Regioselectivity in the ene-reaction of singlet oxygen with cyclic alkenes: photooxygenation of methyl-substituted 1,4-cyclohexadiene derivatives

The photooxygenation of the 1-methyl-, 2,3-dimethyl-, and 1,4-dimethylcyclohexa-1,4-dienes, which are readily available through Birch reduction, yielded the corresponding ene-products. The formed endocyclic dienes were trapped by the addition of singlet oxygen to give the corresponding bicyclic endoperoxy hydroperoxides. In the case of 1-methylcyclohexa-1,4-diene and 1,4-dimethylcyclohexa-1,4,-diene, the cis-effect determined the product distribution. Photooxygenation of 2,3-dimethylcyclohexa-1,4-dienes gave mainly exocyclic olefin, which was attributed to the lowered rotational barrier of the methyl group and increased reactivity of the methyl groups.     

Structural studies of Cr-doped mullite derived from single-phase precursors

Cr-doped mullites were prepared from single-phase precursors containing up to 9.60 wt% Cr₂O₃ using a sol-gel technique followed by thermal treatment. Particle induced X-ray emission spectroscopy and X-ray powder diffraction were used to characterize the samples. Mullites were orthorhombic, space group Pbam. Cr doping caused the increase of unit-cell parameters. Strongest expansion was noticed along c-axis followed by a and b (Δc/c=0.089, Δa/a=0.061, Δb/b=0.045% per mole Cr₂O₃). A second phase, namely θ-(Al,Cr)₂O₃, was revealed by XRD in the sample containing 9.60 wt% Cr₂O₃. The structure of mullites was refined by the Rietveld method, location of Cr³⁺ was performed by the EPR spectroscopy. At low chromium doping level (Cr₂O₃ content less than ∼5 wt%) Cr³⁺ ions were substituted for Al³⁺ in the AlO₆ octahedra of the mullite structure (M1 site). For higher doping level, Cr³⁺ ions were additionally substituted for Al³⁺ in the AlO₆ octahedra of the second phase [θ-(Al,Cr)₂O₃ at 1400 °C, or α-(Al,Cr)₂O₃ at 1600 °C] which segregated in the system. Substitution of Cr³⁺ for Al³⁺ on M1 site in the mullite structure resulted in increase of average distances in (M1)O₆ octahedron and decrease of average distances in T*O₄ tetrahedron, while average distances in TO₄ tetrahedron stayed almost constant.     

Conversion of single-stranded oligonucleotides into cloned duplexes and its consecutive application to short artificial genes.

A general method to convert single-stranded, chemically synthesized oligonucleotides into cloned duplexes is described. Oligonucleotides supplied with 3'-terminal extensions that are complementary to 3'-protruding ends obtained by certain restriction enzymes can be cloned either directly or with the help of an adapter molecule into double-stranded vectors. Two methods have also been developed for consecutive cloning applications. According to these methods, the synthetic oligonucleotides (and their enzymatically prepared complementary strands) are joined, one after the other, inside a cloning vector, each joining requiring one cloning step. Synthetic genes are thus built up from oligonucleotides corresponding to only one strand of the DNA. The sequential assembly of the cloned duplex takes place in the 5' to 3' direction. Each oligonucleotide is supplied with a four-nucleotide-long 3'-terminal extension, but this sequence is eliminated when the joining takes place, leaving no limiting sequence between the oligonucleotides. The two consecutive cloning methods, the adapter and the polycloning site methods, are illustrated by the assembly of short artificial genes.     

Neocompact Sets and the Fixed Point Property

We use a newly introduced concept of neocompactness to study problems from metric fixed point theory. In particular, we give a sufficient condition for a superreflexive Banach space X to have the fixed point property and obtain shorter proofs of some well-known results in that theory.     

Copper-D-penicillamine complex as potential contrast agent for MRI.

In vitro and in vivo proton T1 data are reported that demonstrate that the paramagnetic copper-D-penicillamine complex can be applied as a potential contrast agent to magnetic resonance imaging.     

Specific carbon-13 labelling of leucine residues in human growth hormone.

Biosynthetic human growth hormone specifically 13C-labelled in the carbonyl positions of all 26 leucine residues has been obtained by recombinant DNA techniques using 13C-labelled leucine and an E. coli strain that requires leucine. It is shown that, on the whole, the labelling is specific with no significant mislabelling as would have been the case had the 13C-labelled leucine been metabolized.     

Formation of β-distonic oxonium ions: Study of ROCH2CH2OR′ radical cations

Radical cations derived from the ethers ROCH₂CH₂OR′ (R, R′ = H, CH₃, C₂₅) were studied, since β-distonic oxonium ions are often prepared from ionized ethers of glycol. The first step in the fragmentation is a 1,5-transfer of an α-hydrogen to oxygen of a terminal alkoxy group leading to a δ-distonic oxonium ion. This step is thermo-neutral and reversible in the ROCH₂CH₂OH radical cations and exothermic and irreversible in the dialkyl ether radical cations. Depending on R and R,′ these δ-distonic oxonium ions fragment by three reactions: the loss of an alcohol or a water molecule, the formation of a β-distonic oxonium ion ˙CH₂CH₂O(H)⁺R and a 1,4-H migration between carbon atoms. Competition between these processes is discussed.     

Analysis of fragrance compounds in blood samples of mice by gas chromatography, mass spectrometry, GC/FTIR and GC/AES after inhalation of sandalwood oil.

After inhalation experiments with sandalwood oil and the pure fragrance compounds coumarin and alpha-terpineol, substances were detected and measured in the blood samples of test animals (mice) using gas chromatography/mass spectrometry (GC/MS) (MID) in connection with GC/FTIR (SWC), GC/AES (carbon and oxygen trace) and flame ionization detection/gas chromatography. Using tiglinic acid benzyl ester as the internal standard the following concentrations in serum could be found: alpha-santalol 6.1 ng/mL, beta-santalol 5.3 ng/mL and alpha-santalene 0.5 ng/mL. In separate inhalation experiments with coumarin and with alpha-terpineol the corresponding concentrations were 7.7 ng/mL and 6.9 ng/mL, respectively.