Application of DLLME to Isolation and Concentration of Non-Steroidal Anti-Inflammatory Drugs in Environmental Water Samples

Dispersive liquid–liquid microextraction (DLLME) coupled with liquid chromatography-tandem mass spectrometry detection was applied for determination of selected anti-inflammatory pharmaceuticals: ibuprofen, ketoprofen, naproxen and diclofenac. Development of DLLME procedure included optimisation of several important parameters such as kind and volume of extracting and dispersive solvents as well as sample pH. Under optimised conditions a two-step extraction with sonication was used. Chloroform was applied as the extracting and acetone as dispersing solvent. Calibration curves ranges were 1–500 μg L^?1 for naproxen and ibuprofen and 0.25–500 μg L^?1 for ketoprofen and diclofenac with correlation coefficients at least 0.997. Limits of quantitation were from 0.5 to 10 ng L^?1. The developed analytical method was employed for determination of ibubrofen, ketoprofen, naproxen and diclofenac in river and tap water samples. The results showed that DLLME is a simple, rapid and sensitive analytical technique for the pre-concentration of trace amounts of pharmaceuticals in environmental water samples.     

Assessment of ion imprinted polymers based on Pd(II) chelate complexes for preconcentration and FAAS determination of palladium

New ion-imprinted polymeric (IIP) materials were synthesized by copolymerization of 4-vinylpyridine (VP) and styrene as functional monomers and divinylbenzene as a cross-linking agent with chelating complexes of Pd(II) in the presence of 2,2-azobisisobutyronitrile as an initiator. The complexes of Pd(II) with ammonium pyrrolidinedithiocarbamate (APDC), N,N′-diethylthiourea (DET), and dimethylglyoxime (DMG) were used for this purpose. Chloroform, ethanol, and cyclohexanol were applied as porogens. The ion-imprinted polymers were tested in a flow mode as sorbents for solid-phase extraction of palladium from aqueous solutions. The conditions of Pd(II) separation on all polymers were optimized. The efficiencies of retention of Pd on different polymers in the presence of high excess of interfering ions were compared. The effect of the used porogen on the analytical performance of the prepared polymers was also investigated. The calculated sorbent capacities for Pd(II) were in the range from 9.25 mg g⁻¹ to 13.3 mg g⁻¹. The sorbent with Pd(II) imprinted as Pd-DMG-VP complex in chloroform was used for preconcentration of trace amounts of Pd. The detection limit for 100 mL of the sample was 5 μg L⁻¹ using flame atomic absorption spectrometry (FAAS). The developed method was applied for the determination of Pd in water samples.     

Iron complexes of N-confused pyriporphyrin: NMR studies

Insertion of iron(II) into 6,11,16,21-tetraaryl-3-aza-m-benziporphyrin (N-confused pyriporphyrin, (PyPH)H) yielded the high-spin iron(II) complex, (PyPH)Fe(II)Br. The coordination of iron(II) to the perimeter nitrogen atom of (PyPH)Fe(II)Br resulted in the formation of the diiron species. Oxidation and oxygenation of (PyPH)Fe(II)Br were followed by 1H NMR spectroscopy. The addition of Br2 to the solution of (PyPH)Fe(II)Br in the absence of dioxygen results in a one-electron oxidation yielding the high-spin iron(III) N-confused pyriporphyrin [(PyPH)Fe(III)Br]+ which preserves the side-on interaction between the inverted pyridine ring and metal ion. The reaction of (PyPH)Fe(II)Br with dioxygen ends up with the formation of a five-coordinate species (PyPO)Fe(III)Br] ((PyPOH)H = 3-aza-22-hydroxy-m-benziporphyrin, PyPO = the corresponding dianion) which is formed by oxygenation at the C(22) position. Coordination of a metal ion by 3-aza-22-hydroxy-benziporphyrin imposes a steric constraint on the geometry of the ligand. The halide ligand of (PyPO)Fe(III)Br coordinates on one of the two inequivalent faces of the macrocycle, leading to two distinct species: syn and anti. The (1)H NMR spectra of paramagnetic iron(II) and iron(III) N-confused pyriporphyrin complexes have been examined. The characteristic patterns of pyrrole and pyridine resonances have been found to be diagnostic of the ground electronic state of iron and the donor nature of the C(22)H and N(3) centers. The enormous downfield H(22) paramagnetic shift, determined for the iron(II) N-confused pyriporphyrin, provides a distinct resonance in a peculiar spectroscopic window (350-800 ppm) for a series of axial ligands which can be considered as a diagnostic sign of an agostic Fe(II)...{C(22)-H} interaction. Coordination of the pyridine moiety via the perimeter N(3) atom is reflected unambiguously by the H(2/4) resonance at 201 ppm.     

Fixed-point theorem in classes of function with values in a dq-metric space

We prove a fixed point result for nonlinear operators, acting on some classes of functions with values in a dq-metric space, and show some applications of it. The result has been motivated by some issues arising in Ulam stability. We use a restricted form of a contraction condition.     

Spin Hall effect and spin current generation in two-dimensional systems with random Rashba spin–orbit coupling

We consider a new effect induced by spin–orbit coupling in a two-dimensional electron gas confined in a semiconductor quantum well, i.e. the possibility of spin current generation by fluctuating random Rashba spin–orbit interaction, with the corresponding mean value of the interaction being equal to zero. Our main results suggest that – in contrast to the spatially uniform Rashba spin–orbit interaction – the spin Hall effect does not vanish for typical disorder strengths. We also point out some other possibilities of using such a random Rashba coupling for the generation of spin density and spin current in two-dimensional nonmagnetic structures.     

A psychophysical pitch function determined by absolute magnitude estimation and its relation to the musical pitch scale

A psychophysical pitch function, describing the relation of perceived magnitude of pitch to the frequency of a pure tone, was determined by absolute magnitude estimation. Pitch estimates were made by listeners with relative pitch and by absolute pitch possessors for 27 tones spanning a frequency range of 31.5-12,500 Hz in 1/3 octave steps. Results show that the pitch function, plotted in log-log coordinates, is steeper below 200 Hz than at higher frequencies. It is hypothesized that the pitch function's bend may reflect the diversity of neurophysiological mechanisms of pitch encoding in frequency ranges below and above 200 Hz. The variation of the function's slope implies that pitch distances between tones with the same frequency ratios are perceived as larger below 200 Hz than at higher frequencies. It is argued that this implication may apply only to a purely sensory concept of pitch distance and cannot be extended to the perception of musical intervals, a phenomenon governed by musical cognitive principles. The results also show that pitch functions obtained for listeners with relative and absolute pitch have a similar shape, which means that quantitative pitch relations determined for both groups of listeners do not differ appreciably along the frequency scale.     

Phosphine oxide functionalised imidazolium ionic liquids as tuneable ligands for lanthanide complexation

A series of novel, phosphine oxide functionalised ionic liquids have been synthesised and their application as tuneable lanthanide complexing agents is demonstrated.     

Complexity of scheduling of coupled tasks with chains precedence constraints and any constant length of gap

Coupled tasks scheduling was originally introduced for modelling complex radar devices. It is still used for controlling such devices and applied in similar applications. This paper considers a problem of coupled tasks scheduling on one processor, under the assumptions that all processing times are equal to 1, the gap has a constant exact length and the precedence constraints are strict. Although it is proven that the problem stated above is NP-hard in the strong sense if the precedence constraints have a form of a general graph, it is possible to solve some of its relaxed versions in polynomial time. This paper contains a solution for the problem of coupled tasks scheduling with an assumption that the precedence constraints graph has a form of chains and it presents an algorithm that can solve the problem with such assumption in time O(n?log?n).     

ERD studies of D-ion depth distributions after implantation into some pure metals and alloys

This paper presents a report on experimental results of depth distributions of deuterium ions implanted with 25 keV energy at a fluence interval of (1.2–2.3) × 10²² m⁻² into samples of pure metals (Cu, Ti, Zr, V, Pd) and diluted Pd alloys (Pd-Ag, Pd-Pt, Pd-Ru, Pd-Rh). The post-treatment depth distributions of deuterium and hydrogen atoms were measured within a few hours after implantation with the use of elastic recoil detection (ERD) analysis. After three months the measurements were repeated. The comparison of the obtained results in both series of studies allowed us to make an important observation of the desorption rates of implanted deuterium atoms from pure metals and diluted Pd alloys. The maximum measured concentrations of deuterium atoms in pure Zr and Ti foils with relatively small desorption rate of deuterium atoms within three months after implantation were observed. Also a very high spreading of deuterium atom distributions was observed in all the measured pure metals and alloys. It can be explained by the large diffusion coefficients of deuterium and extremely fast kinetics.     

Ground-state correlation properties of charged bosons trapped in strongly anisotropic harmonic potentials

The core width and Peierls barrier and stress for Shockley partials in InP have been investigated using the improved P-N theory. The core width of 90° partial is about 1.6 times wider than that of 30° partial, and both of them are very narrow: core width ξ < 0.5b. In calculating the Peierls barrier and stress, the contribution from stain energy ignored by classical P-N theory has been considered. The calculated results show that when the dislocation moves, both the misfit and strain energies change periodically. They cancel each other due to the same order but opposite phases. Accordingly, the Peierls barrier and stress calculated from improved P-N theory are much lower than those calculated from the classical P-N theory. The Peierls barrier for 90° and 30° partials obtained by us is respectively about  ~0.047 eV/Å and 0.044–0.075 eV/Å, the Peierls stress is respectively about 3.7–5.0 GPa and 4.2–6.9 GPa.