Kinetics of the reactions of the IO radical with dimethyl sulfide,methanethiol, ethylene,and propylene

The reactions of IO radicals with CH₃SCH₃, CH₃SH, C₂H₄, and C₃H₆ have been studied using the discharge flow method with direct detection of IO radicals by mass spectrometry. The absolute rate constants obtained at 298 K are the following: IO + CH₃SCH₃ → products (1): k₁ = (1.5 ± 0.2) × 10^?14; IO + CH₃SH → products (2): k₂ = (6.6 ± 1.3) × 10^?16; IO + C₂H₄ →products (3): k₃ < 2 × 10^?16; IO + C₃H₆ → products (4): k₄ < 2 × 10^?16 (units are cm³ molecule^?1 s^?1). CH₃S(O)CH₃ and HOI were found as products of reactions (1) and (2), respectively. The present lower value of k₁ compared to our previous determination is discussed.     

Investigation of the atomization mechanisms of copper, platinum, iridium and manganese in graphite furnace atomic absorption spectrometry

Atomization mechanisms of copper, platinum, iridium and manganese were studied by taking into account several parameters affecting the number of gaseous atoms present in the atomizer. The contributions of thermal expansion and diffusion to the dissipation rate of atoms were investigated. It was observed that the dissipation process cannot be described by diffusion only. Thermal expansion substantially contributed to the removal of atoms from the furnace and should not be ignored. It was possible to decide to what extent the several processes affect the concentration of the gaseous atoms at any time. From the E_a values obtained for the elements studied, the last step leading to gaseous atoms for copper, platinum and iridium was found to be the thermal dissociation of dimers in the gas phase; for manganese this was the dissociation of its monoxide in the gas phase.     

351 nm, 0.7 ns laser damage thresholds of monomeric liquid-crystalline systems

The 351 nm laser-damage thresholds (at 0.7 nm pulse length) of monomeric liquid crystals are reported and results from aromatic-core samples are compared with those from fully saturated systems. The role of π-electron conjugation is examined and identified as the key cause for laser damage. For UV laser compatibility of devices, the damage behaviour of an alignment-layer polymer (nylon 6/6) was also investigated.     

Synthesis of 4H-pyrans by O-cyclization of 1,5-diketones

Substituted 4H-pyrans were obtained in high preparative yields by the reaction of 1,5-diketones with acetic anhydride and boron trifluoride etherate in diethyl ether. It is assumed that the heterocyclization of 1,5-diketones includes a step involving the formation and transformations of an acyloxy carbonium ion.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 320–322, March, 1992.     

Acoustic effect of pulsed high-energy proton beams

Experimental data on the generation of acoustic radiation in solid targets by pulsed high-energy proton beams are outlined. The features of ultrasound generation in solids by beams of heavy charged particles are analyzed, and the possibility of using the acoustic effect of heavy charged particles to investigate the interaction between radiation and condensed media and to determine particle energies is shown.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 95–99, August, 1991.     

Fast switching ferroelectric side-chain liquid-crystalline polymer and copolymer

New ferroelectric side-chain liquid-crystalline polymers, a copolymer and a homopolymer, with siloxane backbone and a triaromatic mesogen as the side group have been synthesized. The materials exhibit a chiral smectic C phase over a large temperature range extending to room temperature. They possess high values of spontaneous polarization: 105 nC cm^-2 for the homopolymer and 180 nC cm^-2 for the copolymer. The electro-optic switching time in the chiral smectic C phase is extremely fast (150 μs). In the smectic A phase, an electroclinic effect with switching times less than 100 μs and with field induced tilt angles of 18° is observed.     

Synthesis of poly-yne polymers containing transition metals,disilane, disiloxane and phosphine groups in the main chain

The synthesis and characterization of metal poly-yne polymers containing disilane, disiloxane and phosphine groups in the main chain are described. The platinum and palladium poly-yne polymers were synthesized by polycondensation reactions between a metal chloride and an α, ω-bisethynyl complex in amines in the presence of cuprous iodide as a catalyst. The nickel poly-yne polymers were synthesized by an alkynyl ligand exchange reaction between a nickel acetylide and an α, ω-bisethynyl complex in diethylamine in the presence of cuprous iodide as a catalyst. The reaction of the platinum poly-yne polymer, containing disiloxane groups in the main chain, with copper (I) salts afforded adducts of η-²-bonded σ-acetylide polymer complexes. The reactions of the palladium poly-yne polymer, containing phosphine groups in the main chain, with transition-metal carbonyl complexes afforded polymer complexes which have phosphorus in the main chain-transition-metal bonds. A concentrated solution of the platinum poly-yne polymer containing disiloxane groups in the main chain forms a lyotropic liquid crystal in dichloromethane or 1, 2-dichloroethane.     

A novel derivatization method for peptides to increase sensitivity and backbone fragmentation in liquid secondary-ion mass spectra.

Derivatization is used to increase both negative-ion sensitivity and positive-ion sequence information in the liquid secondary-ion mass spectra (LSIMS) of a series of peptides. The derivatization method involves acylation with pentafluorobenzoyl fluoride in a single-step reaction, and the reaction mixture is applied directly to the probe tip for analysis. Acylation takes place at the unprotected N-terminus, tyrosine, and lysine. The derivatives exhibit increased signal-to-noise ratio for [M-H]- ions, especially where there is not already an acidic amino acid residue in the peptide. In positive-ion LSIMS, the N-terminal group acts to retain the charge at the N-terminus, simplifying the fragmentation by producing N-terminal fragment ions. It also increases positive-ion fragmentation, sometimes very dramatically, making sequence determination more straightforward. The simplicity of the process, together with the enhancements it provides, make this a generally useful method for obtaining peptide structural information.     

Nitroazines. 20. Simple syntheses of nitropyrazolopyridines from aliphatic nitrosynthons and aminopyrazoles

Two variants of a synthesis for nitropyrazolopyridines from aminopyrazoles and two- or three-carbon nitrosynthons are examined.For Communication 19 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1560–1564, November, 1992.