Two Stage Solid Phase Extraction with Subsequent HPLC Isolation for Structure Elucidation of Major Metabolites of (+)-(R)-2-{3-(benzo[1,4]dioxan-2-yl-methylamino)-1-propyl}-3(2H)-pyridazinone (GYKI-16084)

GYKI-16084 – (+)-(R)-2-{3-(benzo[1,4]dioxan-2-yl-methylamino)-1-propyl}-3(2H)-pyridazinone hydrochloride – is a new drug candidate for the treatment of benign prostatic hyperplasia. In our study the major metabolites formed in the rat and dog were isolated from dog and rat urine, then their structures were elucidated by means of MS and NMR. A two stage solid phase extraction (SPE) procedure and a semi-preparative HPLC method were developed utilizing various mechanisms of separation. The major metabolites proved to be isomeric glucuronides of the benzodioxane moiety hydroxylated at positions 6 or 7 and {2-(2-carboxyethyl)-3(2H)-pyridazinone}.     

Examination of proliferation of probiotic microbes by isoperibolic calorimetry

Due to the increasing consumers’ interest in up-to-date nutrition nowadays the production of main part of fermented dairy products (e.g. yogurt, kefir) is performed using probiotic microbes. The majority of this product group are the flavoured variations, the sweetener is, first of all, still refined sugar (e.g. saccharose). Honey of natural origin, consequently preferred from the nutrition-physiological point of view, could be proposed to replace this refined carbohydrate. To check its availability for this purpose the growth of microbes of the Hungarian culture of trade name Prebiolact-2 was examined. The probiotic properties of the culture are proved by clinical tests. At the determination of recipes of control and experimental samples we took into consideration that the milk composition and carbohydrate content of samples should have been the same, and they could differ only in carbohydrate-free component content of honey. During processing of the samples the minimum heat-treatment was applied to protect the biologically active components of honey to the greatest degree. Pasteurized-homogenized milk was used as raw material, in which granulated sugar and the honeys were solved, respectively, at 60 °C. The inoculation was made by Prebiolact-2 culture injected into the batch-wessel; the closed cells were agitated intensively for 10 s. General conclusion of thermal investigation is that the proliferation rate is longer lasting in case of honey treated milks. The acacia- honey resulted in the same probiotic proliferation as sugar did. In case of other herb-honeys the effect was smaller, very probably because of the strong bactericidal effect of herbs, which is very important from medical point of view. According to the results of the consumer survey over 85 % of them think that the consumption of herbs in the form of honey is especially beneficial from both dietary and market view.     

Ecotoxicological characterisation of exhaust particulates from diesel-powered light-duty vehicles

Diesel exhaust is one of the major sources of fine and ultrafine particulate matter in urban air. Toxicity of diesel-powered engine emissions has been quite widely assessed, however, much less information is available on their ecotoxicity. In our study the kinetic version of the Vibrio fischeri bioluminescence inhibition bioassay, based on the ISO 21338:2010 standard, was used to characterise the ecotoxicity of diesel-powered cars. The method is sensitive enough to test the ecotoxic effect of the emission of individual vehicles. In general, significant positive correlation was found between ecotoxicity (expressed as Toxic Unit /TU/values) and total carbon (TC) as well as between TU and polycyclic aromatic hydrocarbon (PAH) concentrations.      

Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy

Iron N‐heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub‐ps X‐ray spectroscopy study of an Fe^IINHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot ³MLCT state, from the initially excited ¹MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the ³MC state, in competition with vibrational relaxation and cooling to the relaxed ³MLCT state. The relaxed ³MLCT state then decays much more slowly (7.6 ps) to the ³MC state. The ³MC state is rapidly (2.2 ps) deactivated to the ground state. The ⁵MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the ³MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition‐metal complexes for similar ultrafast decays to optimize photochemical performance.     

Stable isotope geochemistry of calcrete nodules and septarian concretions in a Quaternary 'red clay' paleovertisol from Hungary

Calcrete nodules and concretions in unusually large amounts are embedded in the Quaternary clay-rich (Vertisol-type) 'red clay' soil-sedimentary complex at the pediment of the Mátra Mountains (Hungary). Stable isotope signatures were studied in nodules and septarian concretions, uncommon due to their several millimeter sized calcite crystals filling voids and fractures, to reveal their origin. The isotope composition of calcrete covers a wide range: delta18O=-5.9 to-10.4 per thousand and delta13C=-8.9 to-12.3 per thousand (vs. V-PDB). Isotope compositions support pedogenic (sensu stricto) and/or shallow groundwater origin for the calcrete nodules and concretions, the role of 'evolved' (isotopically modified) groundwaters in the formation of secondary carbonate was possibly subordinate. Late-stage, large, Mn-rich euhedral calcite crystals in concretions have the lowest delta13C values, which are interpreted as a result of larger contribution of isotopically light organic carbon due to decomposition of organic matter under reducing conditions. Precipitation of late calcite crystals in concretions occurred in early diagenetic environment after shallow burial of the 'red clay' paleovertisol.     

Oriented crystal growth model explains the formation of titania nanotubes

We discuss the formation mechanism of titania nanotubes synthesized by the hydrothermal method. On the basis of a comprehensive analysis of TEM, HRTEM, FT-Raman, and N(2) adsorption data, we point out some major shortcomings of the currently accepted trititanate sheet rollup mechanism. We suggest that a novel formation mechanism, oriented nanotube crystal growth from nanoloop seeds, can explain the experimental findings better than the ones proposed so far.     

Nanophase separation in segmented polyurethane elastomers: Effect of specific interactions on structure and properties

Polyurethanes were prepared from 4,4′-methylenebis (phenyl isocyanate) (MDI), 1,4-butanediol (BD) and poly (tetrahydrofurane) polyether polyol (PTHF). The -OH functional group ratio of polyol/total diol was kept constant at 0.4 in all experiments, while the ratio of the isocianate and hydroxyl groups (NCO/OH) changed between 0.940 and 1.150. Melt polymerization was carried out in an internal mixer. The polymers were characterized with a number of methods including GPC, FTIR, WAXS, DSC, DMA and tensile testing. Changing stoichiometry modifies molecular weight as expected, but the relative concentration of end-groups also changes at the same time. The respective end-groups preferentially associate with each other leading to phase separation. -OH end-groups enter into weaker interactions with each other than urethane and amine groups. The extent of phase separation, as well as the size and properties of the dispersed phase depend on composition. Each property of the polymer is affected differently by molecular weight and phase separation. Melt viscosity depends mostly on the length of the molecules, ultimate tensile properties are influenced also by interactions, while stiffness is determined almost exclusively by phase structure.     

Discretizing the fold bifurcation—A conjugacy result

In the vicinity of fold bifurcation points, the time-h exact and the stepsize-h discretized dynamics are shown to be equivalent via a two-parameter family of conjugacies. The problem of optimal conjugacy estimates remains open. Dedicated to the memory of Professor Miklós Farkas     

Effects of preadsorbed oxygen on the formation and decomposition of NCO on Rh(111) surfaces

The interaction of HNCO with oxygen dosed Rh(111) surface has been investigated by Auger electron, electron energy loss and thermal desorption spectroscopy. The presence of adsorbed oxygen exerted no apparent influence on the weakly adsorbed HNCO (T_p = 130 K). It promoted, however, the dissociative adsorption of HNCO by forming a strong O—H bond which prevented the associative desorption of HNCO. As a result no H₂ and NH₃ formation occurred, in contrast with the clean surface, and the surface concentration of irreversibly bonded NCO was also increased. New products of the surface reaction were H₂O and CO₂, in addition to CO and N₂ observed on a clean surface. From the behavior of the losses characteristic for the adsorbed NCO it appeared that the preadsorbed oxygen exerted a significant stabilizing effect on the NCO bonded to the Rh.     

In Situ Structural Determination of a Homogeneous Ruthenium Racemization Catalyst and Its Activated Intermediates Using X-Ray Absorption Spectroscopy

The activation process of a known Ru-catalyst, dicarbonyl(pentaphenylcyclopentadienyl)ruthenium chloride, has been studied in detail using time resolved in situ X-ray absorption spectroscopy. The data provide bond lengths of the species involved in the process as well as information about bond formation and bond breaking. On addition of potassium tert-butoxide, the catalyst is activated and an alkoxide complex is formed. The catalyst activation proceeds via a key acyl intermediate, which gives rise to a complete structural change in the coordination environment around the Ru atom. The rate of activation for the different catalysts was found to be highly dependent on the electronic properties of the cyclopentadienyl ligand. During catalytic racemization of 1-phenylethanol a fast-dynamic equilibrium was observed.