Depolarization and fine structure effects in half collisions of sodium-noble gas systems

Population ratios and polarization of the Na3P _J fine structure states following far wing photon excitation of Na-noble gas collision pairs are studied with respect to the underlying interaction potentials and molecular coupling schemes. For this purpose spectral profiles of these quantities, i.e. its dependencies on excitation frequency, have been measured up to ±200 cm^?1 detuning from the NaD lines for NaAr and NaHe under nearly single collision conditions. Comparing the measured population ratios with quantummechanical coupled channels calculations the Σ potential well depths differ considerably from results of model potential calculations. Large residualJ=3/2 alignment observed in the far wings disagrees with simple models assuming incoherent excitation and/or full adiabatic reorientation of the radiating dipole along straight trajectories. By comparison with Lewis model calculations, using realistic trajectories and decoupling radius, it is found instead, that realistic trajectories are constitutive for alignment after Σ-excitation (blue wing), whereas coherence between the²Π_1/2 and²Π_3/2 states determine primarily alignment after Π-excitation (red wing).     

Do solid surface potential barriers retard convoy peak electrons?

Using a coaxial cylindric electron spectrometer and an electrostatic ion energy analyzer in tandem, a direct measurement of the difference of the energy of convoy peak electron and the electron equivalent ion energy of protons emerging from the downstream surface of C, Au and Al foils is performed in the proton energy range from 60 to 250 keV. This measurement is made possible using the accepted evidence that for a gas target these energies are equal. It is found that also for the beam foil convoy peak electrons, within an experimental average uncertainty of about ±0.1 eV, there is no difference between these energies. If one accepts that the origin of convoy electrons is from inside the solid, the conclusion is that no retardation by the solid surface potential barrier, which is of the order of a few eV, is observed. This is attributed to the strong electron-ion Coulomb interaction which almost completely overshadows the force exerted on the electron by the field of the surface barrier.     

Chiroptical studies-part 99: The circular dichroism of seven-membered lactams and lactones

This empirical analysis of CD data for 7-membered lactams includes examples of all twelve possible structural types in which the lactam is fused to a cyclohexane ring as part of a polycyclic compound. The CD behaviour of several classes of lactams shows ‘dOgura's sign rule’ to be an over-simplification. The signs and values of Δ? for lactams in which the second ring is fused at the 3,4- or 6,7-positions of the lactam ring show considerable deviations from the “normal’ values for 4,5- or 5,6-fused lactams.No simple pattern of group contributions emerged from this analysis, but a correlation of CD behaviour with the torsion angle in the C-CO-NH-C structural component is suggested, on the basis of a study of Dreiding models, and is supported by the result of an X-ray crystallographic analysis of one of the lactams.This study of CD data is extended to a smaller group of lactones with a seven-membered ring, most of which show Cotton effects opposite in sign and of smaller magnitude than those of the corresponding lactams.     

Ascorbate-induced oxidation of formate by peroxodisulfate: product yields,kinetics and mechanism

The slow reaction between peroxodisulfate and formate is significantly accelerated by ascorbate at room temperature. The products of this induced oxidation, CO₂ and oxalate (C₂O^2– ₄), were analyzed by several methods and the kinetics of this reaction were measured. The overall mechanism involves free radical species. Ascorbate reacts with peroxodisulfate to initiate production of the sulfate radical ion (SO^– ₄), which reacts with formate to produce carbon dioxide radical ion (CO^– ₂) and sulfate. The carbon dioxide radical reacts with peroxodisulfate to form CO₂ or self-combines to form oxalate. Competition occurring between these two processes determines the overall fate of the carbon dioxide radical species. As pH decreases, protonation of the carbon dioxide radical ion tends to favor production of CO₂.     

Bidentate ligands formed by self-assembly

A novel supramolecular strategy to prepare bidentate ligands via the assembly of functionalised monomeric ligands on a dimeric zinc(II) porphyrin template is presented; the assembled bidentate ligands show chelating behaviour and their rhodium complexes display enhanced selectivity in the hydroformylation compared to the non-template analogue.     

Gas-phase fragmentation of the Ag+—phenylalanine complex: Cation—π interactions and radical cation formation

Collision-induced dissociation experiments on the Ag+-phenylalanine complex using several collision energies were shown to yield ten different fragment ions. Unambiguous assignment of these fragment ions were made by careful analysis of deuterium labeling experiments. The losses of H2O, CO, CO2, and AgH were commonly observed; also encountered were the losses of H2, Ag, and H. Deuterium labeling experiments and density functional calculations have been employed to probe fragmentation mechanisms that account for all experimental results.     

The synthesis and transition temperatures of some trans-4-alkylcyclohexylethyl-substituted 2,3-difluorobiphenyls

Terphenyls with two lateral ortho-fluoro-substituents have proved to be excellent host materials for ferroelectric (S_C*) mixtures. The compounds reported here are biphenyls with the same arrangement of lateral substituents but with a trans-4-alkylcyclohexylethyl moiety as one of the terminal substituents. Such three ring systems retain the ability to generate the S_C mesophase and have low melting points. Low temperature lithiation procedures were used to prepare phenylboronic acids, which were then used in palladium catalysed cross-coupling procedures to prepare the desired compounds. The effect of molecular structure on the mesophase types and thermal stabilities is discussed and comparisons are made with analogous terphenyls and biphenyls with open chain terminal substituents.     

Simulation of the electronic and vibrational structure of hydrogenated amorphous silicon using cluster models

A set of simple models of hydrogenated amorphous silicon (a-Si:H) consisting of hypothetical silane molecules with diamond or similar lattices was studied by the semiempirical AM1 method. Densities of states and infrared spectra were calculated for the silane molecules and similar molecules with dangling bonds disorder, and with boron or phosphorus substitution to simulate doping. Some examples are presented, and a comparison is made with experimental properties of a-Si:H. It is proposed to use these models in a study of the Staebler–Wronski photodegradation of a-Si:H and other aspects of amorphous silicon technology. © John Wiley & Sons, Inc.     

On the effect of low-energy ion bombardment on polystyrene and polymethylmethacrylate etch rates in rf plasmas

The effect of low-energy ion bombardment on CD₄/O₂ and CF₃X (X=F, Cl, Br) plasma etching has been assessed by applying controlled rf bias voltages on polystyrene (PS) and polymethylmethacrylate (PMMA) samples. In both cases ion bombardment has been found to have a chemical effect. In the case of CF₄/O₂ discharges, ion bombardment has been found to change the relative etching efficiency of different mixtures. In the case of CF₃X plasmas, ion bombardment has been found to alter PMMA and PS etch rates in a different way. In particular, the ratios between CF₄ and CF₃X (X=Cl, Br) etch rates of PS have been found to decrease with increasing bias voltage. This effect has been tentatively attributed to an ion bombardment-induced enhancement of the reaction between the aromatic ring and halogen molecules formed in CF₃Cl and CF₃Br discharges.     

BINDING, EXCITATION ENERGY TRANSFER AND PHOTOSENSITIZATION IN GRISEOFULVIN-DNA MIXTURES

Abstract— The weak and reversible binding of the antifungal drug, griseofulvin (GF), to calf thymus DNA has been demonstrated by difference spectroscopy and the quenching of the fluorescence of GF by DNA observed. The value of K _n was determined to be 800 M ^-1by fluorescence quenching titration. Adenosine and guanosine also exhibit difference spectra with GF and quench GF fluorescence indicating that they may be the site of both binding and energy transfer. The in vitro photosensitization of DNA by griseofulvin is shown to occur. It is proposed that the clinically observed in vivo photosensitizing action of griseofulvin may result from binding followed by excitation energy transfer and that this may also be important in the antifungal activity of the drug.