Novel halogenated cyclopentasilylene-2,4-dienes via DFT

In view of immense importance of silylenes and the fact that their properties undergo significant changes on substitution with halogens, here, we have used B3LYP/6-311++G** level of theory to access the effects of 1–4 halogens (X = F, Cl, Br, and I) on four unprecedented sets of cyclopentasilylene-2,4-dienes; with the following formulas: SiC₄H₃X ( 1 _X ), SiC₄H₂X₂ ( 2 _X ), SiC₄HX₃ ( 3 _X ), and SiC₄X₄ ( 4 _X ). In going down from F to I, the singlet (s)-triplet (t) energy gap (ΔE_s-t, a possible indication of stability), and band gap (ΔE_H-L) decrease while nucleophilicity (N), chemical potential (μ), and proton affinity (PA) increase. The overall order of N, μ, and PA for each X is 2 _X > 1 _X > 3 _X > 4 _X . Precedence of 2 _X over 1 _X is attributed to the symmetric cross conjugation in the former. The highest and lowest N are shown by 2 _I and 4 _F . The trend of divalent angle () for each X is 4 _X > 1 _X > 3 _X > 2 _X . The results show that in going from electron withdrawing groups (EWGs) to electron donating groups (EDGs), the ΔE_s-t and ΔE_H-L decrease while N, μ, and PA increase. Also, rather high N of our scrutinized silylenes may suggest new promising ligands in organometallic chemistry.     

极化子导电到能带导电的转变

采用交流法测量大功率商用钛酸钡(BT)陶瓷加热器的电阻和加热功率随温度的变化关系.结果显示,BT陶瓷的电导特性在80℃附近出现了明显的转变,从低温时的极化子跳跃导电转变为高温时的能带导电,此时,电阻出现极小值,而加热功率出现极大值.     

Equivalences of comodule categories for coalgebras over rings

In this article we defined and studied quasi-finite comodules, the cohom functors for coalgebras over rings. Linear functors between categories of comodules are also investigated and it is proved that good enough linear functors are nothing but a cotensor functor. Our main result of this work characterizes equivalences between comodule categories generalizing the Morita-Takeuchi theory to coalgebras over rings. Morita-Takeuchi contexts in our setting is defined and investigated, a correspondence between strict Morita-Takeuchi contexts and equivalences of comodule categories over the involved coalgebras is obtained. Finally, we proved that for coalgebras over QF-rings Takeuchi's representation of the cohom functor is also valid.     

Higher Order Peak Algebras

Using the theory of noncommutative symmetric functions, we introduce the higher order peak algebras (Sym(N))_N≥1, a sequence of graded Hopf algebras which contain the descent algebra and the usual peak algebra as initial cases (N=1 and N=2). We compute their Hilbert series, introduce and study several combinatorial bases, and establish various algebraic identities related to the multisection of formal power series with noncommutative coefficients. Received November 19, 2004     

Assignment of conformation-sensitive near-infrared bands in high-spin ferrous haemoproteins. Low-temperature magnetic circular dichroism data

An assignment of the near-infrared bands in the 600–800 nm spectral region observed in magnetic circular dichroism (MCD) spectra of high-spin ferrous haemoproteins is presented. The assignment is based on a relative energy level scheme for iron d-electrons, a comparison of predicted and measured temperature dependences of MCD intensity, a sign of MCD bands and a group theoretical analysis of allowed transitions. The proposed assignment is consistent with the ∼15-nm red shift of the ∼760 nm band on breakage of the Fe-His bond in deoxy-myoglobin at low pH, with low-temperature photolysis experiments available for CO complexes of several haemoproteins. In accordance with the observations, the intensity of the MCD bands for proteins with a sulphur anion of cysteine as proximal haemligand (cytochrome P450 and chloroperoxidase) is predicted to be diminished by at least one order of magnitude compared to that for proteins with an imidazole of a histidine as a protein-derived haemligand (i.e. myoglobin, haemoglobin and horseradish peroxidase). Received: 4 February 1997 / Accepted: 1 May 1997     

Tunable properties of light propagation in photonic liquid crystal fibers

Tunable properties of light propagation in photonic crystal fibers filled with liquid crystals, called photonic liquid crystal fibers (PLCFs) are presented. The propagation properties of PLCFs strongly depend on contrast between refractive indices of the solid core (pure silica glass) and liquid crystals (LCs) filing the holes of the fiber. Due to relatively strong thermo-optical effect, we can change the refractive index of the LC by changing its temperature. Numerical analysis of light propagation in PLCF, based on two simulation methods, such as finite difference (FD) and multipole method (MM) is presented. The numerical results obtained are in good agreement with our earlier experimental results presented elsewhere [1].     

On bimeasurings II

We answer some questions posed in [L. Grunenfelder, M. Mastnak, On bimeasurings, J. Pure Appl. Algebra 204 (2006) 258-269] concerning the universal bimeasuring bialgebra via a construction of suitable subcoalgebras of the universal measuring coalgebra.     

Bidendriform bialgebras, trees, and free quasi-symmetric functions

We introduce bidendriform bialgebras, which are bialgebras such that both product and coproduct can be split into two parts satisfying good compatibilities. For example, the Malvenuto-Reutenauer Hopf algebra and the non-commutative Connes-Kreimer Hopf algebras of planar decorated rooted trees are bidendriform bialgebras. We prove that all connected bidendriform bialgebras are generated by their primitive elements as a dendriform algebra (bidendriform Milnor-Moore theorem) and then is isomorphic to a Connes-Kreimer Hopf algebra. As a corollary, the Hopf algebra of Malvenuto-Reutenauer is isomorphic to the Connes-Kreimer Hopf algebra of planar rooted trees decorated by a certain set. We deduce that the Lie algebra of its primitive elements is free in characteristic zero (G. Duchamp, F. Hivert and J.-Y. Thibon conjecture).     

Characterization of oxide thin films using optical techniques

Thin films of oxide materials are playing a growing role as critical elements in optoelectronic devices and nanoscale devices. In this work, thin films of some typical oxides such as WO₃, Ga₂O₃ and SrTiO₃ were investigated. We present measurements of those films, using various optical techniques like photoconductivity transients over a wide time range and photo-Hall measurements. Analysis of the photo-Hall and photoconductivity data permits the determination of the contribution to the photoconductivity made by the carrier mobility and concentration. A model for dispersive carrier transport was proposed to explain the relaxation of the photoconductivity in oxide thin films. In addition, photoluminescence characterization was used to study microstructures and energy band in oxide thin films. The broad emission from oxide host, consisting of several band peaks, was likely due to a recombination process with several possible paths. The dependence of the luminescent intensity on the annealing atmosphere was associated with the presence of oxygen vacancies. It is suggested that our optical analysis efforts have improved the understanding of oxide thin films, and this should lead to the necessary advancements in a variety of devices.     

The role of water vapour on the oxidation of two Ln-Si-Al-O-N glasses (Ln=Y, La)

The oxidation behaviour of LnSiAlON (Ln=Y, La) glasses was studied at different temperatures (990-1150 °C) and under different water vapour pressures (360-2690 Pa). These results were also compared with those obtained under O₂, N₂/H₂O or O₂/H₂O mixtures. When glasses are treated under a N₂/H₂O mixture, optical and SEM observations show porous scales. Transformations of the reaction rate data and a kinetic model show that there is only one limiting process occurring during oxidation. This rate limiting step is the progress of the chemical reaction at the internal interface. Determination of the pressure law dependence and thermodynamics calculations of water vapour molecules dissociation at the investigated temperatures allow us to suggest that the mechanism of oxidation corresponds to decomposition of water molecules on the oxynitride glass surface.