The Sun is a plasma diffuser that sorts atoms by mass

The Sun is a plasma diffuser that selectively moves light elements like H and He and the lighter isotopes of each element to its surface. The Sun formed on the collapsed core of a supernova (SN) and is composed mostly of elements made near the SN core (Fe, O, Ni, Si, and S), like the rocky planets and ordinary meteorites. Neutron emission from the central neutron star triggers a series of reactions that generate solar luminosity, solar neutrinos, solar mass fractionation, and an outpouring of hydrogen in the solar wind. Mass fractionation seems to have operated in the parent star and likely occurs in other stars as well. The text was submitted by the authors in English.     

Analysis of optodynamic sources generated during laser-induced breakdown in water

We propose a method for evaluating the size of the laser-induced breakdown region in water based on the detection and analysis of optodynamic waves. The breakdown region is an optodynamic source of pressure waves that propagate into the surrounding liquid as an ultrasonic pulse. In the experiment the optical breakdown was generated by a standard ophthalmic Nd:YAG laser with a pulse duration of 10 ns and a maximum energy per pulse of 10 mJ. The pulses were detected inside the liquid with a laser-beam deflection probe. The waveforms were captured in the far-field and analyzed. The analysis provides information about the apparent size of the optodynamic source, which is directly related to the size of the breakdown region. The proposed method can be adapted for online monitoring.     

The applicability of a material-treatment laser pulse in non-destructive evaluations

A practical optodynamic study was performed to determine the usability of different lengths of laser pulses for the generation of ultrasonic transients in a solid material. The aim of the study was to evaluate the possibility of a dual use for a laser pulse-for laser material processing, on the one hand, and for the ultrasonic wave generation on the other-with both processes being combined on the same production line. The propagation of the laser-generated ultrasonic waves is evaluated by detecting and measuring with a PID-controlled stabilized interferometer. Thus, both systems provided the basic tools, the generation and detection of ultrasonic waves, for an ultrasonic, laser-based, non-destructive material evaluation. The ultrasonic transients generated by 'classical' nanosecond laser pulses were compared with the transients generated by industrial laser pulses with a duration of a few tenths of a microsecond. The experimental results are compared with the results of a time-of-flight analysis that also involved part of a mode-conversion analysis for both regimes in a layered material structure. The differences between the two waveforms were assessed in terms of their visibility, wavelength and resolution. The limit values were calculated and estimated for the laser-pulse parameters, when such pulses are intended for use in an ultrasonic, laser-based, non-destructive evaluation. The possibility of using an industrial marking laser for laser ultrasound generation is thus demonstrated.     

A Strategy for Neuraminidase Inhibitors Using Mechanism‐Based Labeling Information

A potent inhibitor for Vibrio cholerae neuraminidase (VCNA) was developed by using a novel two‐step strategy, a target amino acid validation using mechanism‐based labeling information, and a potent inhibitor search using a focused library. The labeling information suggested the hidden dynamics of a loop structure of VCNA, which can be a potential target of the novel inhibitor. A focused library composed of 187 compounds was prepared from a 9‐azide derivative of 2,3‐dehydro‐N‐acetylneuraminic acid (DANA) to interrupt the function of the loop of the labeled residues. Inhibitor 3c showed potent inhibition properties and was the strongest inhibitor with FANA, a N‐trifluoroacetyl derivative of DANA. Validation studies of the inhibitor with a detergent and a Lineweaver–Burk plot suggested that the 9‐substitution group would interact hydrophobically with the target loop moiety, adding a noncompetitive inhibition property to the DANA skeleton. This information enabled us to design compound 4 having the combined structure of 3c and FANA. Compound 4 showed the most potent inhibition (K_i=73 nM , mixed inhibition) of VCNA with high selectivity among the tested viral, bacterial, and mammal neuraminidases.     

Synthesis of the C1-C20 and C15-C27 segments of aplyronine A

The synthesis of C1-C20 and C15-C27 segments of Aplyronine A is described. Oxidative cleavage of cyclic vinyl sulfones has been used to prepare key fragments of Aplyronine A. Key precursors are united by Horner-Wadsworth-Emmons and Julia-Kociensky olefination for the respective elaboration of the C1-C20 and C15-C27 segments.     

Optodynamic study of multiple pulses micro drilling

This paper describes an analysis of pulsed lasers micro-drilling of different metals. Study focuses to an optodynamic phenomenon which appears as thermal effects induced by laser light pulses and leads to dynamic process manifested as ultrasonic shock waves propagating into the sample material. The shock waves are detected by a non-contact optical method by using arm compensated Michelson. Monitoring of the main parameters of the micro drilling such as material ablation rate and efficiency was realized by analysis of the optodynamic signals. The process is characterized by decreasing ablation rate that leads to the finite hole depth. The experimental part of study comprehends a comparison between various metals. In order to describe decreasing ablation rate a theoretical model based on the energy balance is proposed. It considers the energy/heat transfer from the laser beam to the material and predicts a decreasing drilling rate with an increasing number of successive laser pulses. According to the proposed model, the finite depth of the hole appears as a consequence of the increasing surface area through which the energy of the laser beam is conducted away to the material around the processed area. Decreasing ablation rate and the finite hole depth predicted by model were in good agreement with the experimental results.     

Characterisation of sorbate geometrical isomers

trans,trans Isomers of sorbic acid, its potassium salt and ethyl sorbate isomerise under UV irradiation. All four geometrical isomers of the acid, salt and ester were separated using high-performance liquid chromatography on a nonpolar reversed-phase column (C18) and the ester also by gas chromatography on a VOCOL capillary column. The limit of detection and the interval of linearity were determined for all chromatographic methods. Individual isomers were identified with NMR analysis. Resolved chemical shifts of protons adjacent to the double bonds enabled qualitative and quantitative determination of isomers in the mixture. Antimicrobial activity of potassium sorbate isomers was tested on yeast Saccharomyces cerevisiae. Results show that the pure trans,trans isomer has a higher antimicrobial activity than the mixture of isomers.     

Conversion of cyclic vinyl sulfones to transposed vinyl phosphonates

Functionalized cyclic vinyl sulfones were directly converted to the "polarity reversed" vinyl phosphonates through an efficient one pot procedure. Ozonolysis of these vinyl sulfones and vinyl phosphonates furnish complementary sets of termini-differentiated ester-aldehydes. This strategy has been applied for preparation of segments needed for the synthesis of Aplyronine A. The scope and limitations of this transformation were defined.     

Onset of local ordering in some copper-based alloys: critical solute concentration vis-a-vis various solutionhardening parameters

The mode of planar distribution of solute atoms in Cu single crystals alloyed with 0.5 to 8.0 at.%Ge has been investigated via the temperature dependence of the critical resolved shear stress of these alloys. It is found that there exists a critical solute concentration c _m ≈ 5 at.%Ge below which the distribution of solute atoms in the crystal is random, and above which some local ordering occurs. This together with such data available in the literature for Cu-Zn, Cu-Al and Cu-Mn alloys, i.e. c _m ≈7 at. %Zn, 7 at.%Al and 1 at.%Mn, when examined as a function of the size-misfit factor δ = (1/b)(db/dc)of a given binary alloy system, shows that the value of c _m strongly depends on δ; the smaller the magnitude of δ, the greater the value of c _m and vice versa. Also, the value of c _m is found to correlate well with the electron-to-atom ratio (e/a)of the Cu-Zn, Cu-Al, Cu-Ge and Cu-Mn alloys with the solute concentration c = c _m . However, no systematic correlation exists between the critical solute concentration c _m for the onset of local ordering and the modulus-mismatch parameter η = (1/G)(dG/dc).      

Chemoselective and enantioselective oxidation of indoles employing aspartyl peptide catalysts

Catalytic enantioselective indole oxidation is a process of particular relevance to the chemistry of complex alkaloids, as it has been implicated in their biosynthesis. In the context of synthetic methodology, catalytic enantioselective indole oxidation allows a rapid and biomimetic entry into several classes of alkaloid natural products. Despite this potentially high utility in the total synthesis, reports of catalytic enantioselective indole oxidation remain sparse. Here we report a highly chemoselective catalytic system for the indole oxidation that delivers 3-hydroxy-indolenines with good chemical yields and moderate to high levels of enantio- and diastereoselectivity (up to 95:5 er and up to 92:8 dr). These results represent, to our knowledge, the most selective values yet reported in the literature for catalytic asymmetric indole oxidation. Furthermore, the utility of enantioenriched hydroxy-indolenines in stereospecific rearrangements is demonstrated.