Cluster dynamics modeling of niobium and titanium carbide precipitates inα-Fe andγ-Fe

Kinetic behaviors of niobium and titanium carbide precipitates in iron are simulated with cluster dynamics.The simulations,carried out in austenite and ferrite for niobium carbides,and in austenite for titanium carbide,are analyzed for dependences on temperature,solute concentration,and initial cluster distribution.The results are presented for different temperatures and solute concentrations,compared to experimental data available.They show little impact of initial cluster distribution beyond a certain relaxation time and that highly dilute alloys with monomers only present a significantly different behavior from denser alloys or ones with different initial cluster distributions.     

Purification and monolayer study of the thylacoid lipids of moss marchantia polymorpha

The original lipid content of the thylakoid membranes of moss Marchantia polymorpha has been determined for the first time. In particular, the content of SQDG is almost 3 times higher than those for both of the other classes. The ratios for DGDG and MGDG are just a little bit lower than those for green algae, but almost 2 times less than those for plants. The distribution of unsaturated bonds has changed in C₁₈ -residues of fatty acids. The total content of C₁₈-residues in thylacoid lipids have been almost the same but the content of C_18:1, C_18:2 and C_18:3 are altered in the fractions of DGDG, PG and PE. The light stress produces only the quantitative, but no qualitative, changes of the thylakoid lipid composition. The properties of the thylakoid lipids and corresponding fatty acids in the monolayers at the liquid/gas interfaces have been studied. The changes in distribution of unsaturated bonds in C₁₈ residues of fatty acids at light stress have been confirmed by Langmuir method.     

Solvent-induced textural changes of as-synthesized mesoporous alumina, as reported by spin probe electron spin resonance spectroscopy

The effect of solvent used during the synthesis and postsynthesis treatment on textural properties of organized mesoporous aluminas was investigated and related to the behavior of spin probes studied by electron spin resonance (ESR) spectroscopy. It was found that the structure of surfactant aggregates serving in the as-synthesized precipitates as templates could be easily modified by treatment with different solvents. This treatment induces corresponding variations in surface areas, mesopore volumes, and mesopore diameters of the final products. The ESR spectrum of 5-doxyl stearic acid spin probe properly reflects the changes in template structure based on changes of the solvent used and represents an early indicator of the corresponding textural modifications of the mesoporous alumina.     

High-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry and gas chromatography-flame ionization detection characterization of Delta5-polyenoic fatty acids in triacylglycerols from conifer seed oils

Edible conifer seeds can serve as a source of triacylglycerols (TGs) with unusual Delta5 unsaturated polymethylene interrupted fatty acids (UPIFAs), such as cis-5,9-octadecadienoic (taxoleic), cis-5,9,12-octadecatrienoic (pinolenic), cis-5,11-eicosadienoic (keteleeronic) and cis-5,11,14-eicosatrienoic acids (sciadonic). Conifer seed oils from European Larch (Larix decidua), Norway Spruce (Picea abies) and European Silver Fir (Abies alba) have been analyzed by non-aqueous reversed-phase high-performance liquid chromatography (NARP-HPLC) with atmospheric pressure chemical ionisation (APCI)-MS detection. The influence of different positions of double bonds in Delta5-UPIFAs on the retention and fragmentation behavior is described and used for the successful identification of TGs in each oil. TGs containing Delta5-UPIFAs have a higher retention in comparison with common TGs found in plant oils with single methylene interrupted Delta6(9)-FAs and also significantly changed relative abundances of fragment ions in APCI mass spectra. Results obtained from HPLC/MS analyses are supported by validated GC/FID analyses of fatty acid methyl esters after the transesterification. The total content of Delta5-UPIFAs is about 32% for European Larch, 27% for Norway Spruce and 20% for European Silver Fir. In total, 20 FAs with acyl chain lengths from 16 to 24 carbon atoms and from 0 to 3 double bonds have been identified in 64 triacylglycerols from 3 conifer seed oils.     

Application of a modified Pechini method for the synthesis of Ln<Subscript>2</Subscript>MGe<Subscript>4</Subscript>O<Subscript>12</Subscript> (Ln = Y,Eu; M = Ca,Zn, Mn) optical hosts

A modified Pechini method followed by conventional and microwave heating was used to synthesise the new promising Ln₂MGe₄O₁₂ (Ln = Y, Eu; M = Ca, Zn, Mn) optical hosts. Comparison between solid-state and Pechini synthesis methods showed that the latter reduces the temperature required for cyclo-tetragermanate formation. The highest yield of cyclo-tetragermanates for both methods is observed at 1,000–1,100 °C, with significantly shorter time of annealing in the case of the Pechini synthesis. Compositional, structural and morphological characterisations of the samples obtained by both routes were carried out using X-Ray powder diffraction, thermogravimetry, electron spin resonance spectroscopy, energy-dispersive X-Ray spectroscopy and scanning electron microscopy.     

The copigmentation effect of sinapic acid on malvin: a spectroscopic investigation on colour enhancement

The present paper reports on spectroscopic investigation of copigmentation effect of sinapic acid on the malvin molecule. A reaction of copigmentation was investigated by the use of UV-Vis absorption spectra in the whole range of acidic and moderately acidic buffered aqueous solutions (pH range 1.0-6.0). It was observed that the ratio (A-A0)/A0, as a good measure of the copigment effect, has its maximum value at pH 3.6. The influences of the pH of the medium, molecular concentration, and temperature were investigated. The reaction was thermodynamically defined in terms of deltaH0, deltaG0 and deltaS0 values.     

Synthesis, IR and NMR characterization and ion extraction properties of tetranonylcalix[4]resorcinol bearing acetylhydrazone groups

A series of new calix[4]resorcinarenes (rccc-isomer) and resorcinols functionalized by acetylhydrazone binding fragments have been synthesized. The IR and NMR data and stereochemical behaviour of hydrazones are reported and compared with the results of earlier investigations. The barriers of rotation of hydrazone fragments for some octahydrazone derivatives of calix[4]resorcinarenes and their resorcinol analogues have been determined by NMR-measurements. The complexing behaviour of bis- and octahydrazones has been studied by liquid-liquid extraction towards the s-metal ions (Li⁺, Na⁺, K⁺, Cs⁺ and Ca²⁺), p-metal ions (Pb²⁺), d-metal ions (Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺ and Hg²⁺) and f-metal ions (La³⁺, Gd³⁺ and Lu³⁺). The stoichiometry of complexes and the extraction constants have been determined. It has been established that octahydrazones do not extract alkali metal cations but show excellent selectivity towards transition and soft heavy metal cations (especially Hg²⁺ or Pb²⁺).     

DFT based Monte Carlo simulations of poly(9,9-dialkylfluorene-2,7-diyl) polymers in solution

The dilute solution properties of poly(9,9-dihexylfluorene-2,7-diyl) (PDHF) were studied by coupled SEC/light scattering and MALDI-TOF over a large molecular weight (MW) span ranging from PDHF oligomers (1-8-mer) to high MW polymer. The results were compared with Monte Carlo simulations based on realistic PDHF models obtained from X-ray data and density functional theory (DFT) calculations and with a DFT based Kratky-Porod-Benoit-Doty (KPBD) worm-like chain. The simulations called "selective random walk" (SRW) and the corresponding "selective self-avoiding random walk" (SSAW) explicitly take into account the rotationally labile bonds between the fluorene units in that four distinct torsion angles (+/-37.5 and +/-143 degrees) between the units are chosen randomly. The simulations better account than the KPBD model for the experimental data obtained by us and others for various poly(9,9-dialkylfluorene-2,7-diyl) polymers but still give somewhat larger values for the radii of gyration and hydrodynamic volumes. The torsion angle selectivity of the SRW and SSAW simulations predict long chain sections punctuated by sudden sharp loops.     

Sets of Unique Continuation for Heat Equation

We study nodal lines of solutions to the heat equations. We interested in the global geometry of nodal sets, in the whole domain of definition of the solution. The local structure of nodal sets is a well understander subject, while the global geometry of nodal lines is much less clear. We give a detailed analysis of a simple component of a nodal set of a solution of the heat equation. Our results are motivated by some applied problems. They related to classical problems of the unique continuation and the backward uniqueness for parabolic equations.