Side-chain liquid-crystalline copolymers containing charge transfer groups

A series of side-chain liquid crystal copolymers have been prepared based on a polystyrene backbone and having 4-nitro-4'-oxyazobenzenealkyloxy and 4-methoxy-4'-oxyazobenzenealkyloxy pendant groups. All the polymers exhibit solely smectic behaviour. The thermal stability of the smectic phase is significantly enhanced in the copolymers when compared to the homopolymers. This is compared to the behaviour of the analogous monomeric compounds. The enhancement of the thermal stability is attributed to a specific interaction, possibly charge transfer.     

Molecular dynamics of a smectic liquid-crystalline side-chain polymer. The dielectric properties of aligned and nonaligned material studied over a wide range of frequency and temperature

The dielectric relaxation behavior of a nonaligned and an aligned liquid-crystalline (LC) polymer are reported for the ranges 10^?3.5 to 10⁵ Hz and 274–363 K. Multiple processes (δ and α) are observed that follow a Vogel equation for the temperature dependence related to the apparent glass transition temperature. The occurrence of these processes and the variation in their relaxation strengths as sample alignment is changed is interpreted in terms of a molecular theory for the dielectric behavior of a LC polymer that involves the director order parameter S_d, the mesophase order parameter S, the dipole moment components of the mesogenic head groups, and their associated relaxation functions.     

DNA that is dispersed in the liquid crystalline phases of phospholipids is actively transcribed

We report that a 4.3 kbp linearised T7 DNA plasmid is actively transcribed when it is dispersed in the hexagonal liquid crystalline phase of dioleoylphosphoethanolamine (DOPE).     

Stability of Thin-Walled Open Beams Under Nonconservative Loads

ABSTRACT

A finite element formulation for free-vibration analysis of straight prismatic beams of general thin-walled open cross-section, under conservative and nonconservative loads, is presented. The formulation is used to calculate the flutter load for a number of beam problems and is verified by comparison with pre-existing numerical solutions.     

Reliable measurements of interfacial slip by colloid probe atomic force microscopy. II. Hydrodynamic force measurements

Here we report a new study on the boundary conditions for the flow of a simple liquid in a confined geometry obtained by measuring hydrodynamic drainage forces with colloid probe atomic force microscopy (AFM). In this work, we provide experimental data obtained using a best practice experimental protocol and fitted with a new theoretical calculation (Zhu, L.; Attard, P.; Neto, C. Langmuir 2010, submitted for publication, preceding paper). We investigated the hydrodynamic forces acting on a silica colloid probe approaching a hydrophobized silicon surface in a single-component viscous Newtonian liquid (di-n-octylphthalate), a partially wetting system. The measured average slip lengths were in the range of 24-31 nm at approach velocities of between 10 and 80 μm/s. Using our experimental approach, the presence of nanoparticle contaminants in the system can be indentified, which is important because it has been shown that nanoparticles lead to a large apparent slip length. Under our stringent control of experimental conditions, the measurement of the slip length is reproducible and independent of the spring constant of the cantilever.     

In-plane buckling of prismatic funicular arches with shear deformations

The in-plane buckling behavior of funicular arches is investigated numerically in this paper. A finite strain Timoshenko beam-type formulation that incorporates shear deformations is developed for generic funicular arches. The elastic constitutive relationships for the internal beam actions are based on a hyperelastic constitutive model, and the funicular arch equilibrium equations are derived. The problems of a submerged arch under hydrostatic pressure, a parabolic arch under gravity load and a catenary arch loaded by overburden are investigated. Buckling solutions are derived for the parabolic and catenary arch. Subsequent investigation addresses the effects of axial deformation prior to buckling and shear deformation during buckling. An approximate buckling solution is then obtained based on the maximum axial force in the arch. The obtained buckling solutions are compared with the numerical solutions of Dinnik (Stability of arches, 1946) [1] and the finite element package ANSYS. The effects of shear deformation are also evaluated.     

Selective clean-up applicable to aqueous acetone extracts for the determination of carbendazim and thiabendazole in fruits and vegetables by high-performance liquid chromatography with UV detection

Fungicide residues in vegetables (benomyl, carbendazim, thiabendazole) are analyzed through a clean-up procedure that uses a portion of the aqueous acetone extract prepared for multiresidue methodology. A portion of the aqueous acetone extract (equivalent to 5 g of vegetables) is loaded onto an Extrelut-20 cartridge (the cartridge is filled with a coarse, large-pore diatomaceous material). Then, acetone is partially removed by an upward stream of nitrogen at 2l/min for 30 min. Benzimidazolic fungicides are recovered by percolating the cartridge with 100 ml of 0.1 M phosphoric acid solution, which also serves to convert benomyl to carbendazim. The percolating acid solution is drained on-line through a strong cation-exchange (SCX) solid-phase extraction cartridge with the aid of a slight vacuum. Benzimidazolic fungicides are retained on the SCX cartridge. The phosphoric acid solution is discarded together with the washings of the SCX cartridge, i.e., water followed by methanol-water (75:25), that remove unwanted coextractives. Finally, benzimidazolic fungicides are recovered by eluting the SCX cartridge with methanol-ammonium formate buffer (75:25). The final extract is then analyzed by reversed-phase HPLC with UV detection. Recoveries from crops such as apples, lettuce, strawberries and citrus fruits are generally greater than 80% and no interferences were observed. The clean-up is simple and straightforward, requires only disposable items, water solutions and a few milliliters of solvent and a minimum number of manipulations, and does not require concentration steps or electrical equipment.     

Monte Carlo simulation methodology of the ghost interface theory for the planar surface tension

A novel "ghost interface" expression for the surface tension of a planar liquid-vapor interface is derived in detail from consideration of the free energy of the system, and a methodology for utilization of this new technique is given. An augmented Monte Carlo computer simulation procedure is developed specifically for the ghost interface, including derivation of long-range corrections resulting from potential truncation and a modified Gibbs ensemble technique for the simulation of adjacent coexisting phases. Results generated from the ghost interface theory for the surface tension are presented and found to be in good quantitative agreement with those resulting from the Kirkwood-Buff equation. Applications of this new approach to curved and to supersaturated systems are also discussed.     

Statistical mechanical theory for the structure of steady state systems: application to a Lennard-Jones fluid with applied temperature gradient

The constrained entropy and probability distribution are given for the structure that develops in response to an applied thermodynamic gradient, as occurs in driven steady state systems. The theory is linear but is applicable to gradients with arbitrary spatial variation. The phase space probability distribution is also given, and it is surprisingly simple with a straightforward physical interpretation. With it, all of the known methods of equilibrium statistical mechanics for inhomogeneous systems may now be applied to determining the structure of nonequilibrium steady state systems. The theory is illustrated by performing Monte Carlo simulations on a Lennard-Jones fluid with externally imposed temperature and chemical potential gradients. The induced energy and density moments are obtained, as well as the moment susceptibilities that give the rate of change of these with imposed gradient and which also give the fluctuations in the moments. It is shown that these moment susceptibilities can be written in terms of bulk susceptibilities and also that the Soret coefficient can be expressed in terms of them.     

Statistical mechanical theory for steady state systems. VIII. General theory for a Brownian particle driven by a time- and space-varying force

A Brownian particle subject to a time- and space-varying force is studied with the second entropy theory for nonequilibrium statistical mechanics. A fluctuation expression is obtained for the second entropy of the path, and this is maximized to obtain the most likely path of the particle. Two approaches are used, one based on the velocity correlation function and one based on the position correlation function. The approaches are a perturbation about the free particle result and are exact for weak external forces. They provide a particularly simple way of including memory effects in time-varying driven diffusion. The theories are tested against computer simulation data for a Brownian particle trapped in an oscillating parabolic well. They accurately predict the phase lag and amplitude as a function of drive frequency, and they account quantitatively for the memory effects that are important at high frequencies and that are missing in the simplest Langevin equation.