Total synthesis of (±) maculalactone A, maculalactone B and maculalactone C and the determination of the absolute configuration of natural (+) maculalactone A by asymmetric synthesis

Maculalactones A, B and C from the marine cyanobacterium Kyrtuthrix maculans are amongst the only compounds based on the tribenzylbutyrolactone skeleton known in nature and (+) maculalactone A from the natural source possesses significant biological activity against various marine herbivores and marine settlers. We now report a concise synthesis of racemic maculalactone A in five steps from inexpensive starting materials. Maculalactones B and C were synthesized by a minor modification to this procedure, and the synthetic design also permitted an asymmetric synthesis of maculalactone A to be achieved in around 85% ee. The (+) and (−) enantiomers of maculalactone A were assigned, respectively, to the S and R configurations on the basis of the chiral selectivity expected for catecholborane reduction of an unsymmetrical ketone in the presence of Corey's oxazoborolidine catalyst. Surprisingly, it appeared that natural (+) maculalactone A was biosynthesized in K. maculans in a partially racemic form, comprising ca. 90-95% of the (S) enantiomer and 5-10% of its (R) enantiomer. Coincidentally therefore, the percentage enantiomeric excess of the product obtained from asymmetric synthesis almost exactly matched that found in nature.     

Regional elemental signatures related to combustion of lignites

In ambient air, arsenic to selenium ratio (As/Se) is generally found to be less than 1, except in areas influenced by specific point sources, such as Cu smelters. However, the annual average of this ratio is found to be much higher than unity in Turkey. This finding is rather unique and may provide a marker for air masses influenced by the coal-related emissions in Turkey. This revised version was published online in August 2006 with corrections to the Cover Date.     

Phase formation and control of morphology in sputtered Cu-In alloy layers

The dependence of structural properties and surface morphology of Cu-In alloy layers on the composition and sputtering deposition sequence were investigated by X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray spectroscopy. The properties of the co-sputtered alloy layers changed abruptly around the composition boundary when the Cu/In ratio reached 1/2. This can be explained by the effective heat of formation (EHF) model, which has been used to predict the sequence of phase formation for metal diffusion couples. The use of a co-sputtered alloy layer with a high In concentration was not suitable for fabricating solar cells, because the film had a very rough morphology due to large In islands formed on the CuIn₂ phase. However, it was possible to minimize this phase by In sputtering followed by co-sputtering with a Cu/In ratio of 1 (Cu-In/In/Glass). This permitted the fabrication of a homogeneous Cu-In alloy layer, which was not possible through the simple co-sputtering.     

On quasi-solution to infeasible linear complementarity problem obtained by Lemke’s method

For a linear complementarity problem with inconsistent system of constraints a notion of quasi-solution of Tschebyshev type is introduced. It’s shown that this solution can be obtained automatically by Lemke’s method if the constraint matrix of the original problem is copositive plus or belongs to the intersection of matrix classes P ₀ and Q ₀.     

Frequencies of Free Oscillations of a Truncated Spherical Sector Covered with a Thin Elastic Spherical Shell

An analytic solution of the problem concerning the frequencies and shapes of free axially symmetric oscillations of a truncated spherical sector filled with an ideal compressible fluid is constructed. A spherical wall of smaller radius and the radial wall of the sector are absolutely rigid. A thin elastic shell whose edge is clamped in the radial wall is located on a spherical boundary of larger radius. The outer surface of the shell borders vacuum. The phenomenon of an anomalous decrease in the fundamental frequency as the spherical walls approach each other is discovered. An approximate formula for determination of the lowest fundamental frequencies, which are approximately proportional to the square root of the difference of the radii of spherical walls for small values of this difference, is constructed and tested numerically. Bibliography: 13 titles.     

The Classification of Complex Factor-Representations of the Three-Dimensional Heisenberg Group over a Countable Group Field of Finite Characteristic

We consider a field F that is a direct limit of an increasing chain of finite fields, and describe the Bratteli diagram, complex factor-representations, and projective moduli of the Heisenberg group of 3 × 3 upper-triangular matrices with elements from F. Bibliography: 3 titles.     

Penetration of radionuclides across the skin: Rat age dependent promethium permeation through skin in vitro

The composition and the permeation properties of the skin are dependent on age. In the animal models for permation studies, age affects the mechanical as well as the permeation properties significantly. The time dependence of permeation of ¹⁴⁷Pm³⁺ from aqueous solution was established by the animal skin model and the age dependence of promethium permeation through the skin was examined. The aim was to find the optimum rat skin age model for radionuclide permeation studies and to assess the relative importance of the main permeation pathways: transepidermal and transfollicular permeation. The skin from 5-day-old rats (5DR) was found to represent the optimum animal model to study transepidermal permeation of ions. The skin from 9-day-old rats (9DR) was selected to study transfollicular permeation of ions. Comparison of the permeated amounts of promethium through the skin without hairs (3 DR to 6 DR) and with hairs (7DR to 12DR) showed that the additional permation mode via follicles significantly contributed to the permeation rate and extent.