FT-EPR and HPLC study of the mechanism of 4-chlorophenol photolysis

The mechanism of 4-chlorophenol (4CP) photolysis was investigated with the aid of Fourier Transform Electron Paramagnetic Resonance (FT-EPR) and pulsed-laser photolysis combined with High Performance Liquid Chromatography (HPLC) detection-of stable (diamagnetic) products. With FT-EPR transient free radicals produced by pulsed-laser excitation of solutions of 4CP in alcohols could be identified. Time profiles of the FT-EPR spectra provided information on reaction kinetics and Chemically Induced Dynamic, Electron Polarization (CIDEP) effects. It was found that 4CP photolysis in alcohols leads to the simultaneous formation of the phenoxyl radical and radicals produced by hydrogen abstraction from the solvent. CIDEP patterns establish that these radicals are formed in a reaction sequence involving a triplet state precursor and radical pair intermediate. Results of earlier transient optical absorption measurements indicate that the triplet precursor must be the carbene 4-oxocyclohexa-2,5-dienylidene. This assignment is supported by the finding that photolysis of quinone diazide in a hydrogen-donating solvent gives the same free radical products as those obtained from 4CP. The formation of the phenoxyl radical intermediate accounts for the finding that photolysis of deoxygenated solutions of 4CP in alcohols gives phenol as stable diamagnetic product. By contrast, photolysis of aerated and deoxygenated aqueous solutions of 4CP produces benzoquinone and hydroquinone as primary products, respectively.     

The nonlinear effects of quantum electrodynamics at high energies

In this paper we considere ⁺ e ^? scattering with intermediate photon-photon scattering as a possibility for getting information about the nonlinear effects of quantum electrodynamics (QED) at high energies. This process is a higher-order correction to double bremsstrahlung. However, these two processes have quite different behaviour with the photon-photon scattering angle. Here we calculate the unpolarized differential cross section of thee ⁺ e ^? scattering with intermediate γγ scattering and also the interference terms with the double bremsstrahlung. Moreover, we show that the sum of these two contributions predominates over the contribution of the double bremsstrahlung for sufficiently large scattering angles of the photons. This result enables us to extract the differential cross section of the γγ scattering. Through extrapolation to different kinematical conditions we can get the cross sections for nearly real photon-photon scattering, photon splitting and Delbrück scattering. As a quantitative example we use the result for a test of the electron propagator in a gauge-invariant way with the usual minimal interaction. We give also numerical examples of this test, which will improve the present values of the testing parameters.     

The phase composition of tin-nickel electrodeposited alloys

It was studied the tin phase composition of the electrodeposited alloys produced at different temperatures and current densities from an acid chloride/fluoride electrolyte and an acid chloride bath. Mössbauer spectra were consistent with a Ni₃Sn₄ intermetallic compound, dissolved tin, and a Cu?Sn intermetallic compound formed at the interface of the copper substrate.     

Optical properties of F.I.R. metallic grids: Reflection phase shift measurements

Utilization of metallic grids stacks for F.I.R filters needs a good knowledge of optical properties of each grid. We study here an experimental method in order to determine the wave's change of phase by reflection on a wire grid. We use a Perot-Fabry interferometer constituted by these grids.     

Conversion of single-stranded oligonucleotides into cloned duplexes and its consecutive application to short artificial genes.

A general method to convert single-stranded, chemically synthesized oligonucleotides into cloned duplexes is described. Oligonucleotides supplied with 3'-terminal extensions that are complementary to 3'-protruding ends obtained by certain restriction enzymes can be cloned either directly or with the help of an adapter molecule into double-stranded vectors. Two methods have also been developed for consecutive cloning applications. According to these methods, the synthetic oligonucleotides (and their enzymatically prepared complementary strands) are joined, one after the other, inside a cloning vector, each joining requiring one cloning step. Synthetic genes are thus built up from oligonucleotides corresponding to only one strand of the DNA. The sequential assembly of the cloned duplex takes place in the 5' to 3' direction. Each oligonucleotide is supplied with a four-nucleotide-long 3'-terminal extension, but this sequence is eliminated when the joining takes place, leaving no limiting sequence between the oligonucleotides. The two consecutive cloning methods, the adapter and the polycloning site methods, are illustrated by the assembly of short artificial genes.     

Observation of a new metastable liquid-crystalline phase in supercooled blue phase systems

A new metastable liquid-crystalline phase BPS was observed in pure chiral compounds. The BPS is transformed reversibly from the supercooled BPI and is thermodynamically stable with respect to the BPI and metastable to the cholesteric phase. Rhombic single crystals of the BPS probably indicate a cubic lattice structure as in other BPs, but the lattice constant exhibits an anomalous temperature dependence.