Electron beam induced modification of poly(ethylene terephthalate) films

Electron beam processing of poly(ethylene terephthalate) (PET) films is found to promote significant changes in the melting heat, intrinsic viscosity and polymer film-liquid (water, isooctane and toluene) boundary surface tension. These properties are featured with several maximums depending on the absorbed dose and correlating with the modification of PET surface functionality. Studies using adsorption of acid-base indicators and IR-spectroscopy revealed that the increase of PET surface hydrophilicity is determined by the oxidation of methylene and methyne groups. Electron beam treatment of PET films on the surface of N-vinylpyrrolidone aqueous solution provided graft copolymerization with this comonomer at optimum process parameters (energy 700 keV, current 1 mA, absorbed dose 50 kGy).     

Vibrational EELS and DFT study of propionic acid and pyruvic acid on Ni(1 0 0): Effects of keto group substitution on room-temperature adsorption and thermal chemistry

The room-temperature adsorption and thermally induced processes of propionic acid and pyruvic acid on Ni(1 0 0) have been investigated by electron energy loss spectroscopy (EELS). Computational vibrational analysis of the optimized bidentate structures for acid-Ni model complexes (involving the organic acid and a Ni atom) has been performed by using the two-layer ONIOM method with the Density Functional Theory and used to interpret the vibrational EELS data. Dehydrogenation of the hydroxyl group is found to result in bonding of the carboxylate group in the propionate and pyruvate adspecies to either a single Ni surface atom in a bidentate configuration or two neighbouring Ni atoms in a bridge configuration. Given the similarities in the total energies and related vibrational frequencies obtained by the calculations in the case of pyruvate adspecies, it is difficult to differentiate the alternate adsorption structure, in which the keto O and hydroxyl O atoms are bonded to a Ni atom in a five-member chelate ring configuration. Furthermore, temperature-dependent EELS studies show that both the propionate and pyruvate adspecies could decompose upon annealing to above 400 K and further dissociate to CO adspecies above 550 K and to C and/or O above 600 K.     

EPR investigations of oxidation effects in (V1−xMox)2−δO3

Electron paramagnetic resonance (EPR) investigations has been carried out on the new family of molybdenum doped vanadium sesquioxides (V_1−xMo_x)_2−δO₃. The oxidation effects were monitored from the rate of paramagnetic V⁴⁺ created when the sample is exposed to the air. The effects of the oxidation time, sample temperature, and annealing at 1000 °C under a diluted hydrogen atmosphere on the EPR signal features are analyzed. The V⁴⁺ concentration in the oxidized samples is determined and the relaxation effects driven by the conduction electrons are pointed out from the thermal behaviour of the EPR line features. EPR spectra of all the oxidized samples also reveal a small ferromagnetic contribution strongly correlated with the V⁴⁺ content.     

Luminescence enhancement by hydrogenation of Si:Er,O

Erbium (Er)- and oxygen (O)-doped Cz–Si was additionally doped with hydrogen, using plasma enhanced chemical vapour deposition. Photoluminescence (PL) spectra show a large enhancement especially for samples treated with solid phase epitaxy before hydrogenation and annealing at 900°C later. Secondary ion mass spectroscopy measurements give evidence for an enhanced diffusion of O and Er at this temperature towards the surface. Etching shows that the PL does not stem from the heavily doped surface layer but from a deeper region with lower Er concentration. This conclusion is supported by the appearance of the so-called “cubic” centre with low solubility. Comparing the PL yield of the hydrogenated samples to that of samples with similar Er volume concentration but without hydrogenation still gives a large enhancement. We thus conclude that hydrogen can enhance the solubility of the cubic centre in Si:Er,O.     

Decay distribution of spontaneous emission from atoms in one-dimensional photonic crystal

Spontaneous emission behavior from atoms (or molecules) in one-dimensional photonic crystal with a defect is investigated. Taken all the TE and TM modes into account, the normalized spontaneous emission rate of the atom is calculated as a function of the position of the atom in the crystal. Results for both nonabsorbing dielectric structure and absorbing dielectric structure are presented. With the increase of the thickness of the defect in which the atoms are embedded, the oscillations of the spontaneous emission rate versus the position of the atom become dense and the lifetime distribution becomes narrow and sharp. The PC effect may lead to the coexistence of both accelerated and inhibited decay processes.     

Organocatalysis: quantum chemical modeling of nucleophilic addition to α,β‐unsaturated carbonyl compounds

One of the successful transformations within the field of organocatalysis, the organocatalytic asymmetric addition of nitromethane to α,β‐unsaturated aldehydes and ketones, has been studied by quantum chemical modeling. The level of accuracy of the hybrid density functional theory method B3LYP/6‐31G(d) was compared to a high level ab initio benchmark for this reaction. It is concluded that B3LYP/6‐31G(d) performs very well for this reaction type, giving good estimates of critical energies. The reaction between acrolein and nitromethane was studied in detail. The reaction mechanism revealed an intermediate oxazolidin structure, which is currently unknown. Alkyl substitution in various positions on the amine catalyst or α,β‐unsaturated carbonyl compound influences the reactivity in a predictive fashion. The iminium ion, prop‐2‐en‐iminium, is less activated towards nucleophilic attack compared to protonated acrolein. Copyright © 2007 John Wiley & Sons, Ltd.     

A Generalized Unpaired Electron Spin Density Equation and Organic Hyperconjugation Mechanism

A large class of stereochemcial and related interactions in organic chemistry are repulsive and others are attractive, but the relative orientation of two methyl groups and the amount of energy required to twist one relative to the other (the hindered rotation energy barriers), or the alignment of such a group with respect to a conjugated ring to which it is attached (widely attributed to a mechanism called “hyperconjugation”) are estimated to be small in compared with the total energy of the molecule. We used theories of both isotropic and anisotropic proton hyperfine interactions in the π‐electron systems developed in the early sixties. They are approximated by the magnetic dipole nteractions between each proton and an electron spin magnetization that is distributed in 2s and 2p Slater atomic orbitals center on carbon atoms. We have extended these theories to the non‐planar olefinic cation radicals, which are very important in biochemistry as well as in petroleum catalysis. A three dimensional electron spin density equation has been developed in this paper to handle some Jahn‐Teller vibronic molecules. The new electron spin density equation related the observed proton hyperfine splittings to the non‐planar structures of the open‐chain alkene cation radicals generated by radiolysis and various chemical oxidation methods. The spin densities and the conformational calculations based on valence bond theory and symmetry principles are compared with some more elaborated molecular orbital calculations in the literature. The localized valence bond approaches are better in accord with our experimental results. The anomalous line‐width effect of the four methyl groups observed in the 2,3‐dimethyl‐2‐butene cation radicals also confirmed the positive sign of the electron‐proton hyperfine constant of hyper‐conjugation mechanism. A methyl substituent attached to a conjugated molecule often behaves as if it formed part of the region of conjugation; the charge appears to flow from the methyl group into the π electron system and it may also give rise to an appreciable dipole moment. Methylation also gives rise to an appreciable dipole moment, and the resultant red shift of electronic absorption bands is of some importance in the design of dye molecules.     

绿色荧光粉YAGG∶Tb,Gd用于FED的尝试

FED器件的发展迫切需要具有化学和热稳定性 ,高亮度 ,长寿命的新型荧光材料。本文合成了Gd3 +离子共掺杂的YAGG∶Tb获得了YAGG∶Tb ,Gd ,并将其用于 0～ 30 0 0V低压范围 ,对其在不同电压和电流密度下的发光特性进行了测试。结果表明 ,该种材料特性优于ZnO∶Zn并且不存在电压与电流饱和     

Theoretical study of cyclization of 2′-hydroxychalcone

The isomerization mechanism of 2′(OH)chalcone (1) in flavanone (2) was studied. The calculations were performed with the semiempirical method AM1, using totally optimized molecular geometries. A 6-step mechanism including several equilibrium states was proposed. It was concluded that: (a) At the conformational equilibrium of 1 there could be 43.9% of s-cis conformer; (b) The acid dissociation of 1 trans-s-trans is considerable; (c) The E_E, ΔH_f and net charges show that the rotation of ring A of 1 and the formation of ring C of 2 occurs without greater impairments; (d) Although the keto structure is the most stable one, the enolate of 2 is present in the reaction medium; (e) The conversion of enol of 2 in the keto form would be the limiting step of the analyzed isomerization rate.