Phosphonate electrochemical recognition by molecularly imprinted deposited film

In this paper, thin films of titanium oxide imprinted with O,O-dimethyl-(2,4-dichlorophenoxyacetoxyl)(3′-nitrobenyl) methinephosphonate (Phi-NO₂) were prepared via liquid phase deposition (LPD) method on a glassy carbon electrode. The imprinted molecular in the films was removed by treatment with immersion in CH₂Cl₂. X-ray diffraction (XRD) and electrochemical methods were introduced to show the evidence of the molecular imprinting phenomenon. It was also found that the recognition ability of the sensor depended on the substituents associated with tridimensional structures of the nitro-compounds. Under the optimized condition, the sensor showed better sensitivity, selectivity and reproducibility to the imprinted molecule and the linear relationship between the current and the concentration of analyte in the range of 0.1-50 μM was obtained. LPD proved to be a powerful method for imprinting titanium oxide thin sense films.     

新型含氧亚甲基和亚胺桥键液晶化合物分子结构与光谱的密度泛函理论研究

采用密度泛函理论方法在B3LYP/6-31G*水平上对6个新型含氧亚甲基和亚胺桥键液晶化合物分子的几何结构进行优化计算,讨论了取代基H,CH3,CH3O,C2H5O,NO2,Cl对分子电荷、前线轨道能量和电子吸收光谱等性质的影响.在此基础上使用含时密度泛函理论方法计算了分子第一激发态的电子垂直跃迁能,得到最大吸收波长λmax.计算表明,取代基的引入导致最大吸收波长红移.     

Dynamics of liquid membranes. II: Adaptive finite difference methods

Two domain-adaptive finite difference methods are presented and applied to study the dynamic response of incompressible, inviscid, axisymmetric liquid membranes subject to imposed sinusoidal pressure oscillations. Both finite difference methods map the time-dependent physical domain whose downstream boundary is unknown onto a fixed computational domain. The location of the unknown time-dependent downstream boundary of the physical domain is determined from the continuity equation and results in an integrodifferential equation which is non-linearly coupled with the partial differential equations which govern the conservation of mass and linear momentum and the radius of the liquid membrane. One of the finite difference methods solves the non-conservative form of the governing equations by means of a block implicit iterative method. This method possesses the property that the Jacobian matrix of the convection fluxes has an eigenvalue of algebraic multiplicity equal to four and of geometric multiplicity equal to one. The second finite difference procedure also uses a block implicit iterative method, but the governing equations are written in conservation law form and contain an axial velocity which is the difference between the physical axial velocity and the grid speed. It is shown that these methods yield almost identical results and are more accurate than the non-adaptive techniques presented in Part I. It is also shown that the actual value of the pressure coefficient determined from linear analyses can be exceeded without affecting the stability and convergence of liquid membranes if the liquid membranes are subjected to sinusoidal pressure variations of sufficiently high frequencies.     

Improvement of the properties of polyarylate reinforced with liquid crystalline polymers

Blends of polyarylate of bisphenol A, PAr, with two commercial main chain liquid crystalline polymers, Vectra A950 and Vectra B950, are studied. From dynamic viscoelastic measurements it is deduced that both systems (PAr/Vectra A950 and PAr/Vectra B950) are immiscible and scanning electron microscopy (SEM) micrographs show the presence of spherical domains of the liquid crystalline polymer when PAr constitutes the matrix. Extrusion capillary measurements reveal that, under conditions of temperature and shear rate similar to those of processing, the viscosity is reduced to approximately 10% of its value when the content of liquid crystalline polymer is only 20%. This great improvement of the rheological properties is observed in both PAr/Vectra A950 and PAr/Vectra B950 blends. The effect of draw ratio on Young's modulus for different compositions is also analyzed, pointing out the reinforcing action of both liquid crystalline polymers on polyarylate: for instance, 20% of Vectra B950 in the blend gives rise to a 700% increase of the modulus of fibres prepared at a draw ratio of 50. SEM of the extrudates reveals that the spherical domains are elongated at the entrance of the capillary giving rise to a microfibrillar morphology which is related to the excellent rheological and mechanical properties of the blends.     

Use of a long-spacer-side-chain liquid crystalline polysiloxane containing a crown ether as a stationary phase for capillary gas chromatography

A new kind of side chain liquid crystalline polysiloxane containing a crown ether with a longer spacer (PSC-11) has been prepared and coated on a fused silica capillary column. The main chroma-tographic characteristics including efficiency, polarity, and selectivity have been examined. The phase exhibits the retention properties of both liquid crystal and crown ether stationary phases and possesses higher efficiency and better selectivity than PSC-3, which has a shorter spacer between the main polysiloxane chain and liquid crystalline side chain.     

Anomalous behavior of conductivity of the confined Q1D electron system over liquid helium

Conductivity of electrons in a quasi-one-dimensional (Q1D) system over liquid helium in narrow channels with the parabolic profile of the potential well has been investigated at temperature T, from 0.4 to 1.8 K, for different driving electric fields and radius of channel curvature. The interval of linear electron densities varied from 2.18×10³ up to 1.7×10⁶ cm⁻¹.

The inverse mobility (1/μ_eff) in the electron-ripplon scattering region at the high linear densities of charges in the channel increases with temperature decreasing. This anomalous behavior of the electron transport in the low-temperature region has been explained by either the electron ordering or the polaronic effects in confined conducting channels. The nonlinear behavior of the electron velocity as a function of a driving electric field is supposed to be due to Breg–Cherenkov radiation of the ripplons. The radiation occurred if the velocity of electrons in the channel approaches to the critical value.     

Recognition of Monohydrogen Anions of Geometrical and Positional Isomers of Dicarboxylic Acids Based on Polymeric Liquid Membranes Incorporating Polyamine Host

Macrocyclic lipophilic polyamines were applied as the sensory elements of polymeric liquid membrane electrodes. These hosts gain the anion receptor functionality upon protons uptake from the aqueous solutions. The electrodes studied were able to distinguish potentiometricaly isomers of monocharged and doublecharged forms of ethylene and benzene dicarboxylic acids. The selectivity of interaction between protonated hosts and anionic guests relays not only on the electrostatic interactions, but on hydrogen bounds formations as well. The influence of lipophilicity of protonated hosts on the potential response generation was discussed.     

Kinetic theories and mesoscopic models for solutions of nonhomogeneous liquid crystal polymers

We present a systematic derivation of hydrodynamic theories for nonhomogeneous nematic liquid crystal polymers (LCPs) by approximating the molecules as rigid ellipsoids, which can be either uniaxial molecules (spheroids) or biaxial ones. The short range interaction is assumed to be dominated by the excluded volume effect. Additional molecular properties with ellipsoidal molecules, e.g., a dipole–dipole interaction in extended nematics and chiral molecular structure in cholesterics, are accounted for through additional intermolecular potentials. Long-range molecular interaction is implemented through an averaged mean-field potential characterized by interaction functions. The extra elastic stress tensor is calculated using an extended virtual work principle consistent with conservation of angular momentum on the material volume, whereas the extra viscous stress is obtained by Batchelor’s volume averaging method. In the isothermal case, the theories are shown to satisfy the second law of thermodynamics, i.e., they admit positive production of entropy or energy dissipation. In the case of cholesterics, the kinetic theory reduces to the Leslie–Ericksen theory in the limit of weak translational diffusion, weak long range interaction, and weak flow.