Microbial Baeyer-Villiger Oxidation of Ketones by Cyclohexanone and Cyclopentanone Monooxygenase – A Computational Rational for Biocatalyst Performance

Summary. Recombinant Escherichia coli overexpressing Pseudomonas sp. NCIMB 9872 cyclopentanone monooxygenase (CPMO, EC 1.14.13.16) and Acinetobacter sp. NCIMB 9871 cyclohexanone monooxygenase (CHMO, EC 1.14.13.22) have been utilized in whole-cell Baeyer-Villiger biotransformations of prochiral bicycloketones. A significant difference in substrate acceptance and stereoselectivity was observed for bicyclo[3.3.0] and bicyclo[4.3.0] substrates. A plausible mechanism of these transformations was established by means of high level DFT/B3LYP calculations suggesting an essential difference in electronic requirements for a successful enzymatic conversion, which was similarly encountered in recombinant whole-cell mediated biooxidations. Some of the lactones produced in the biocatalytic Baeyer-Villiger oxidation represent key intermediates for the synthesis of indole alkaloids.     

Magnetic force microscopy studies of domain walls in nickel and cobalt films

A magnetic force microscopy is used to examine the domain walls in nickel and cobalt films deposited by argon ion sputtering. Thin nickel films deposited at high substrate temperatures exhibit coexistent Bloch and Neel walls. Films grown at room temperature display alternative Bloch lines with cap switches. These films agglomerate to form grains after annealed at high temperatures. The film composed of larger grains behaves better nucleation implying magnetic domains of closure, while the film composed of smaller grains exhibits more defects implying alternative Bloch lines. We have also observed domain displacements and cap switches, which occur due to precipitation of particles in small grain size films. Stripe domains are observed for film thicknesses larger than 100 nm. They become zigzag cells when an external field of 1.5 T is applied perpendicular to the surface of the films. This experiment indicates that the domain sizes in thin films and the strip widths for thick films both depend on the square-root of the film thickness, which varies from 5 to 45 nm and from 100 to 450 nm, respectively.     

Growth, structure, and properties of KTiOPO4 crystals doped with iron

A series of iron-doped KTiOPO₄ (KTP: Fe) single crystals in which iron substitutes for 0.1–0.3% titanium was grown. The structure of the KTP: Fe crystals was determined, and their dielectric and conducting properties were studied. An X-ray diffraction analysis failed to reveal such asmall amount of Fe⁺³ ions in titanium octahedral positions of the structure. It was found that an increase in the iron concentration results in a lowering of the symmetry of Ti(1)O₆ and Ti(2)O₆ octahedra. The splitting of the dielectric anomaly due to the ferroelectric phase transition was explained by the mechanism of incorporation of an impurity into different growth pyramids of the crystals. It was established that the aging of the KTP: Fe crystals leads to changes in the permittivity and electrical conductivity during long storage.     

Creep of composites with a porous fibre/matrix interface under variable loading

A micromechanical model of island-type fibre/matrix interface is described and experimental data are represented and analysed. Changes in the interface strength during a cycle loadings and, correspondingly, changes in the creep resistance of a composite due the island-like scheme of the fibre/matrix interface are described.     

Models for incommensurate phases in crystals withPcmn symmetry

A discussion is given of the relation between different models for systems with incommensurate phases. Moreover, a generalisation of such models is introduced, which shows an alternative explanation for similar phase diagrams. To get this one may vary the range of the interactions and the numbers of degrees of freedom per site.Another generalization involves coupling to elastic degrees of freedom. Such a coupling may change the type of the incommensurate phase transition.     

Analysis of triallate residues in cereals and soil by gas chromatography with ion-trap detection.

Triallate residues in barley seedlings and soil samples were determined by gas chromatography with ion-trap detection. Soil was extracted with methanol on a mechanical shaker, and plants were extracted with acetonitrile in a Sorvall homogenizer. After evaporation of the organic solvents, the residue was dissolved in hexane, and plants extracts were cleaned-up on an alumina column. Gas chromatographic analysis was carried out using a BP-1 fused-silica capillary column with helium as carrier gas. To quantitate residues the total-ion chromatogram was obtained and then the selected-ion monitoring chromatograms were displayed at m/z 86 for triallate and at m/z 154 for the internal standard, methyl-(4-amino-2-chloro)-benzoate. The average recovery through the method from barley and soil samples was always higher than 80%. The limit of detection in the selected-ion mode was 0.01 mg/kg. Barley and soil samples treated with triallate were also analysed. A good agreement was observed between results obtained by this method and by gas chromatography with nitrogen-phosphorus detection.     

Problems associated with interferences in the analysis of serum for polychlorinated biphenyls

During a recent survey to determine serum concentrations of polychlorinated biphenyls (PCBs) among people living around New Bedford, MA, U.S.A., an unidentified contaminant precluded the quantification of some early eluting Webb and McCall peaks. Loss of data is estimated to have reduced reported serum levels by 12%. Efforts to identify the contaminant by gas chromatography with an electron-capture detector, a Hall electrolytic condutivity detector, and mass spectrometer were not successful. Researchers ascertained, however, that the contaminant is not a PCB, it does not contain halogens, but it may contain phthalates. Vacutainer tubes and closures for serum storage bottles are suspected sources of contamination.     

Strained layer quantum well semiconductor optical amplifiers: Polarization insensitive amplification

Polarization insensitive optical amplification was demonstrated in newly developed semiconductor optical amplifiers that have strained GalnAsP quantum well structures. We tailored the active region of the quaternary strained layer quantum well structure with a small biaxially tensile strain of 0.2% in the well layers for polarization insensitive operation.     

Photolysis of 2-dialkylamino-3-methyl-1,4-naphthoquinones

The photolysis of 2-dialkylamino-1,4-naphthoquinones is significantly more efficient when a methyl group is at C³. The quantum yields are 2–6 times greater than for 2-dialkylaminonaphthoquinones lacking a methyl group. 2-Monoalkyl-amino-1,4-naphthoquinones also undergo photochemical dealkylation.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2387–2392, October, 1991.