Structure and Structural Nonrigidity of Tetrachlorodibenzo-p-Dioxin Radical Cations

Ab initio calculations showed that the tetrachlorodibenzo-para-dioxin radical cations (TCDD RCs) with a planar structure have two steady states with asymmetric dioxin cycles. The activation barriers between these states are up to 2 kcal/mole, so that the RCs may be regarded as being structurally nonrigid within the dioxin cycle. The 2,3,7,8-TCDD RC is more stable than the 1,4,6,9-TCDD RC, the energy difference being 5.2 kcal/mole. The adiabatic ionization potential of 2,3,7,8-TCDD (7.54 eV) is 0.1 eV smaller than the corresponding potential of 1,4,6,9-TCDD. These factors account for the increased hemoproteide affinity and hence increased biological activity of 2,3,7,8-TCDD.     

Synthesis and Crystal Structure of the Hydrogen Polyphosphide Bis(Tetraphenylphosphonium) hydrogenheptaphosphide‐ammonia(1/3) (PPh4)2HP7 · 3NH3

(PPh₄)₂HP₇ · 3NH₃ was prepared by the reaction of K₃P₇ with a proton‐charged ion exchange resin in the presence of (PPh₄)Br in liquid ammonia, and characterized by low temperature X‐ray structure analysis. The thermally very unstable compound contains the hydrogenheptaphosphide anion HPequation/tex2gif-stack-1.gif, the nortricyclane‐like cage of which is slightly distorted by the attachment of the hydrogen atom.     

Numerical simulations of a filament in a flowing soap film

Experiments concerning the properties of soap films have recently been carried out and these systems have been proposed as experimental versions of theoretical two‐dimensional liquids. A silk filament introduced into a flowing soap film, was seen to demonstrate various stable modes, and these were, namely, a mode in which the filament oscillates and one in which the filament is stationary and aligns with the flow of the liquid. The system could be forced from the oscillatory mode into the non‐ oscillatory mode by varying the length of the filament. In this article we use numerical and computational techniques in order to simulate the strongly coupled behaviour of the filament and the fluid. Preliminary results are presented for the specific case in which the filament is seen to oscillate continuously for the duration of our simulation. We also find that the filament oscillations are strongly suppressed when we reduce the effective length of the filament. We believe that these results are reminiscent of the different oscillatory and non‐oscillatory modes observed in experiment. The numerical solutions show that, in contrast to experiment, vortices are created at the leading edge of the filament and are preferentially grown in the curvature of the filament and are eventually released from the trailing edge of the filament. In a similar manner to oscillating hydrofoils, it seems that the oscillating filaments are in a minimal energy state, extracting sufficient energy from the fluid to oscillate. In comparing numerical and experimental results it is possible that the soap film does have an effect on the fluid flow especially in the boundary layer where surface tension forces are large. Copyright © 2004 John Wiley & Sons, Ltd.     

LINEAR ACTIVE STRUCTURES AND MODES (Ⅱ)--DISCRETE SYSTEMS AND BEAMS

The basic concepts about the active structures and some attributes of the modes were presented in paper "Liner Active Structures and Modes ( Ⅰ ) ". The characteristics of the active discrete systems and active beams were discussed, especially, the stability of the active structures and the orthogonality of the eigenvectors. The notes about modes were portrayed by a model of a seven-storeyed building with sensors and actuators. The concept of the adjoint active structure was extended from the discrete systems to the beams that were the representations of the continuous structures. Two types of beams with different placements of the measuring and actuating systems were discussed in detail. One is the beam with the discrete sensors and actuators, and the other is the beam with distributed sensor and actuator function. The orthogonality conditions were derived with the modal shapes of the active beam and its adjoint active beam. An example shows that the variation of eigenvalues with feedback amplitude for the homo-configuration and non-homo-configuration active structures.     

Measurements of Time-Varying Characteristics of Optical Signals and Inhomogeneities of Tested Substances with Additional Phase Modulation

The problem of investigation of the amplitude and phase structure of a time-varying probing optical signal and the structure of time-varying inhomogeneities of a substance tested by this signal is considered. The analysis is concerned, in particular, with determination of the structure of signals and processes with resolution in the pico- and femtosecond range. The scheme used for the analysis is based on registration of four spatially separated spectra of the studied radiation. The spectra are formed in a four-channel scheme with a twin-wave Michelson interferometer and a spectral device. Modulators based on electrooptical crystals (perovskites) are placed in the channels. The sum spectra are formed: without modulators, with the effect of either of the modulators, and with both of them affecting the radiation. The effect of the studied substance implies either modulating the radiation (in this case it is described by multiplication) or redistributing the radiation (then it is described by convolution).     

Stereological simulations of asymmetric polymerization in channels of bile acid inclusion compounds: A detailed analysis of the monomer arrangements in the channels

We studied simulations by computer graphics to estimate the steric mechanism of the asymmetric polymerization of prochiral diene monomers in channels of inclusion compounds of steroidal bile acids, such as deoxycholic acid (DCA) and cholic acid. We applied a hierarchization method to interpret the crystal structures of bile acids, clarifying that the chiral host molecules associated to form characteristic 2₁-helical assemblies with uneven surfaces. A detailed analysis of the uneven channels in a close-packing state indicated that there were many possible arrangements of the monomers in the channels. The plausible arrangements in the channel could explain a previous study, which showed that the polymerization in the DCA channel yielded chiral polymers with a predominant configuration from prochiral diene monomers, such as 2-methyl-trans-1,3-pentadiene. On the basis of such simulation studies of the arrangements of guest monomers in the channel, we examined a plausible steric mechanism for asymmetric inclusion polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4648–4655, 2004     

Changes in the near-edge X-ray absorption fine structure spectra of long-chain diacetylene derivatives through photopolymerization in Langmuir–Blodgett films

Photopolymerization of cadmium 10,12-pentacosadiynoate (CdDA) in Langmuir–Blodgett (LB) films, with the molecular packing well arranged by moderate preannealing, was investigated with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Greenish films of polydiacetylene with an absorption wavelength of 705 nm were obtained through the photopolymerization of preannealed monomer LB films, and this resulted in an extended π-conjugate system based on the well-ordered monomer in a two-dimensional arrangement. The electronic structures of the polydiacetylenes were found to be correlated to the variation of the molecular arrangements in the films from the changes in the NEXAFS spectra through photopolymerization in the LB films. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2329–2336, 2004     

Geometrical Molecular Structure Design Concept in Approach to Homo- and Heterometallic Precursors of Advanced Materials in Sol–Gel Technology

The article describes the principles of the Single Source Precursor approach to inorganic materials and introduces the Geometrical Molecular Structure Design Concept (MSDC) based on the choice of a proper molecular structure type for the desired precursor and completing it with ligands providing both the necessary number of donor atoms and the sterical protection of the chosen core. Application of MSDC is illustrated with examples taken from development of new approaches in the synthesis of oxide and sulfide catalysts and ferroelectric oxide materials.     

Structure,morphology, and crystallization process of isotactic polypropylene/hydrogenated hydrocarbon resin blends

The structure, morphology, and isothermal and nonisothermal crystallization of isotactic polypropylene/low‐molecular‐mass hydrocarbon resin blends (iPP/HR) (up to 20% in weight of HR) have been studied, using optical and electron microscopy, wide‐ and small‐angle X‐ray and differential scanning calorimetry. New structures and morphologies can be activated, using appropriate preparation and crystallization conditions and blend composition. For every composition and crystallization condition, iPP crystallizes in α‐form, with a spherulitic morphology. The size of iPP spherulites increases with resin content, whereas the long period decreases. In the range of crystallization temperatures investigated, HR modifies the birefringence of iPP spherulites, favoring the formation of radial lamellae and changing the ratio between tangential and radial lamellae. Spherulitic radial growth rates, overall crystallization rates, and melting temperatures are strongly affected by resin, monotonically decreasing with resin content. This confirms miscibility in the melt between the two components of the blends. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3368–3379, 2004     

螺旋线径向挤压变形对其慢波结构冷测特性的影响

 介绍了用MAFIA软件的准周期边界条件计算螺旋线行波管慢波结构的色散和耦合阻抗，以及用ANSYS软件对螺旋线径向挤压变形建模的方法，并对螺旋线受挤压径向变形对其冷测特性的影响进行了详细的分析。结果表明:螺旋线径向挤压变形会导致相速增大，而在通常的变形范围内耦合阻抗也会增加；当变形继续增大时耦合阻抗上升到最大值后开始下降。