contain tricoordinated (3b) atoms and no vacancies in the framework positions. As a consequence of the transformation of the framework, the majority of the guest tellurium atoms form a single covalent bond with the host framework and thus the title compounds are the first representative of semiclathrates with covalent bonding. A comparison is made with silicon clathrates and the evolution of the crystal structure upon changing the tellurium content is discussed.     

Conductivity and thermal stability of proton-conducting electrolytes at confined geometry of polymeric gel

The proton-conducting gel electrolytes based on poly(methyl methacrylate) (PMMA) doped by acid solutions in aprotic solvents were synthesized and discussed in this work. The gel conductivity as a function on concentrations of acid and polymer as well as of molecular mass of PMMA has been analyzed. The thermal stability of electrolytes was estimated and discussed. Extreme dependence of the conductivity on concentration is found to be for the gel (at a concentration of PMMA from 5 to 15 wt.%). The increase of electrical conductivity in the concentration range from 5 to 10 wt.% of PMMA with an increase in viscosity of the system is discussed as an indication of an involvement of the polymer matrix in increasing the mobility of the charge carriers in frame of Grotthuss mechanism.     

Scattering characteristics of structures of lossy metamaterial–semiconductor cylinders

Here, we present for the first time the rigorous boundary problem solution of the Maxwell’s equations for the determination of scattering characteristics of a structure. The structure consists of a finite set of infinite parallel circular cylinders that can be made of different lossy isotropic materials. We numerically analyzed two structures that differ only in the symmetrical arrangement of semiconductor cylinders in relation to a central metamaterial cylinder. The electrical radii of cylinders can be arbitrary. Both polarizations of the incident microwave are considered in this work. The Poynting vector of the plane microwave that reflected from and transmitted through the structures analyzed here. We investigated dependency on the radius of an arc where are placed the semiconductor cylinders, the semiconductor-specific resistivity, the operating frequency at two radii of the metamaterial cylinder. We discovered that the structure can have features of a band gap photonic crystal dependent on the topology and the polarization of the incident microwave. We have found that the structure can operate as a microwave reflector at the certain radius of the arc on which are located thirteen n-Si cylinders. The Poynting vector is very sensitive to the change of semiconductor-specific resistivity when the incident microwave has the parallel polarization.     

Aromatization of methane on pentasil-containing catalysts

Russian Chemical Bulletin -