Stereocontrolled synthesis of (3Z,5E)-6-aryl-3-methylhexa-3,5-dien-1-ols,intermediates in the synthesis of strobilurin antibiotics

(2E,4E)-5-Aryl-2-(2-benzyloxyethyl)penta-2,4-dien-1-als (aryl is phenyl and 4-methox-yphenyl) were reduced with NaBH₄ quantitatively and stereospecifically to the corresponding penta-2(E),4(E)-dien-1-ols. The hydroxymethyl group in the latter was transformed into a methyl one with a stereoselectivity of 92–97%. Debenzylation of the resulting (1E,3Z)-1-aryl-6-benzyloxy-4-methylhexa-1,3-dienes with AlCl₃ in the presence of PhNMe₂ afforded the target (3Z,5E)-6-aryl-3-methylhexa-3,5-dien-1-ols; the configuration of the C=C bonds in the conjugated aryl diene systems was retained at 95%.     

Formal synthesis of strobilurins A and X

Known synthetic precursors of strobilurins A and X, i.e., methyl (3Z,5E)-6-aryl-3-methylhexa-3,5-dienoates (aryl is phenyl, 4-methoxyphenyl), were synthesized by highly stereospecific reactions from 2-(2-tert-butyldimethylsilyloxyethyl)- and 2-[2-(4-methoxybenzyloxy)-ethyl]-5-arylpenta-2E,4E-dien-1-ols. These dienols were efficiently dehydroxylated to (1E,3Z)-4-methyl-6-(4-methoxybenzyloxy)hexa-1,3-dienylarenes with their subsequent demethoxyben-zylation to (3Z,5E)-6-aryl-3-methylhexa-3,5-dien-1-ols. The latter through the step of corresponding aryldienals and aryldienoic acids were transformed to the target methyl (3Z,5E)-6-aryl-3-methylhexa-3,5-dienoates, which completes a formal synthesis of strobilurins A and X. Configuration of the C=C bonds of the conjugated aryldiene system is preserved in the considered transformations by 95–97%.     

Interfering modes and an axial wave in an underwater sound channel

Experiments on long-range propagation of low-frequency sound that were conducted starting from the mid-1980s indicate a complex character of propagation in an underwater sound channel, in which a source and a receiver are located close to the channel axis. A burst of energy propagating along the axis follows early arrivals, which are well described by the formulas of geometrical acoustics, in plots of acoustic intensity as a function of propagation time and hydrophone depth. This energy burst cannot be described using geometrical acoustics because of caustics with caustic beaks located near the channel axis. Very complex interference processes occur near these caustics. As the distance from the source grows, the dimensions of the interference vicinity increase and start to overlap producing a peculiar “axial wave.” For an arbitrary two-dimensional underwater sound channel, the axial wave can be represented as a sum of the first normal modes and a residue. This conclusion is based on the use of two representations for an acoustic field. The first of them includes the sum of ray components and an axial wave. The second representation consists of ray addends, the sum of the first normal modes, and a residue. Numerical results are obtained for a canonical profile of sound velocity at the frequency of 200 Hz for the distances of 1600–1650 km.     

Circular dichroism in laser-assisted short-pulse photoionization

A remarkable effect of circular dichroism, i.e., a difference in photoelectron spectra produced by right and left circularly polarized light in two-color multiphoton ionization of atoms, is predicted for the case when the atom is ionized by an extreme ultraviolet or x-ray femtosecond pulse in the field of a strong infrared laser pulse, both pulses being circularly polarized. We show that the sidebands formed in the spectra exhibit different circular dichroism often of different signs both in angle-resolved and angle-integrated experimental conditions. The effect can be used for detecting and measuring circular polarization of x rays in a spectral range where other methods are not effective.     

Reversible Modulation of Surface Plasmons in Gold Nanoparticles Enabled by Surface Redox Chemistry

Switchable surface redox chemistry is demonstrated in gold@iron/iron oxide core–shell nanoparticles with ambient oxidation and plasmon‐mediated reduction to modulate the oxidation state of shell layers. The iron shell can be oxidized to iron oxide through ambient oxidation, leading to an enhancement and red‐shift of the gold surface plasmon resonance (SPR). This enhanced gold SPR can drive reduction of the iron oxide shell under broadband illumination to reversibly blue‐shift and significantly dampen gold SPR absorption. The observed phenomena provide a unique mechanism for controlling the plasmonic properties and surface chemistry of small metal nanoparticles.     

Manganese minerals from the Miassovo freshwater lake: Composition and structure

The mineral, chemical, and trace element composition and the microstructures of manganese minerals in bottom nodules and crusts collected from the Bolshoe Miassovo freshwater lake (South Urals) were studied. Freshwater manganese species were shown to have more diversified mineral compositions than in marine species. In addition to (9.6- and 7.2 Å) layered manganese mineral structures, various manganese-containing carbonates were frequently present in lacustrine samples. As opposed to marine samples, lacustrine samples were poor in trace elements, in particular rare-earth elements, but have higher contents of Sr, As, Ti, and V. A structural analysis of lacustrine manganese species showed their biomorphic nature, which manifested itself as organic bacterial species ranging from spherulitic to filamentary ones.     

Slow and Fast Oscillations in a Model of an Optoelectronic Oscillator with Delay

Doklady Mathematics - The local dynamics of a well-known model of an optoelectronic oscillator with delayed feedback is studied. In a neighborhood of zero equilibrium, normalized equations are...     

Synthesis and structures of silicon-, germanium- and tin-containing tungsten imido alkyl complexes (ArN)2W(CH2EMe3)2 (E = Si, Ge, Sn)

The novel silicon-, germanium- and tin-containing imido alkyl complexes of tungsten of the type (ArN)₂W(CH₂EMe₃)₂ (; E = Si (1), Ge (2), Sn (3)) have been prepared by the reactions of (ArN)₂WCl₂(dme) (dme = 1,2-dimethoxyethane) with heteroelement-containing alkyllithium or Grignard reagents Me₃ECH₂Li (E = Si, Ge), Me₃ECH₂MgCl (E = Ge, Sn). The title compounds were isolated in high yields as crystalline solids and characterized by elemental analysis, IR, ¹H, ¹³C, ²⁹Si and ¹¹⁹Sn NMR spectroscopy and X-ray diffraction studies. The geometry of the W atoms in the compounds can be described as a distorted tetrahedron.