Radiophysical investigations of sea roughness (radiooceanography) at the Ukrainian Academy of Sciences

Experiments on the scattering of radio waves in the range 200 m to 3 cm from a rough sea surface are described. Amplitude, frequency, and space-time characteristics of scattered radio signals at different states of the sea surface are presented. It is shown that the problem of the short and medium wave scattering from the sea can be solved by the perturbance method. In this case the mechanism of scattering is of "resonant" character. The intensity of the backscatter signals is proportional to the density of the spatial spectrum on the half-length of the radio waves. The high frequency radio wave scattering is well described by a two-scale model of the scattering surface, "ripple on the large wave." The intensity of scattered radio signals is also proportional to the spectrum density of "ripples" whose length is approximately equal to half a radio wave. The effect of the large waves is to modulate the amplitude of a scattered radio signal and to broaden its frequency spectrum. Methods of solution of the reverse problem were considered. This allowed determination of parameters of sea roughness by characteristics of scattered radio signals. The principles of design of the corresponding equipment are described.     

Isoperimetric inequalities for a class of nonlinear parabolic equations

Abstrac Existence theorems and a priori bounds for a class of nonlinear parabolic equations are established. By means of an iteration process and symmetrization methods the solution in an arbitrary domain is compared with the one for the sphere of the same volume. It is shown that among all domains of given volume the sphere is the least stable.

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Zusammenfassung Mit Hilfe von Symmetrisierungen und Iterationsmethoden werden Existenzsätze und a priori Schranken für eine Klasse von nichtlinearen parabolischen Differentiagleichungen hergeleitet. Die Lösung für ein allgemeines Gebiet wird mit derjenigen für die Kugel vom gleichen Volumen verglichen. Es zeigt sich insbesondere, dass unter allen Gebieten mit demselben Volumen die Kugel am wenigsten stabil ist.

     

Ag6(PMo10V2O40](CH3COO).8H2O: A 3D macrocationic polyoxometallic Keggin complex

Silver atoms and strongly interlinking Keggin units ensure the tridimensionnal macrocationic structure of [Ag(6)(PMo(10)V(2)O(40))](CH(3)COO).8H(2)O, which catalyzes O(2)-based oxidation of p-methoxytoluene in acetic acid by air.     

Selective covalent binding of a positively charged water-soluble benzoheterocycle triosmium cluster to single- and double-stranded DNA

The water-soluble triosmium cluster [Os₃(CO)₉(μ-η²-(4-CHO)C₉H₅N)(μ-H)(P(OCH₂CH₂N(CH₃)₃I)₃)] (4) was tested for its reactivity with plasmid DNA. In contrast to the band retardation previously observed with a related series of positively charged clusters, an intensification and retardation of three discrete bands was observed with increasing cluster concentration. In order to further investigate the apparent modification of DNA by 4, its interaction with a 22-oligomer (sequence 5′-AGT TGT GGT GAC TTT CCC AGG C-3′) was examined. Incubation with this oligonucleotide (pH 7.4 in Tris-HCl buffer and 100 mM NaCl) followed by HPLC analysis revealed the formation of three dose dependent products assigned as covalent modifications at three sites of the oligonucleotide. Incubation of 4 with ³²P-ATP labeled oligonucleotide at the 5′-end followed by treatment with piperidine and comparison with the standard Maxam-Gilbert sequencing protocol products revealed only general background cleavage, indicating that the modification products are piperidine labile and suggesting that the modification involved formation of a Schiff base. An alternative approach was then pursued which involved annealing the 4-oligonucleotide products with their complementary strand and treatment of the resulting duplex DNAwith the exonuclease, Exo III. This assay indicated three exonuclease stops, consistent with the three products observed by HPLC whose electrophoretic mobility approximately matched guanine containing fragments when compared with the Maxam-Gilbert sequencing lanes. Reduction of the 4-oligonucleotide products with borohydride reducing agents, followed by treatment with piperidine, resulted in the formation of one product (by HPLC) with the same electrophoretic mobility as the AGTT fragment based on comparison with the Maxam-Gilbert sequencing lanes. This product most likely results from reduction of an initially formed Schiff base adduct (to the corresponding amine) with the guanine of the TGT fragment of the oligonucleotide, and corresponds to the most stable of the three Schiff base adducts detected by HPLC and by incubation with the exonuclease. The other two products are less stable and competitive reduction of the free aldehyde functionality on the cluster in equilibrium with these adducts precludes their detection after treatment with the reducing agents. The formation of the Schiff base adduct is further corroborated by the model reaction of [Os₃(CO)₁₀(μ-η²-(4-CHO)C₉H₅N)(μ-H)] (4′) with acetylated guanine in nonaqueous solvents where disappearance of the aldehyde resonance and the appearance of several new resonances in the 6-9 ppm region of the ¹H NMR of the reaction mixture is noted.     

A practical method for the stereoselective generation of beta-2-deoxy glycosyl phosphates

Beta-2-Deoxy sugar nucleotides are substrates used by a variety of glycosyltransferases (Gtfs). We have developed a chemical route to synthesize beta-2-deoxy sugar phosphates that starts from alpha-glycosyl chlorides. Our approach reliably provides access to a range of NDP beta-2-deoxy sugars essential for studying glycosyltransferases involved in the synthesis of biologically active natural products.     

Simultaneous determination of the Cd and Zn total body burden of individual,nearly microscopic,nanoliter-volume aquatic organisms (<Emphasis Type="Italic">Hyalella azteca</Emphasis>) by rhenium-cup in-torch vaporization (ITV) sample introduction and axially viewed ICP-AES

The Cd and Zn total body burden of individual, up to 7-day-old aquatic organisms (Hyalella azteca benthic amphipod) with an average volume of approximately 100 nL was determined simultaneously by using rhenium-cup (Re-cup) in-torch vaporization (ITV) sample introduction and an axially viewed inductively coupled plasma atomic emission spectrometry (ICP-AES) system. The direct elemental analysis capabilities of this system (i.e., no sample digestion) reduced sample preparation time, eliminated contamination concerns from the digestion reagent and, owing to its detection limits (e.g., in the low pg range for Cd and Zn), vit enabled simultaneous determinations of Cd and Zn in individual, neonate and young juvenile specimens barely visible to the unaided eye (e.g., nearly microscopic). As for calibration, liquid standards and the standard additions method were tested. Both methods gave comparable results, thus indicating that in this case liquid standards can be employed for calibration, and in the process making use of the standard additions method unnecessary. Overall, the ITV-ICP-AES approach by-passed the time-consuming acid digestions, eliminated the potential for contamination from the digestion reagents, improved considerably the speed of acquisition of analytical information and enabled simultaneous determinations of two elements using individual biological specimens.     

Preparation and structure of an unexpected dehydrogenation product from 2,6-diphenylcyclohexanone oxime

The synthesis, spectroscopic studies, computational analysis, and crystal structure of (6S)-2,6-diphenylcyclohex-2-enone oxime are described. The oxime crystallizes in the monoclinic space group P2 _l /c with a = 11.5269(11) Å, b = 6.6724(6) Å, c = 19.0105(18) Å, = 100.863(3)°, V = 1435.9(2) ų, and Z = 4. Semi-empirical (AM1), ab initio (MP2/6-31G*), and density functional theory (B3LYP/6-31G*) calculations suggest that there are two low-energy conformations available for the oxime. Significant differences were observed between the dihedral angles in the conformers. Good agreement was found between the crystal data and one of the conformers from the calculations. The absence of certain splitting patterns in the ¹H NMR spectrum of the title compound is in contrast to what would be expected on the basis of the dihedral angles and suggests that rapid interconversion is possible in solution. Analysis of the crystal packing suggests that one conformer is favored in the solid state, stabilized by packing interactions, and interconversion is prohibited due to a blocking effect.     

Adult-child differences in acoustic cue weighting are influenced by segmental context: children are not always perceptually biased toward transitions

It has been proposed that young children may have a perceptual preference for transitional cues [Nittrouer, S. (2002). J. Acoust. Soc. Am. 112, 711-719]. According to this proposal, this preference can manifest itself either as heavier weighting of transitional cues by children than by adults, or as heavier weighting of transitional cues than of other, more static, cues by children. This study tested this hypothesis by examining adults' and children's cue weighting for the contrasts /saI/-/integral of aI/, /de/-/be/, /ta/-/da/, and /ti/-/di/. Children were found to weight transitions more heavily than did adults for the fricative contrast /saI/-/integral aI/, and were found to weight transitional cues more heavily than nontransitional cues for the voice-onset-time contrast /ta/-/da/. However, these two patterns of cue weighting were not found to hold for the contrasts /de/-/be/ and /ti/-/di/. Consistent with several studies in the literature, results suggest that children do not always show a bias towards vowel-formant transitions, but that cue weighting can differ according to segmental context, and possibly the physical distinctiveness of available acoustic cues.