Reactions of carbanions derived from α-substituted-methyl tolyl sulfones with quinone methides as Michael acceptors

Nucleophilic addition of α-halo-4-tolylsulfonyl methyl anions to quinone methides and subsequent reactions were studied. Three kinds of consecutive reaction products were isolated, depending on the substrate structures and reaction conditions. Two of them were identified as rearrangement products and one as the vicarious nucleophilic substitution (VNS) product. An unexpected 1,2-migration of the tosyl group was observed. The mechanism of the reactions is briefly discussed.     

First chemoenzymatic synthesis of (R)- and (S)-1-(9H-fluoren-9-yl)ethanol

A simple chemoenzymatic synthesis of 1-(9H-fluoren-9-yl)ethanol stereoisomers is described. The enantiomers were resolved by a kinetically controlled transesterification with vinyl acetate in the presence of commercially available lipases. High-throughput screening and subsequent exhaustive investigation of the utility of the lipases in a stereoselective process of introducing chirality have been carried out. Lipase A from Candida antarctica as a cross-linked aggregate (CAL-A-CLEA) was the most efficient enzyme for the resolution of the title compound providing (S)-1-(9H-fluoren-9-yl)ethanol and its (R)-acetate in enantiopure form (>99% ee). Under mild reaction conditions, excellent enantioselectivity (E = 407), and good isolated yields of the products were obtained.     

Electron beam treatment of high NOx concentration off-gases

High concentration of NO_x removal from simulated off-gases was investigated using electron beam (EB) technology. Simulated off-gases were prepared by combusting Polish light oil or nature gas with addition of NO from a NO gas cylinder. Irradiation was carried out under a ILU-6 accelerator. It was found that removal efficiency of NO_x was influenced by inlet concentration of NO, temperature, SO₂ concentration, absorbed dose and irradiation dose rate. Methods of enhancing NO_x removal efficiency with additives using EB were also discussed.     

Plasmid DNA damage induced by helium atmospheric pressure plasma jet

Recently demonstrated ghost interference using correlated photons of different frequencies, has been theoretically analyzed. The calculation predicts an interesting nonlocal effect: the fringe width of the ghost interference depends not only on the wave-length of the photon involved, but also on the wavelength of the other photon with which it is entangled. This feature, arising because of different frequencies of the entangled photons, was hidden in the original ghost interference experiment. This prediction can be experimentally tested in a slightly modified version of the experiment.     

Decomposition of complete graphs into (0, 2)-prisms

R. Frucht and J.Gallian (1988) proved that bipartite prisms of order 2n have an α-labeling, thus they decompose the complete graph K _6nx+1 for any positive integer x. We use a technique called the ? ⁺-labeling introduced by S. I. El-Zanati, C. Vanden Eynden, and N. Punnim (2001) to show that also some other families of 3-regular bipartite graphs of order 2n called generalized prisms decompose the complete graph K _6nx+1 for any positive integer x.     

Decompositions of pseudographs into closed trails of even sizes

We consider a graph L_n, with n even, which is a complete graph with an additional loop at each vertex and minus a 1-factor and we prove that it is edge-disjointly decomposable into closed trails of even lengths greater than four, whenever these lengths sum up to the size of the graph L_n. We also show that this statement remains true if we remove from L_n two loops attached to nonadjacent vertices. Consequently, we improve P. Wittmann’s result on the upper bound of the irregular coloring number c(G) of a 2-regular graph G of size n, by determining that this number is, with a discrepancy of at most one, equal to if all components of G have even orders.     

Synthesis and characterization of novel polythiourethane hardeners for epoxy resins

A novel thiol-terminated polythiourethanes were synthesized from low-molecular-weight di- and multifunctional mercaptans and diisocyanates and employed as curing agent of epoxy resin. The curing reaction of epoxy resin and thermal properties of cured products were investigated with differential scanning calorimetry. Evaluation of climatic ageing resistance was made by the change in mechanical properties. Mechanical studies indicated that the application of polythiourethane has toughening effect and significantly increases ageing resistance of the cured resins. The results of this study indicate that molecular structure and functionality of polythiourethane oligomers are of critical importance in governing the curing mechanism, structure of the network and final properties of epoxy compositions.     

Why are SiX5(-) and GeX5(-) (X = F, Cl) stable but not CF5(-) and CCl5(-)?

The possible existence of the CF(5)(-), CCl(5)(-), SiF(5)(-), SiCl(5)(-), GeF(5)(-), and GeCl(5)(-) anions has been investigated using ab initio methods. The species containing Si and Ge as central atoms were found to adopt the D(3h)-symmetry trigonal bipyramidal equilibrium structures whose thermodynamic stabilities were confirmed by examining the most probable fragmentation channels. The ab initio re-examination of the electronic stabilities of the SiF(5)(-), SiCl(5)(-), GeF(5)(-), and GeCl(5)(-) anions [using the OVGF(full) method with the 6-311+G(3df) basis set] led to the very large vertical electron detachment (VDE) energies of 9.316 eV (SiF(5)(-)) and 9.742 eV (GeF(5)(-)), whereas smaller VDEs of 6.196 and 6.452 eV were predicted for the SiCl(5)(-) and GeCl(5)(-) species, respectively. By contrast, the high-symmetry and structurally compact anionic CF(5)(-) and CCl(5)(-) systems cannot exist due to the strongly repulsive potential predicted for the X(-) (F(-) or Cl(-)) approaching the CX(4) (CF(4) or CCl(4)). The formation of weakly bound CX(4)···X(-) (CF(4)···F(-) and CCl(4)···Cl(-)) anionic complexes (consisting of pseudotetrahedral neutral CX(4) with the weakly tethered X(-)) might be expected at low temperatures (approaching 0 K), whereas neither CX(5)(-) (CF(5)(-), CCl(5)(-)) systems nor CX(4)···X(-) (CF(4)···F(-) and CCl(4)···Cl(-)) complexes can exist in the elevated temperatures (above 0K) due to their susceptibility to the fragmentation (leading to the X(-) loss).