Electrooptic study of antiferroelectric mixtures for display application

The aim of this paper is to study the influence of electric field on alignment of para-, ferro- and antiferroelectric phases in the vicinity of SmA^* — SmC^* or SmC^* — SmC _A ^* phase transitions as to obtain mono-domain cells. Four mixtures studied (W-193B, W-193B-1, W-201, W-204D) show the SmC _A ^* phase in a wide room temperature range. Measurements of the spontaneous polarization versus temperature by using reversal current method give an answer to the question, what kind of the transitions take place between para-, ferro- or antiferroelectric phases using the Landau mean field theory. Optimal electrooptic parameters for different compositions of the mixtures such as tilt angle, spontaneous polarization and saturation voltage have been measured to compare parameters of the mixtures studied.     

A new type of five-ring banana-shaped mesogens with strong dielectric response

Three new homologous bent-shaped mesogens with terminal octyloxy P8, decyloxy P10 and dodecyloxy P12 groups were synthesized. Calorimetric, X-ray and electro-optic investigations prove the existence of two mesophases of the SmCP_A type for compound P10 but only one SmCP_A phase for the homologues P8 and P12. The static dielectric permittivities of compound P12 and that of the low-temperature phase of substance P10 are in the order of 30 and agree with results on bent-core mesogens published before. Surprisingly, the dielectric permittivities of P8 and of the high-temperature phase of P10 are of about 1000. We explain this extremely high dielectric response with the soft reaction of ferroelectric units in the external electrical field.     

The confinement of smectics with a strong anchoring

We examine several geometric features of the confinement of lamellar materials in complex geometries. When the anchoring of a sample at its boundaries (smectic-fluid interfaces or smectic-solid substrates interfaces) is strong enough, the geometric approximation of parallel layers can be extended to the bounding surface of the sample. Depending on the concavity of the interface, a strong planar anchoring is then compatible (or not) with a smectic organization in the bulk. We give the simplest smectic organization which satisfies a planar anchoring everywhere on the interface of axisymmetric inverse SmA droplets and compute its curvature energy. Eventually, the reason is given why the textures of direct and inverse SmA droplets are so much different (as it was first noticed in the pioneering work on SmA of Friedel and Grandjean). Received 11 May 2000     

Synthesis and properties of high tilted antiferroelectric esters with partially fluorinated alkoxyalkoxy terminal chains

Novel chiral esters with partially fluorinated alkoxyalkoxy terminal chains are described. Their phase transition temperatures, enthalpies, and electrooptical properties are reported. A helical pitch in pure compounds and their mixtures based on selective reflection of light is also characterized.     

Sulfonium-aided coupling of aromatic rings via sigmatropic rearrangement

Biaryl synthesis continues to occupy a central role in chemical synthesis. From blockbuster drug molecules to organic electronics, biaryls present numerous possibilities and new applications continue to emerge. Transition-metal-catalyzed coupling reactions represent the gold standard for biaryl synthesis and the mechanistic steps, such as reductive elimination, are well established. Developing routes that exploit alternative mechanistic scenarios could give unprecedented biaryl structures and expand the portfolio of biaryl applications. We have developed metal-free C–H/C–H couplings of aryl sulfoxides with phenols to afford 2-hydroxy-2′-sulfanylbiaryls. This cascade strategy consists of an interrupted Pummerer reaction and [3,3] sigmatropic rearrangement. Our method enables the synthesis of intriguing aromatic molecules, including oligoarenes, enantioenriched dihetero[8]helicenes, and polyfluorobiaryls. From our successes in aryl sulfoxide/phenol couplings and a deeper understanding of sigmatropic rearrangements for biaryl synthesis, we have established related methods, such as aryl sulfoxide/aniline and aryl iodane/phenol couplings. Overall, our fundamental interests in underexplored reaction mechanisms have led to various methods for accessing important biaryl architectures.     

Experimental evidence of chiral crown ether complexation with aromatic amino acids

The complexation of L ‐ and D ‐enantiomers of phenylglycine, phenylalanine, and tryptophan with D ‐mannonaphto‐crown‐6‐ether in methanol solution was studied by NMR and isothermal titration calorimetry (ITC) at 298.15 K. The total heat effects attributed to the binding phenomena were measured in the range of 1.8 to 7.7 mJ, and the complexation was found stereo‐specific. The binding topologies were estimated basing on ¹H 2D‐ROESY experiments. The analysis of Job plots obtained from ¹H NMR‐monitored titrations proved the coexistence of 1:1 and 1:2 (crown ether:amino acids) complexes, which thermodynamic parameters, K_s, ΔG, ΔH°, and TΔS were determined with the aid of ITC. The 1:1 complexes were found enthalpically stabilized, generally by electrostatic interactions between the charged NH group of amino acid and crown ether macrocyclic moiety, while the binding of the second amino acid molecule was driven entropically due to solvatophobic effect. Strong enthalpy–entropy compensation points towards the uniform binding mode of all complexes studied. The mode of complex formation was found solvent dependent. For phenylalanine guest studied in various solvent systems, in contrast to the aqueous media, the noticeable chiral recognition is observed in methanol solution, and the complex stoichiometry (1:2 ether:Phe) differs from the 2:1 one, determined previously for the same host‐guest system in water (J. Thermal. Anal. Cal. 2006; 83: 575–578). Copyright © 2007 John Wiley & Sons, Ltd.     

SERF-filtered experiments: new enantio-selective tools for deciphering complex spectra of racemic mixtures dissolved in chiral oriented media

The use of chiral liquid crystals as NMR solvent is a powerful tool to visualize and quantify enantiomers. This technique is much more robust than traditional liquid state techniques. Recent developments have been performed to simplify proton spectra obtained in these solvents which are usually complex to analyze. In the different published sequences the enantiomeric differentiation can be visualized but none of them rely the different (1)H-(1)H couplings to have a coherent set for each enantiomer especially in cases of racemic mixtures. In this work to overcome such limitations, we present a new NMR pulse sequence using semi-selective pulses to assign for each enantiomer the different (1)H-(1)H couplings. The aim is to obtain the signal of only one enantiomer, through a first Selective ReFocussing (SERF) filtering block implemented for the enantio-selection followed by a second SERF block for measuring a chosen coupling. The whole sequence is called (1)H SERF-filtered-SERF. These techniques permit for the first time to assign all dipolar couplings to each enantiomer of racemic mixtures dissolved in chiral oriented media. We demonstrate that using this experiment it is possible to visualize enantio-differentiation even in the case where the multiplets are not resolved in the SERF experiments, pushing back the limits of the enantiomeric visualization.     

加绕变升角宽频带椭圆螺旋天线

 椭圆螺旋天线的结构比传统的圆柱螺旋天线更加适合于卫星通信的终端,然而由于其圆极化特性变差而限制了其广泛应用。把改善轴向模螺旋天线辐射特性的两种方法结合起来应用于椭圆螺旋天线,提出了带有附加螺旋线的变升角轴向模椭圆螺旋天线。以一个5圈、短轴长轴之比为0.65的椭圆螺旋天线为例,用FEKO软件对其辐射特性进行了仿真。结果表明,这种方法提高了椭圆螺旋天线的方向性系数,同时具有较好的圆极化特性。在2.2~4.2 GHz频率范围内,最高增益为12.86 dB,比单绕均匀升角的椭圆螺旋天线提高了1.2 dB。     

Helical twisting power of antiferroelectric chiral terphenyls in different matrices

To determine the influence of chemical structure on the Helical Twisting Power (HTP), we tested four optically active dopants having a terphenyl rigid core and the same chiral centre but differing in the length of nonchiral terminal chain and the substitution of benzene rings with fluorine atoms. The compounds were added to different achiral liquid crystalline matrices: nematic and smectic C. It was found that HTP as well as its temperature variation depends on the kind of used matrices. It gives a conclusion that information about HTP obtained in one matrix cannot be uncritically transferred to another one.     

加绕变升角宽频带椭圆螺旋天线

椭圆螺旋天线的结构比传统的圆柱螺旋天线更加适合于卫星通信的终端,然而由于其圆极化特性变差而限制了其广泛应用。把改善轴向模螺旋天线辐射特性的两种方法结合起来应用于椭圆螺旋天线,提出了带有附加螺旋线的变升角轴向模椭圆螺旋天线。以一个5圈、短轴长轴之比为0.65的椭圆螺旋天线为例,用FEKO软件对其辐射特性进行了仿真。结果表明,这种方法提高了椭圆螺旋天线的方向性系数,同时具有较好的圆极化特性。在2.2~4.2 GHz频率范围内,最高增益为12.86 dB,比单绕均匀升角的椭圆螺旋天线提高了1.2 dB。     

Low frequency dielectric spectroscopy of two room temperature chiral liquid crystal mixtures

Dielectric spectroscopy of two room temperature chiral liquid crystal mixtures (W-96 and W-97) have been carried out in the frequency range of 100?mHz–10?MHz. Low frequency dielectric relaxation modes corresponding to collective behavior of molecules (Goldstone- and soft-modes) in the SmC* phase have been found to be masked by the ionic conductance. Two slow modes of dielectric relaxation due to the ionic conductance have been detected (below 15?Hz) in planar-aligned samples. It has been observed that the effect of ionic conductance decreases with the number of thermal annealing cycles on the materials. With large number of thermal annealing cycles it has been possible to wipe out the effects of ionic conductance and then to detect other weak modes of dielectric relaxation which are otherwise masked.     

Dielectric properties of LC mixture with induced antiferroelectric phase

Mixture of two liquid crystalline components exhibits the antiferroelectric phase in a broad temperature range at room temperatures, though the two components separately do not show an antiferroelectric phase in a temperature range applied. The dielectric spectroscopy technique combined with measurements of the selective light reflection was used for identification and characterization of the phases and subphases existing in the mixture. In the SmC*_A phase, the low frequency mode characteristic of antiferroelectric phase has been detected. In the broad temperature range between SmC*_A and SmA* phases, no relaxation mode has been detected. The soft mode registered near the phase transition to SmA* phase follows the Curie-Weiss law.     

Quantum chemical study of a new class of sensitisers: influence of the substitution of aromatic rings on the properties of copper complexes

We present a computational study of new copper complexes with potential applications as sensitisers for solar cells. The applied methodology for this study is based on the density functional theory (DFT) and time-dependent DFT, using the B3LYP, PBE0 and M06 functionals with the LANL2DZ (D95V on first row), 6-31G(d,p), 6-311G(d,p) and DZVP basis sets. Optimised molecular structure, the absorption spectra, the molecular orbitals energies and the chemical reactivity parameters that arise from conceptual DFT were calculated. Solvent effects have been taken into account by an implicit approach, namely, the polarisable continuum model (PCM), using the non-equilibrium version of the integral equation formalism of the PCM model. Interesting work for experimentalists in the dye sensitised solar cells’ field.     

(PbBa)(Zr,Sn,Ti)O_3反铁电/弛豫型铁电相界陶瓷的相变与介电、热释电性质

通过对(Pb087Ba01La002)(Zr06TixSn04-x)O3(004≤x≤020)固溶体的介电和偏压热释电性质的研究发现,当Ti含量004≤x≤007时,材料是反铁电四方相,而当009≤x≤020时,材料向弛豫型铁电体转化.在温度Ti含量相图中,x=009附近形成了反铁电铁电顺电三相共存点(Ttr).该点的相变温度最底;对于004≤x≤007的反铁电四方相,低温下呈现介电弛豫特征,并可被外电场诱导为亚稳铁电态,温度升高时,亚稳铁电→反铁电相变,反铁电→顺电相变引起两个热释电流峰,偏置电场下峰位和峰强均发生移动,在温度电场相图中也形成了铁电反铁电顺电三相点.从复杂化合物纳米相分离的观点和晶格动力学出发,讨论了相变与电学性能随Ti含量(x)和外电场(E)变化的物理机理. 关键词： 反铁电/弛豫型铁电相界 介电性能 偏压热释电性质 铁电-反铁电-顺电三相点     

Third-order nonlinear optical studies of new anthraquinone derivatives

Four new donor-acceptor-donor anthraquinone derivatives were synthesized and characterized by UV, IR, ¹H NMR and elemental analysis. Their off-resonant third-order nonlinear optical properties were measured using femtosecond laser and degenerate four-wave mixing technique. The third-order nonlinear optical susceptibilities χ⁽³⁾ were 3.36-3.76 × 10⁻¹³ esu. The nonlinear refractive indexes n₂ were 6.19-6.91 × 10⁻¹² esu. The second-order hyperpolarizabilities γ of the molecules were 3.36-3.76 × 10⁻³¹ esu. The response times were 101-115 fs. The results show that these compounds have potential nonlinear optical applications.     

Chemical modification of silica gel with synthesized new Schiff base derivatives and sorption studies of cobalt (II) and nickel (II)

In this study, three Schiff base ligands and their complexes were synthesized and characterized by infrared spectroscopy (IR), thermogravimetric analyses (TGA), nuclear magnetic resonance (NMR), elemental analysis and magnetic susceptibility apparatuses. Silica gel was respectively modified with Schiff base derivatives, (E)-2-[(2-chloroethylimino)methyl]phenol, (E)-4-[(2-chloroethylimino)methyl]phenol and N,N′-[1,4-phenilendi(E)methylidene]bis(2-chloroethanamine), after silanization of silica gel by (3-aminopropyl)trimethoxysilane (APTS) by using a suitable method. Characterization of the surface modification was also performed with IR, TGA and elemental analysis. The immobilized surfaces were used for Co(II) and Ni(II) sorption from aqueous solutions and values of sorption were detected by atomic absorption spectrometer (AAS).     

W波段螺旋波纹波导回旋行波管注波互作用的非线性分析

本文从有源麦克斯韦方程组出发, 系统地推导了螺旋波纹波导的色散方程及非线性注波互作用理论, 数值计算结果与已有的实验报道基本相符.在此基础上,设计了W波段螺旋波纹回旋行波管, 工作电压80 kV, 工作电流5 A, 中心频率95 GHz, 3 dB带宽约4.5%, 饱和增益52 dB, 最大输出功率142 kW, 电子效率达20%-35%.最后,本文计算了电流, 电压及输入功率的改变对W波段螺旋波纹波导回旋行波管输出性能的影响.