Band 11, Heft 5

The present review shows the utility of using mass spectrometry (MS) in obstetrics and gynecology. In this review different gas chromatography / mass spectrometry and liquid chromatography / mass spectrometry methods developed before to be used in obstetrics and gynecology are described. These methods are very useful to determine different hormones in pregnancy, fatty acids esters (related to the use of ethanol) in human meconium and toxic compounds in umbilical cord (as ethanol, steroids, morphine, cocaine, methadone and other drugs). It is also shown in this review the progress during last decades in the field of using mass spectrometry in obstetrics and gynecology (for screening in utero exposure of the child to alcohol, drugs and other toxic compounds). In the field of using mass spectrometry in obstetrics and gynecology are still many problems to solve. For example, the detection of fatty acids esters in meconium has several limitations, which affects the results. One limitation is multiple births. Also in fetal distress, meconium may be passed before birth, and in this case, the collection is impossible. Moreover the meconium is formed starting from the fourth month of pregnancy, so the fetal exposure at any toxic compounds during the first three months cannot be detected at all. To solve all of these, the best would be to combine the results obtained from meconium, with other results obtained from pregnancy serum, placenta or umbilical cord. The main reason for using MS in obstetrics and gynecology is that MS is a noninvasive and a complementary method. It offers the results at a very early point in time, even before the act of birth. Sometimes the use of mass spectrometry is the only alternative. This shows that these methods are of great interest for the future and need to be developed further.

Chelatoaromaticity (aromaticity of chelate complexes) has been recently recognized as an important property influencing the stability of chelate compounds. In this paper, aromaticity of various forms of 8-hydroxyquinoline (anion, neutral molecule, zwitterion and cation) as well as its chelate complexes with magnesium and aluminium ions are investigated. Aromatic properties of these compounds are analyzed using several aromaticity indices based on energetic, geometric, magnetic and electronic physical manifestations of this phenomenon. Results of performed calculations have shown different aromatic properties for the two rings (pyridine and benzene) occurring in the studied ligand. Aromaticity of these rings in metal complexes of 8-hydroxyquinoline is significantly higher than that in corresponding ligand anion. This means that during complexation the aromaticity of the ligand increases and the chelatoaromatic effect stabilizes the studied metal complexes. In contrast, metallocyclic rings of studied metal complexes have non-aromatic properties, and, consequently, the metallocyclic ring is not stabilized by chelatoaromaticity. We conclude that, in the complex, every 8-hydroxyquinoline unit and the metal ion are separated p-electronic systems.

This article describes results of a recent study of SOFC (Solid Oxide Fuel Cell) material properties using a numerical tool. The created model was validated against experimental data collected for two different solid oxide fuel cells. With focus on ionic and electronic conductivities, temperature influence was investigated. Results are presented, compared with available data, and discussed. Model of a micro-CHP (Combined Heat and Power) unit based on a SOFC stack was used for evaluation of system performance with different cells. On-site generated bio-syngas was considered as a fuel fed for the unit. The overall system efficiency was analyzed using an Aspen HYSYS modeling environment. Properties of two generic electrolyte materials were implemented in the models for evaluation of a co-generative unit operation. Electrical and overall efficiencies of systems based on those cells were compared and differences were observed. Micro-scale power units with fuel cells are a promising technology for highly efficient distributed cogeneration. As it was concluded, selection of a proper cell is crucial to assure high system efficiency.

Lead (+2) was selectively adsorbed on a solid phase extraction (SPE) gel (molecular recognition technology, MRT), quantitatively extracted, and spectrophotometrically determined as the Pb(II)-PAR (4-(2-pyridylazo)-resorcinol) complex. The linear range was 0.01 to 0.75 mg L−1 and the detection limit was 6.4 µg L−1. The MRT-SPE allows selective Pb(II) extraction from complex ion-rich matrices, which is difficult with other techniques. Interference from common matrix ions such as Fe2+, Ni2+, Cu2+ or Co2+ is minimized.

A comprehensive study of biogenic amines and related drugs as free radical scavengers and potential antioxidants was carried out using the stable free radical 2,2-diphenyl-1-picrylhydrazyl (DPPH·). The results of the effect of test duration and the relative concentration on the ability of the compounds to scavenge the DPPH· were investigated and discussed. The antiradical activity of amines was compared with the activity of some reference antioxidants (phenols, phenolic acids, flavonols and other antioxidants). Some particular insights related to the mechanism of reactivity toward the DPPH· were investigated by carrying out kinetic studies in methanol for different relative concentrations. According to the obtained results, catecholamines and especially their related drugs (D-dopa, adrenalone, S-(−)-carbidopa and isoprenaline) showed a fast reactivity towards DPPH· and the highest antiradical activity which increased in a concentration-dependent manner. Moreover, catecholamines proved to be more powerful scavengers than ascorbic and caffeic acids even at low concentrations while their related drugs (D-dopa, adrenalone and S-(−)-carbidopa) showed higher antiradical activity than gallic acid for all of the investigated concentrations.

The hydration reaction of α-pinene in the presence of natural clays treated with monochloroacetic acid as catalyst to obtain oxygenated compounds was studied. Catalysts were characterized using X-ray diffraction, differential thermal analysis, programmed thermal desorption of adsorbed pyridine, and infrared spectroscopic analysis of adsorbed pyridine to determine Brønsted and Lewis acid sites. Catalytic tests revealed that treatment of the natural clay with the acid improved the catalytic activity and the selectivity toward oxygenated products by increasing the acidity of the catalyst. The selectivity toward oxygenated compounds increased with the augment of the α-pinene conversion because of greater contact between water molecules with the remaining α-pinene molecules. The natural clay without treatment produced compounds resulting from α-pinene isomerization, whereas the treated clays produced alcohols and other products in addition to isomerization compounds. After a certain time, the α-terpineol was isomerized into cineols. Studies of the reusability of the JAL catalyst were performed (clay treated with monochloroacetic acid). As the number of reuses increased, the percent conversion decreased; however, the selectivity toward oxygenated compounds increased.

The use of an electrogalvanic device for scale neutralisation is descibed in this paper. Physico-chemical analyses were performed before and after the treatment. The results were compared with those obtained by using magnetic water treatment device. By measuring some individual parameters and the implementation of chemical analysis, the satisfactory functioning of the electrogalvanic device was demonstrated. The quality of drinking water did not change much after the water treatment method. The results of determination of calcium carbonate saturating index showed that the raw drinking water is in carbonate equlibrium as well as both treated water samples. The calcite/aragonite ratio was studied by means of microscopy and X-ray powder diffraction. Inspection of crystals formed during the experiments with microscopy indicated that aragonite crystal structure of the precipitates prevailed over the calcite stucture. The diffractograms showed that the share of aragonite increased after using the electrogalvanic device compared with raw drinking water samples where the share of calcite was higher.

Reboxetine (RBX) electrochemical redox behavior at hanging mercury drop (HMDE) and glassy carbon electrodes (GCE) was studied in various pH Britton-Robinson universal buffers using cyclic voltammetry and square-wave voltammetry. RBX was reduced at the HMDE and oxidized at the GCE with reversible adsorption controlled and irreversible diffusion controlled processes respectively. The anodic peak is due to the amine and the cathodic peak may correspond to oxygen protonation. An oxidation reaction mechanism is proposed. The linear relation between peak currents and RBX concentration allowed simple, sensitive, precise and inexpensive voltammetric procedures to be developed. The limit of detection was 0.04 µM RBX. The procedures were successfully applied to human urine and RBX tablet assay. Therapeutic RBX concentrations in human serum were not detected due to strong drug-protein binding. Using bovine serum albumin, the methods were used to investigate the effect of serum protein binding on RBX determination.

A new HPLC method was developed for the determination of amlodipine and perindopril in their binary mixture as a part of a routine control of combined formulations. For the first time an HPLC method was used for an in vitro dissolution study of tablets containing the above drugs. The presented method was validated to meet official requirements and this validation included specificity, stability, linearity, precision and accuracy. Chromatography was carried out using a LiChrospher RP-18 column, a mixture containing acetonitrile and phosphate buffer of pH 3.0 (50:50, v/v) as mobile phase and UV detection at 225 nm. The dissolution test was performed using 900 mL of phosphate buffer at pH 5.5 containing 1% cetylpyridini chloride (CPC) at 37°C and 75 rpm, using the paddle method. Robustness procedure was done according to the plan defined by the Plackett-Burman design. The effects of acetonitrile content, pH of the buffer and flow rate of the mobile phase, column temperature, pH and CPC content in the dissolution medium as well as rotation speed of the paddle were considered. After that, both graphical and statistical methods were used for identification of significant and non-significant effects.

Thermal and catalytic degradation of polystyrene waste over two different samples of natural volcanic tuff catalyst comparative with Florisil catalyst has been carried out in order to establish the conversion degree into styrene monomer. The polystyrene waste (PS) was subjected to a thermal degradation process in the range of 380–500°C in presence of studied catalysts in a ratio of 1/10 in mass, catalyst/PS. The catalysts were characterized by N2 adsorption-desorption isotherms (BET), Scanning Electron Microscopy (SEM) and Fourier-transform infrared spectrometry (FTIR). Influences of temperature and type of catalysts on the yields and on the distribution of end-products obtained by thermal and catalytic degradation of polystyrene waste have been studied. The maximum yields of liquid products were obtained at 460°C degradation temperature and were calculated between 83.45% and 90.11%. The liquid products were characterized by gas chromatography mass spectrometry (GC-MS) and FTIR analytical techniques. The GC-MS results showed that the liquid products contained styrene monomer up to 55.62%. The FTIR spectra of liquid products indicated the specific vibration bands of the functional groups of compounds of liquid products. The amounts of styrene monomer obtained were influenced by structural and textural properties of studied catalyst and the contribution on product distribution is discussed.

The renewable mercury film electrode, applied for the determination of papaverine traces using differential pulse adsorptive stripping voltammetry (DP AdSV) is presented. The calibration graph obtained for papaverine is linear from 1.25 nM (0.42 µg L−1) to 95 nM (32.2 µg L−1) for a preconcentration time of 60 s, with correlation coefficient of 0.998. For the renewable mercury electrode (Hg(Ag)FE) with a surface area of 9.1 mm2 the detection limit for a preconcentration time of 60 s is 0.7 nM (0.24 µg L−1). The repeatability of the method at a concentration level of the analyte as low as 17 µg L−1, expressed as RSD is 3.3% (n=5). The proposed method was successfully applied and validated by studying the recovery of papaverine from drugs, urine and synthetic solution.

Elements that enter the aquatic environment may pose a health risk to wildlife and humans. The aims of this study were: to determine how the introduction of activated carbon for a water purification system will improve the quality of the water produced; and to investigate the sorption of metals on activated carbons, including determination of the accumulation, as well as changes in concentrations of elements in carbons. The tests were carried out on three types of activated carbons with different granular structure. All samples were collected from Water Treatment Plant Goczalkowice, Poland. Concentrations of elements were measured using an optical emission spectrometer with inductively coupled plasma. The experiment showed that metals accumulating in the activated carbons during the operation included: Ca, Mn, Zn, and Cu. In each of the three types of carbons, it can distinguish such elements as Ba, Al, Cr, Ni, Ti, which are characterized by irregular accumulation during the operation of the filter. The introduction of carbon sorbent for water treatment largely contributed to improvement in the quality of raw material supplied to customers, mainly with regard to taste and smell, as well as to reduction of basic parameters: color, absorbance in the UV range and oxidability.

A detailed stability testing of solid state imidapril hydrochloride (IMD) was performed and its degradation products were identified. The analysis was conducted according to ICH guidelines Q1A(R2). Pure IMD samples were exposed to stress conditions of elevated temperature and relative humidity (T = 363 K, RH = 76.4%) in order to accelerate degradation. The regular loss of IMD content with time, and the formation of two degradation impurities were observed. The appropriate reaction rate constants k (for IMD degradation and for the formation of product I and II) were calculated using Prout-Tompkins equation. The obtained degradation products were separated and identified by means of LC-MS technique. Based on the obtained m/z values, the masses and the structures of the formed degradation impurities were established. Also IMD degradation scheme was constructed. It was demonstrated that under the applied analytical conditions, IMD degradation follows an autocatalytic reaction model with the rate constant k = (4.764 ± 0.34)×10 −6 s −1 and with the parallel formation of two degradation products: imidaprilat and the diketopiperazine derivative. The obtained experimental results are in agreement with IMD degradation pathways proposed theoretically.

A facile and easily controlled route was designed to synthesize nano-structured Fe2O3, CuO, and CuO/Fe2O3 hybrid oxides with different Cu/Fe molar ratios via a hydrothermal procedure. The samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM) and field-emission scanning electron microscopy (FE-SEM). The results showed that the morphologies of the samples changed with different Cu/Fe ratios. The electrocatalytic properties of the samples modified on a glassy carbon electrode for p-nitrophenol reduction in a basic solution were investigated. The results indicated that CuO/Fe2O3 hybrids with lower Cu/Fe ratio exhibited higher electrocatalytic activity. The photocatalytic performances of the samples for methyl orange degradation with assistance of oxydol under irradiation of visible light were studied. The results revealed that CuO/Fe2O3 hybrids with higher Cu/Fe ratio showed efficient photocatalytic activity.

The thermal decomposition of the four nitrogen-rich salts of ammonia (NH4), aminoguanidine (AG), carbohydrazide (CHZ) and 5-aminotetrazo (ATZ) based on trinitrophloroglucinol (H3TNPG) was investigated using the differential scanning calorimetry (DSC), thermogravity (TG), and dynamic vacuum stability test (DVST). DSC and TG methods research the complete decomposition, while DVST method researches the very early reaction stage. The peak temperatures of DSC curves are consistent with the temperatures of maximum mass loss rates of TG curves. The apparent activation energies of these H3TNPG-based salts obtained by DSC and DVST have the same regularity, i.e., (ATZ)(H2TNPG)·2H2O 2O 4(H2TNPG) 2TNPG). The thermal stability order is (ATZ)(H2TNPG)·2H2O 2O 2TNPG) 4(H2TNPG), which was evaluated by DVST according to the evolved gas amount of thermal decomposition. DVST can monitor the real-time temperature and pressure changes caused by thermal decomposition, dehydration, phase transition and secondary reaction, and also evaluate the thermal stability and kinetics.

The effect of hydrothermal treatment on the structure of an aluminosilicate polymer prepared by a polycondensation reaction between silicate and hydroxoaluminate in alkaline aqueous solution was studied. The structural changes were investigated using X-ray diffraction analysis, Fourier-transform infrared spectroscopy, scanning electron microscopy imaging and thermogravimetric analysis. The results indicated that the amorphous aluminosilicate polymer transformed into a crystalline product during the hydrothermal treatment at 145°C. The crystalline phase was identified as a mineral of the zeolite group, most likely phillipsite. This transformation required an alkaline environment during the hydrothermal treatment.

A new procedure for the determination of mercury(II), copper(II), lead(II), cadmium(II) and zinc(II) traces in food matrices by square wave anodic stripping voltammetry and standard addition method is proposed. A rapid, inexpensive and multi-analyte analytical method suitable for food safety control is provided. Comestible vegetables were chosen as samples. A two-step, sequential determination was defined, employing two working electrodes: a gold electrode (GE) for mercury(II) and copper(II), and subsequently a hanging mercury drop electrode (HMDE) for copper(II), lead(II), cadmium(II) and zinc(II). No sample pre-treatment was needed. Spinach leaves, tomato leaves and apple leaves were employed as standard reference materials to optimize and defined the analytical procedure. The new method shows good selectivity, sensitivity, detectability and accuracy. A critical comparison with spectroscopic measurements is discussed. Spinach, lettuce and tomato samples sold on the market were analysed as real samples. Lead(II) and cadmium(II) concentration exceeded the relevant legal limits.

The electric properties of bacteria determine their non-specific interactions with the environment, in particular their pathogenic activity. The electric polarizability of Escherichia coli HB101 (K-12 strain) was studied while inactivation with ethanol (20–40 vol.%). The current investigation might be regarded as a continuation of previous research on the polarizability of E. coli at lower ethanol concentration (≤ 20 vol.%) and higher frequencies (≥ 20 kHz). The bacteria polarizability at low frequencies (4 Hz) shows anomalies (unexpected increase in the polarizability at certain ethanol concentrations), while the parameter decreases with an increase in the ethanol concentration at higher frequencies. We investigated for the possible reasons causing the anomalies — in our case reduced to the medium dielectric permittivity, the average cell length and the surface electric charge density distribution, related to bacterial lipopolysaccharides. We suggest a hypothesis for the molecular mechanism of changing the surface charge of E. coli, carried by lipopolysaccharides, induced by the non-ionic ethanol.

In this study, the addition of boranes to (E)-(η5-C5H5)2Zr(CH=CHPh)Cl (3) has been examined in order to investigate the regioselectivity of these ‘hydroboration’ reactions. We have found that these additions proceed with remarkable selectivity to give exclusive formation of a saturated organic molecule where one carbon atom has both the boron and the zirconium fragments. These reactions do not proceed via a conventional hydroboration reaction, but instead go through an initial transmetalation step to generate (E)-(η5-C5H5)2Zr(H)Cl (1) and the corresponding alkenyl boron intermediate, whereupon subsequent hydrozirconation of this latter species gives the geminal products. An x-ray diffraction study has been conducted on gem-(η5-C5H5)2Zr(CH(Bpin)CH2Ph)Cl (pin = 1, 2-O2C2Me4) (2). Crystals of 2 were orthorhombic with a = 18.545(3) Å, b = 15.713(3) Å, c = 16.157(3) Å in the space group Pccn. An x-ray diffraction study has also been conducted on the trinuclear zirconium oxide species (η5-C5H5)2ZrO2[ZrCl(η5-C5H5)2]2(4). Crystals of 4 were orthorhombic with a = 13.6000(8) Å, b = 14.2252(8) Å, c = 17.6500(10) Å in the space group P2(1)2(1)2(1).

A daily cycle of tests was conducted to specify the concentration variation of phosphorous compounds and other chemical parameters at surface microlayers of a shallow lagoon lake located on the Baltic Coast. The water for analyses was collected from Lake Dołgie Wielkie in one hour cycles for the period of 24 hours. Samples were collected from the surface microlayers that had a thickness of 80–115 µm and 250–300 µm as well as from the subsurface water at the depth of 15 cm. Data analysis shows information concerning the migration of phosphorous compounds between the analyzed layers. Correlations were estimated for the obtained concentrations of phosphorous compounds and the nitrogen compounds and other physico-chemical values which were described in the first part of the cycle. The content of nutrients in the examined surface water layers correlated with the oxygen consumption due to the value of the oxygen consumption mostly depending on the concentration of organic matter.