High Performance Liquid Chromatography‐Electrochemistry‐Electrospray Ionization Mass Spectrometry (HPLC/EC/ESI‐MS) for Detection and Characterization of Roscovitine Oxidation Products

On‐line LC‐EC/ESI‐MS has been established as a fast and simple method to mimic some types of oxidation reaction of various drugs and to study the formation and structure of the resulting products. This technique has been applied to a 2,6,9‐trisubstituted purine, R‐roscovitine, which is known to be an inhibitor of some cyclin‐dependent kinases (CDKs) and a potential anticancer drug. Oxidation of R‐roscovitine in an electrochemical cell (EC), operated under various conditions, resulted in appearance of 6 major products. These were further analyzed by high‐resolution mass spectrometry, their structures were elucidated by accurate mass measurement and compared to previously identified R‐roscovitine in vitro/in vivo metabolites. Although none of the observed products was structurally identical to those identified previously in vitro/in vivo, all of them, except for the methoxylated products, resembled similarity due to appearing through the same reaction type. R‐roscovitine in the EC cell underwent N‐dealkylation of the isopropyl moiety, hydroxylation of the aromatic side‐chain, dihydroxylation, methoxylation and dimer formation. The hydroxylation product was identified as Olomoucine II, a R‐roscovitine derivative, which displays 10‐times higher CDK‐inhibiting activity than R‐roscovitine and the occurrence of which, as R‐roscovitine product, has not yet been observed in vitro/in vivo.     

Thermal Pretreatment of Harvest Residues and Their Use in Anaerobic Co-digestion with Dairy Cow Manure

Several batch experiments were conducted on the anaerobic co-digestion of dairy cow manure (DCM) with three harvest residues (HR) (soybean straw, sunflower stalks, and corn stover). The influence of thermal pretreatment of HR on biogas production was investigated, where the HR were thermally pretreated at two different temperatures: T = 121 °C and T = 175 °C, during t = 30 and t = 90 min, respectively. All anaerobic co-digestion batch experiments were performed simultaneously under thermophilic regime, at T = 55 °C. Biogas and methane yields were significantly improved in experiments performed with corn stover thermally pretreated at 175 °C for 30 min (491.37 cm³/g VS and 306.96 cm³/g VS, respectively), if compared to experiments performed with untreated corn stover. The highest VS and COD removal rates were also observed in the same group of experiments and were 34.5 and 50.1%, respectively. The highest biogas and methane yields with soybean straw (418.93 cm³/g VS and 261.44 cm³/g VS, respectively) were obtained when soybean straw pretreated at 121 °C during 90 min. The highest biogas and methane yields with sunflower stalk (393.28 cm³/g VS and 245.02 cm³/g VS, respectively) were obtained when sunflower stalk was pretreated at 121 °C during 90 min.     

Trace determination of arsenic species by capillary electrophoresis with direct UV detection using sensitivity enhancement by counter- or co-electroosmotic flow stacking and a high-sensitivity cell

Stacking techniques used independently and also with a high-sensitivity cell (HSC) were employed to optimise sensitivity and detection limits in the direct photometric detection of the following eight arsenic species by capillary zone electrophoresis (CZE): arsenite, arsenate, monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), 4-hydroxy-3-nitrophenylarsonic acid (Roxarsone), p-aminophenylarsonic acid (p-ASA), 4-nitrophenylarsonic acid (4-NPAA), and phenylarsonic acid (PAA) (target analytes). The stacking mechanisms, optimised stacking and separation conditions, and concentration sensitivity enhancement factors were discussed and compared for (i) normal stacking mode (NSM, sometimes also referred to as field-amplified stacking) in an uncoated fused-silica capillary in the counter-electroosmotic flow (EOF) mode, (ii) large-volume sample stacking (LVSS) with polarity switching, and (iii) the less often applied stacking method of co-EOF NSM stacking with EOF reversal using a poly(diallydimethylammonium chloride) (PDDAC)-coated capillary. The optimal injection volumes were 7.4, 60 and 17.2% of the total capillary volume, for the above three methods, respectively. LVSS with polarity switching gave the lowest limit of detection (LOD). The use of the HSC further reduced the LOD of each target analytes by a factor of 5-8 times. By combining LVSS and HSC, LODs of the target analytes could be reduced by a factor of 218-311, to 5.61, 9.15, 11.1, and 17.1 microg/L for As(III), DMA, MMA, and As(V), respectively. The method was demonstrated to be applicable to the determination of the target analytes in tap water and lake water, with recoveries in the range of 89.4-103.3%.     

Reliable electrophoretic mobilities free from Joule heating effects using CE

Ionic electrophoretic mobilities determined by means of CE experiments are sometimes different when compared to generally accepted values based on limiting ionic conductance measurements. While the effect of ionic strength on electrophoretic mobility has been long understood, the increase in the mobility that results from Joule heating (the resistive heating that occurs when a current passes through an electrolyte) has been largely overlooked. In this work, a simple method for obtaining reliable and reproducible values of electrophoretic mobility is described. The electrophoretic mobility is measured over a range of driving powers and the extrapolation to zero power dissipation is employed to eliminate the effect of Joule heating. These extrapolated values of electrophoretic mobility can then be used to calculate limiting ionic mobilities by making a correction for ionic strength; this somewhat complicated calculation is conveniently performed by using the freeware program PeakMaster 5. These straightforward procedures improve the agreement between experimentally determined and literature values of limiting ionic mobility by at least one order of magnitude. Using Tris-chromate BGE with a value of conductivity 0.34 S/m and ionic strength 59 mM at a modest dissipated power per unit length of 2.0 W/m, values of mobility for inorganic anions were increased by an average of 12.6% relative to their values free from the effects of Joule heating. These increases were accompanied by a reduction in mobilities due to the ionic strength effect, which was 11% for univalent and 28% for divalent inorganic ions compared to their limiting ionic mobilities. Additionally, it was possible to determine the limiting ionic mobility for a number of aromatic anions by using PeakMaster 5 to perform an ionic strength correction. A major significance of this work is in being able to use CE to obtain reliable and accurate values of electrophoretic mobilities with all its benefits, including understanding and interpretation of physicochemical phenomena and the ability to model and simulate such phenomena accurately.     

The B2–B7 phase transition in symmetrical bent‐shaped mesogens with methoxy substitution

New mesogens composed of achiral bent molecules with thermally stable ester linkages, and laterally substituted by a methoxy group symmetrically near the central benzene ring, were synthesized. Texture, calorimetric, electro‐optical, X‐ray and dielectric measurements were performed. In most of studied compounds the antiferroelectric B₂ phase was found on cooling from the isotropic phase, followed by the B₇ phase at lower temperatures. Undulation of layers in the B₇ phase was confirmed by precise synchrotron studies.     

Pressurised solvent extraction of nitrated derivatives of polycyclic aromatic hydrocarbons from roadside dust

An analytical method based upon the pressurised solvent extraction and gas chromatography and mass spectrometry (GC-MS) for analysis of nitrated derivatives of polycyclic aromatic hydrocarbons (nitro-PAHs) in roadside dust has been developed. Five nitro-PAHs (1-nitronaphthalene, 1-nitropyrene, 9-nitroanthracene, 2-nitrofluorene, 6-nitrochrysene) were chosen for this study because of their variable physical properties and effect on human health. Experiments with spiked inert matrix were used for the best extraction conditions finding. Different extraction conditions (temperature, pressure, solvents and duration of extraction cycle) were examined. The highest recoveries were observed at the extraction pressure of 14?MPa, temperature of 100°C and two cycles of 5?min extraction time, when dichloromethane was used as an extraction solvent. These conditions were applied to the extraction of nitro-PAHs from roadside dust. After extraction the nitro-PAHs fraction was isolated by the silica gel column chromatography. The GC-MS detector was used for analyses of the extracts. Recoveries of nitro-PAHs after extraction from roadside dust ranged from 60% for 9-nitroanthracene to 108% for 6-nitrochrysene.     

The effect of specific nucleation on molecular and supermolecular orientation in isotactic polypropylene

The molecular and supermolecular orientation, morphology and structural changes observed during cold drawing of injection moulded isotactic polypropylene modified by specific α, and β nucleating agents were studied by polarised photoacoustic FTIR spectroscopy, wide-angle X-ray diffraction and differential scanning calorimetry. Significantly lower molecular orientation was found in the core of the β-nucleated injection moulded specimens as compared to unmodified and α-nucleated materials. This has been ascribed to the fast growth of the β-crystallites which inevitably dislocates the flow-induced orientation within the crystalline regions and in their vicinity. Moreover, it was found that the presence of the developed β-crystallites distinctly diminishes the efficiency of the orientational solid-state drawing assessed on both levels of the hierarchical structure (molecular and crystalline). This structural observation is directly connected with macroscopic softening effect of the β-phase: lowering the yield stress and flattening the neck shoulder. Thus, the interrelation between the microstructural and macroscopic effects of the β-phase could be described as a feedback process.     

Highly oriented crystalline Er:YAG and Er:YAP layers prepared by PLD and annealing

High quality, thick, highly oriented crystalline thin films of Yttrium Aluminum Garnet (Y₃Al₅O₁₂) and Yttrium Aluminum Perovskite (YAlO₃) doped with Erbium were prepared by pulsed laser deposition. Samples were created in vacuum or oxygen environment. Depositions were arranged at room temperature, or at high substrate temperatures ranging from 800 to 1100 °C. Amorphous layers were annealed by laser, or in oven (argon flow, temperatures in range from 1200 to 1400 °C). Fused silica and sapphire (0 0 0 1) were used as substrates. Properties of films were characterized by X-ray diffraction, atomic force microscopy, and by photoluminescence measurement. Size of crystalline grains was in the range 116-773 nm. Thickness of layers was up to 17 μm.     

The Bremsstrahlung Equation for the Spin Motion in?Electromagnetic?Field

The influence of the bremsstrahlung on the spin motion is expressed by the equation which is the analogue and generalization of the Bargmann-Michel-Telegdi equation. The new constant is involved in this equation. This constant can be immediately determined by the experimental measurement of the spin motion, or it follows from the classical limit of quantum electrodynamics with radiative corrections.     

Vapor pressure of selected aliphatic alcohols by ebulliometry. Part 2

Vapor pressures of six pentanols, 2-methyl-1-butanol (CAS Registry Number 137-32-6), 2-methyl-2-butanol (CAS Registry Number 75-85-4), 3-methyl-1-butanol (CAS Registry Number 123-51-3), 3-methyl-2-butanol (CAS Registry Number 598-75-4), 2-pentanol (CAS Registry Number 6032-29-7) and 3-pentanol (CAS Registry Number 584-02-1), were measured by the precision ebulliometry over an approximate pressure range from 9 to 99 kPa. The absolute uncertainties in pressure and temperature are estimated to be less than or equal to 7 Pa and 0.02 K, respectively. The results are represented by the Antoine equation and compared with available literature data.