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.     

A density functional theory computational study of the role of ligand on the stability of CuI and CuII species associated with ATRP and SET‐LRP

Atom transfer radical polymerization (ATRP) and single electron‐transfer living radical polymerization (SET‐LRP) both utilize copper complexes of various oxidation states with N‐ligands to perform their respective activation and deactivation steps. Herein, we utilize DFT (B3YLP) methods to determine the preferred ligand‐binding geometries for Cu/N‐ligand complexes related to ATRP and SET‐LRP. We find that those ligands capable of achieving tetrahedral complexes with Cu^I and trigonal bipyramidal with axial halide complexes with [Cu^IIX]⁺ have higher energies of stabilization. We were able to correlate calculated preferential stabilization of [Cu^IIX]⁺ with those ligands that perform best in SET‐LRP. A crude calculation of energy of disproportionation revealed that the same preferential binding of [Cu^IIX]⁺ results in increased propensity for disproportionation. Finally, by examining the relative energies of the basic steps of ATRP and SET‐LRP, we were able to rationalize the transition from the ATRP mechanism to the SET‐LRP mechanism as we transition from typical nonpolar ATRP solvents to polar SET‐LRP solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4950–4964, 2007     

Thermal Behavior of Urea-(D) Tartaric Acid and Urea-(DL) Tartaric Acid Crystals

The thermal behavior of two new non-linear optical (NLO) materials, urea-(D) tartaric acid (UDT) and urea-(DL) tartaric acid (UDLT) were studied by using DSC, TG and TMA. The results show that: 1) The two crystals have different melting points but similar decomposition temperatures due to the influences of intermolecular forces, which is attributed to the stereo effects of (D)-tartaric and (DL)-tartaric acid molecules; 2) There was only thermal expansion and no thermal contraction when the UDT and UDLT crystals were heated; 3) There was no phase transition within the measured temperature range; 4) The thermal expansion of the UDT and UDLT crystals shows a small anisotropy; 5) The specific heats of UDT and UDLT change linearly with temperature in the measured temperature range and the value for UDT is 1.321 J g-1 K-1 at 320 K while the specific heat of UDLT is 1.357 J g-1 K-1 at the same temperature. This revised version was published online in July 2006 with corrections to the Cover Date.