Phenylsulfonyl ene-allenes as efficient precursors to bicyclic systems via intramolecular [2 + 2]-cycloaddition reactions

Various phenylsulfonyl allene derivatives were prepared with double bonds tethered either to the alpha-position or the gamma-position of the allene. These substrates underwent a highly regio- and stereospecific thermal [2 + 2]-cycloaddition across the nonactivated cumulene double bond, forming distal cycloadducts (i.e., 57) in the case of alpha-tethered allenes and proximal adducts (i.e., 25) in the case of gamma-tethered allenes. The mechanistic rationale for the observed stereospecificity involves initial diradical formation, followed by a rapid ring closure to the more stable cis-fused ring system. The tether may be equipped with heteroatoms, allowing for the formation of fused heterocycles (e.g., 61), and the cycloaddition can be facilitated by the introduction of sterically bulky groups and/or by conformational rigidity to the tether. Other modes of cyclization were observed in the presence of sodium benzenesulfinate or Lewis acids, in which cases polar mechanisms prevail. The chemoselectivity is reversed for [4 + 2]-cycloadditions, which prefer instead to engage the vinyl sulfone moiety, independent of whether the tether is attached to the alpha- or gamma-position of the allene.     

Chloroantimonate(III): Die Kristallstruktur des 4,4′-Dipyridylium-pentachloroantimonats, (C10H8N2H2)SbCl5

Chloroantimonates(III): Crystal Structure of 4,4′-Dipyridylium Pentachloroantimonate, (C₁₀H₈N₂H₂)SbCl₅ (C₁₀H₈N₂H₂)SbCl₅ crystallizes in the triclinic space group P1 with a= 843.1(5), b = 958.6(8), c = 1098.0(10) pm, α = 112.45(6), β = 101.95(6), γ = 97.78(6)° and Z = 2. The structure is built up of 4,4 °-dipyridylium cations and pentachloroantimonate anions. The Sb atoms are distorted octahedrally coordinated. Mean distances are Sb? Cl = 242 pm (1×), Sb? Cl = 255 pm (2×), Sb ? Cl = 275 pm (2×) and Sb…?Cl.= 319 pm (1× ). The anions build up dimers.     

Enantioseparation of chiral N-imidazole derivatives by electrokinetic chromatography using highly sulfated cyclodextrins: mechanism of enantioselective recognition

Baseline separation of ten new substituted [1-(imidazo-1-yl)-1-phenylmethyl)] benzothiazolinone and benzoxazolinone derivatives, with one chiral center, was achieved by CD-EKC using highly sulfated CDs (alpha, beta, gamma highly S-CDs) as chiral selectors. The influence of the type and concentration of the chiral selectors on the enantioseparations was investigated. The highly S-CDs exhibit a very high enantioselectivity power since they allow excellent enantiomeric resolutions compared to those obtained with the neutral CDs. The enantiomers were resolved with analysis times inferior to 2.5 min and resolution factors R(s) of 3.73, 3.90, 1.40, and 4.35 for compounds 1, 2, 3, and 5, respectively, using 25 mM phosphate buffer at pH 2.5 containing either highly S-alpha-CD, highly S-beta-CD, and highly S-gamma-CD (3 or 4% w/v) at 298 K, with an applied field of 0.30 kV/cm. The determination of the enantiomer migration order for the various analytes and the study of the analyte structure-enantioseparation relationships display the high contribution of the interactions between the analytes phenyl ring and the CDs to the enantiorecognition process. The thermodynamic study of the analyte-CD affinities permits us to improve our knowledge about the enantioseparation mechanism.     

Enantiomeric analysis of baclofen analogs by capillary zone electrophoresis, using highly sulfated cyclodextrins: Inclusion ionization constant pKa determination

Using cyclodextrin-capillary zone electrophoresis (CD-CZE), baseline separation of baclofen phaclofen, saclofen, and hydroxy-saclofen, potent gamma-aminobutyric acid(B) (GABA(B)) agonist or antagonists was achieved. A method for the enantioresolution of those analogs of GABA was developed using anionic cyclodextrins (highly sulfated CD or highly S-CD) as chiral selectors and capillaries dynamically coated with polyethylene oxide (PEO). With charged CDs we observed good resolutions due to the large electrophoretic mobility of these chiral selectors opposite to the mobility of the solutes. The highly S-alpha-CD and S-beta-CD were found to be complementary and the most effective complexing agent, allowing good enantiomeric resolution in short runtimes. The complete resolution was obtained using 25 mM phosphate buffer at pH 2.5 containing 3% w/v of highly S-alpha-CD or S-beta-CD at 25 degrees C with an applied field of 0.30 kV/cm. The apparent binding constants of the inclusion complexes were evaluated and the migration order was determined. A comparison was possible to investigate the importance of the anionic group of the molecules in the separations. The pK(a) values were determined for all four compounds in order to explain relative electrophoretic migration of the solutes.     

Lexicographic products with high reconstruction numbers

The reconstruction number of a graph is the smallest number of vertex-deleted subgraphs needed to uniquely determine the graph up to isomorphism. Bollobás showed that almost all graphs have reconstruction number equal to three. McMullen and Radziszowski published a catalogue of all graphs on at most ten vertices with reconstruction number greater than three. We introduce constructions that generalize the examples identified in their work. In particular, we use lexicographic products of vertex transitive graphs with certain starter graphs from the work of Myrvold and from the work of Harary and Plantholt to generate new infinite families of graphs with high reconstruction numbers. In the process, we settle a question of McMullen and Radziszowski.     

Magnetic Study of Doped Ba Ferrites Prepared by Citrate Method

The M-type barium ferrite is doped with either Co²⁺-Ti⁴⁺ or Co²⁺-Zr⁴⁺ pairs to reduce its intrinsically high uniaxial magnetic anisotropy in order to make fine particles for magnetic recording. The magnetic parameters were investigated by magnetic measurements and the Mössbauer spectroscopy. Compounds (BaF) obtained from BaCo _x (Ti,Zr) _x Fe_12-2x O₁₉ with 0x1.0 have been prepared by the modified citrate method with the initial ratio of Ba:Fe equal to 1:10.8. The substitution of Co - Ti or Co - Zr for Fe³⁺ ions affects mainly the positions 2a and 4f ₂. Ba ferrite with the substitution x 0.8 is promising for perpendicular recording media applications.     

Mössbauer Spectroscopy on Nuclear Power Plant Materials

Experimental results of original irradiated reactor pressure vessel surveillance specimens are presented and discussed in the paper. In 1994, the new Extended Surveillance Specimen Program for Nuclear Reactor Material Study was started in collaboration with the nuclear power plant (NPP) Bohunice and NPP Research Institute Trnava (Slovakia). Three batches of special prepared Mössbauer samples (after 1, 2 and 3 years stay in irradiation channels) were measured and interpreted using the new four components approach of Mössbauer spectra evaluation with the aim to observe microstructural changes due to thermal and neutron treatment resulting from operating conditions in NPP. The systematic changes in the relative areas of Mössbauer spectra components were observed and discussed.     

Dehydration of synthetic lepidocrocite (γ-FeOOH)

The thermal decomposition of synthetic lepidocrocite,γ-FeOOH, was studied using DTA, infrared and Mössbauer spectroscopy and X-ray diffraction, and the dependence of the phase composition of the dehydration products on the method of preparing the initialγ-FeOOH was described. The results demonstrated thatγ-Fe₂O₃ formed by dehydration ofγ-FeOOH consists of very small particles with a broad size distribution and that, depending on the method of preparation, the initialγ-FeOOH can contain a large amount of amorphous ferric hydroxide. A preparation method yieldingγ -FeOOH which is not contaminated with other ferric oxide-hydroxides is recommended.     

Application of Mössbauer spectroscopy on corrosion products of NPP

Steam generator (SG) is generally one of the most important components at all nuclear power plants (NPP) with close impact to safe and long-term operation. Material degradation and corrosion/erosion processes are serious risks for long-term reliable operation. Steam generators of four VVER-440 units at nuclear power plants V-1 and V-2 in Jaslovske Bohunice (Slovakia) were gradually changed by new original “Bohunice” design in period 1994–1998, in order to improve corrosion resistance of SGs. Corrosion processes before and after these design and material changes in Bohunice secondary circuit were studied using Mössbauer spectroscopy during last 25 years. Innovations in the feed water pipeline design as well as material composition improvements were evaluated positively. Mössbauer spectroscopy studies of phase composition of corrosion products were performed on real specimens scrapped from water pipelines or in form of filters deposits. Newest results in our long-term corrosion study confirm good operational experiences and suitable chemical regimes (reduction environment) which results mostly in creation of magnetite (on the level 70 % or higher) and small portions of hematite, goethite or hydrooxides. Regular observation of corrosion/erosion processes is essential for keeping NPP operation on high safety level. The output from performed material analyses influences the optimisation of operating chemical regimes and it can be used in optimisation of regimes at decontamination and passivation of pipelines or secondary circuit components. It can be concluded that a longer passivation time leads more to magnetite fraction in the corrosion products composition.     

Separations of antifungal compounds in capillary electrophoresis with two anionic cyclodextrins

CD‐CZE methods were developed for complete stereoisomeric separations of a series of six γ‐lactam analogues, of which some were neutral, or cationic depending on the background electrolyte nature. The tested cyclodextrin was the versatile sulfobutylether‐ β‐CD, used either in a phosphate buffer using capillaries dynamically coated with polyethylene oxide or in a borate buffer using uncoated capillaries. Long‐end and short‐end modes and concentration variations of chiral selectors allowed finding conditions of complete separation of four out of the six derivatives (i.e., 1 , 2 , 3, and 4 ) in short run times, confirming their broad range of applications. To separate the two last compounds, the highly sulfated‐ γ‐CD was examined as chiral selector in acidic phosphate conditions. The enantiomers of the γ‐lactam analogues 5 and 6 were baseline resolved with 5.5 and 4%, respectively as concentration in the buffer.