First total synthesis of the E type I phytoprostanes

The first total synthesis of two E type I phytoprostanes from furan, azelaic acid monomethyl ester and rac-1,2-epoxybutane is described. The key features of our synthetic strategy encompass an enzymatic kinetic resolution of a hydroxycyclopentenone, a Co-salen hydrolytic kinetic resolution of a terminal epoxide and a tandem conjugate addition/diastereoselective protonation sequence to construct the protected phytoprostanes. Mild cleavage of the silyl protective groups followed by enzymatic ester hydrolysis afforded the free E-type phytoprostanes.     

Effect of the incomplete accommodation of the heterogeneous recombination energy on heat fluxes to a quartz surface

Taking both the heterogeneous catalytic processes, including the surface formation of particles with excited internal degrees of freedom, and the processes of multicomponent diffusion and heat transfer in the MESOX apparatus fully into account makes it possible to obtain a recombination coefficient and an accommodation coefficient of the oxygen-atoms-on-quartz recombination energy which are in good agreement with the experimental data. The heterogeneous catalysis model constructed can be used effectively for predicting the heat fluxes to the surface of reentry vehicles on their entry into the Earth’s atmosphere.     

Solid-phase oxidative halodecarboxylation of β-arylacrylic acids with the ceric ammonium nitrate—alkali halide system

The solid-phase oxidation of cinnamic, 4-methoxy- and 3,4-dimethoxycinnamic acids with Ce(NH₄)₂(NO₃)₆—MHal system leads to β-halostyrenes. Similar procedure in the absence of a metal halide results in a cleavage of the C=C bond giving the corresponding benzaldehydes. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 114–118, January, 2008.     

First measurement of the helicity-dependent γ p?pη differential cross-section

The helicity dependence of the γ p↦pη reaction has been measured for the first time at a center-of-mass angle θ^* _η = 70^° in the photon energy range from 780 MeV to 790 MeV. The experiment, performed at the Mainz microtron MAMI, used a 4π-detector system, a circularly polarized, tagged photon beam, and a longitudinally polarized frozen-spin target. The helicity 3/2 cross-section is found to be small and the results for helicity 1/2 agree with predictions from the MAID analysis. Received: 19 December 2002 / Accepted: 10 March 2003 / Published online: 20 May 2003     

Mechanism of the thermal decomposition of nitrates from graphite furnace mass spectrometry studies

A basically new mechanism of the thermal decomposition of solids is proposed to explain the mass spectral observations of gaseous molecules of CoO, CuO, Cu₂O, NiO, PbO and Mg(OH)₂ during the low-temperature decomposition of the anhydrous and hydrated nitrates of these metals. The mechanism consists of two stages: congruent gasification of all reaction products irrespective of their saturated vapor pressure and subsequent condensation of the low-volatility species (oxides and hydroxides). The partial pressures of these species at the appearance temperatures calculated from this theory for the first stage of the process (1–50 mPa) are in agreement with the detection limits of the quadrupole mass spectrometers used in these experiments. The proposed mechanism is supported by other available data obtained by thermal analysis.     

Nitroxyl free radical binding to Si(1 0 0): a combined scanning tunneling microscopy and computational modeling study

The ultra-high vacuum scanning tunneling microscope (UHV-STM) was used to investigate the addition of the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) radical to the Si(1 0 0) surface. Room temperature studies performed on clean Si(1 0 0)-2 × 1 confirm the proposed binding of the unpaired valence electron associated with the singly occupied molecular orbital (SOMO) of the molecule with a Si dangling bond. A strong bias dependence in the topography of isolated molecules was observed in the range of −2.0 to +2.5 V. Semiempirical and density functional calculations of TEMPO bound to a three-dimer silicon cluster model yield occupied state density isosurfaces below the highest occupied (HOMO) and unoccupied state densities isosurfaces above the lowest unoccupied molecular orbital (LUMO) which trend in qualitative agreement with the bias dependent STM topography. Furthermore, the placement of TEMPO molecules on dangling bonds was controlled with atomic precision on the monohydride Si(1 0 0) surface via electron stimulated desorption of H, demonstrating the compatibility of nitroxyl free radical binding chemistries with nanopatterning techniques such as feedback controlled lithography.     

Phenomenological πN→ππN amplitude and the modelling of the Olsson–Turner and Chew–Low approaches

The phenomenological amplitude for the reaction πN→ππN fixed by fittings to the experimental data in the energy region 0.300 ≤P _Lab≤ 500 MeV/c is used for modelling the Chew–Low extrapolation and Olsson–Turner threshold approach. It is shown that the uncritical application of the former results in enermous theoretical errors, the extracted values being in fact random numbers. The results of the Olsson–Turner method are characterized by significant systematic errors coming from unknown details of the isobar physics. Received: 10 December 1997     

Low-energy fission investigated in reactions of 750 AMeV 238U-ions on 208Pb. II: Isotopic distributions

Projectile fission of 750 AMeV ²³⁸U-ions interacting with a Pb target was studied by means of the spectrometer FRS, GSI-Darmstadt. One of the two fission fragments was detected with a transmission of few percent and identified in mass and charge. Low-energy fission (E^* < 25 MeV) events were selected by their magnetic rigidity. Whereas the production of asymmetric fission events is dominated by the GDR excitation, very asymmetric fission and symmetric fission take place after a GQR or DGDR excitation or after a nuclear interaction. Cross sections of more than 250 isotopes were measured. Isotopic distributions of low-energy fission were reconstructed for elements from Se to Te. The fission modes SI, SII and SL were clearly shown in these distributions and in the mass and TKE distributions. Charge polarization and mass dispersion were deduced for each fission mode. Finally, the characteristics of the low-energy fission process explain the production rates of neutron-rich species. Received: 14 July 1997 / Revised version: 6 October 1997