Dielectric studies and critical behaviour in the vicinity of nematic–isotropic phase transition of a smectogenic binary mixture showing induced nematic phase

The phase diagram of a binary mixture composed of compounds, one having NCS terminal group (4DBT, showing smectic A₁ phase) and the other with CN terminal group (11OCB, showing smectic A_d phase), exhibiting induced nematic phase in a certain concentration range (0.100 < x_4DBT < 0.951) is reported here. Results of the static dielectric parameters measurement on this binary system within the entire mesomorphic range are presented. Evidence of strong pretransitional behaviour near the nematic–isotropic (N–I) phase transition, indicating the influence of tricritical behaviour, is observed. Precise determination of discontinuity (ΔT) and the critical exponent (α) of N–I phase transition have been carried out. Moreover, the order parameter critical exponent β is correctly predicted by the tricritical hypothesis through the dielectric anisotropy data for all the investigated mixtures.     

The phase behaviour and optical properties of a nematic/chiral dopant liquid crystalline mixture system

The phase behaviour and aggregation states of a binary mixture of a nematic liquid crystal and a chiral dopant have been investigated. The nematic liquid crystal E7 was miscible with the chiral dopant S811 over their entire concentration range. Binary E7/S811 mixtures formed the N* phase for S811 contents under 20%, and the SmA* phase for S811 contents between 40% and 90%. BP and TGBA* frustrated phases were found during cooling, for S811 contents between 25% and 35%. The helical pitches of the binary mixtures decreased with increasing chiral dopant content. From XRD profiles, the orientational ordering of the binary composites was found to increase with increasing chiral dopant content.     

Chromatographic behaviour of flavonoid compounds in reversed-phase HPLC systems

Summary Reversed-phase HPLC retention behaviour of different flavonoid compounds in different columns and with a range of methanol-buffer eluents was examined. Repeatibility and reproducibility of logk′ and Δlogk′ values were analyzed. Sharp group contributions, expressed as Δlogk′, were observed. These did not depend significantly on acid modifier type, column packing characteristics (C8 and C18) and dimensions (5,7 and 10μm) or the percentage of methanol in the mobile phase. A list of twelve group contributions is presented which is in agreement with literature data.     

Dielectric relaxation spectroscopy and electro-optical studies of phase behaviour of a chiral smectic liquid crystal

Dielectric relaxation processes in various phases of a chiral smectic liquid crystal compound have been investigated over a wide range of frequencies from 10 to 300 kHz. Dielectric spectroscopy reveals the existence of two relaxation frequencies corresponding to the ferroelectric and ferrielectric Goldstone modes in the range of temperature where two different phases coexist. This phenomenon of coexistence is examined with respect to the cell thickness and reversal temperature.     

Experimental studies on the phase diagram and physical properties of mixture of calamitic and discotic nematic liquid crystals

Physical studies on mixture of calamitic and discotic nematic liquid crystals are meagre although they are potential for optimising physical properties. Here, we report experimental studies on the phase diagram and physical properties of mixtures of ambient temperature discotic and calamitic nematic liquid crystals. A substantial decrease in several physical properties such as birefringence, dielectric anisotropy and elastic constants are observed with increasing wt% of discotic compound. On the other hand a large increase in the rotational viscosity is observed. Based on the experimental results a simple model of mutual orientation of the rod-like and disc-like molecules is proposed.     

Optimization of the separation of a mixture of unknown composition by reversed-phase HPLC

A method is presented for the computer-assisted optimization of mobile phaseselection for the separation of a synthetic intermediate of unknown composition by reversed-phase HPLC.The method is based on recognition of the order of the peaks by comparisonof peak area ratio and followed by the BSOS-L(Binary Solvent Optimization System forHPLC)method.Excellent agreement was obtained between predicted data and experimentalresults.     

Chromatographic separation of benzo(a)pyrene isomers on nematic liquid crystal GC and polymeric reversed-phase HPLC phases

Summary The use of two nematic liquid crystals (BABT and BPhBT) as GC stationary phases for the separation of monohydroxybenzo(a)pyrenes. as their TMS ethers, and monomethylbenzo(a)pyrenes was developed and compared with the separation of these isomers by HPLC using a polymeric ODS reversed-phase column. It was found that while HPLC and GC gave comparable separation of the hydroxy isomers, 10 out of 12 separated, better separation of the methyl isomers was obtained using HPLC. A simultaneous use of both HPLC and GC would resolve the twelve hydroxy isomers in about 70min. The results indicated that HPLC, using polymeric reversed-phase columns, is as powerful a tool as GC using nematic liquid crystal phases, for the separation of benzo(a)pyrene isomers. A discussion of the effect of solute length-to-breadth ratio on elution order is presented.Presented in part at the 1981 Pittsburgh Conference on Analytical Chemistry and Applied Spectroscopy, Atlantic City, NJ; paper No. 51.     

Development and validation of a reversed-phase HPLC method for determination of nitrendipine in rat plasma: application to pharmacokinetic studies

A simple and sensitive method for the determination of nitrendipine in rat plasma was developed using high-performance liquid chromatography (HPLC). The procedure involves extraction of nitrendipine in dichloromethane/sodium hydroxide, followed by reversed phase HPLC using a Waters, Spherisorb ODS2 (250 x 4.6 mm, 5 microm) column and UV detection at 238 nm. The retention times of nitrendipine and internal standard (felodipine) were 5.0 min and 7.5 min, respectively. The calibration curves were linear over the range of 5 ng/mL (lower limit of quantification, LOQ) to 200 ng/mL for nitrendipine. The intra- and inter-day coefficients of variation for all criteria of validation were less than 15% over the linearity range. The sensitivity and precision of the method were within the accepted limits (< 15%) throughout the validation period. The present method was also successfully applied for the study of plasma pharmacokinetics of nitrendipine loaded solid lipid nanoparticles (SLN) in rats.     

Nanostructure and dielectric properties of a twist-bend nematic liquid crystal mixture

We present freeze-fracture transmission electron microscopy (FF-TEM), dielectric spectroscopy and electro-optic measurements on a dimeric liquid crystal mixture, which previously was proposed to form the twist-bend nematic (N_tb) phase. Our FF-TEM studies provide a direct image of a 10.5 nm periodic structure, consistent with the expected nanoscale, heliconical twist-bend modulation of the molecular orientation. Dielectric measurements in the 100 Hz to 10 MHz range reveal three nearly Debye-type dispersion processes in the nematic and the twist-bend phase. Low frequency 8 V/µm electric fields applied on planar cells cause the optical-scale stripe texture (another characteristic feature of the N_tb phase) to disappear. Higher (>16 V/µm) fields gradually realign the heliconical axis along the electric field; it relaxes back after the field removal.     

Phase behaviour and electro-optical response of systems composed of nematic liquid crystals and poly (2-ethylhexylacrylate)

Experimental studies of phase diagram and morphology of mixtures composed of linear poly(2-ethylhexylacrylate) (poly-2EHA) of molecular weight M_w = 92000g/mol and E7, an eutectic blend of nematic liquid crystals (LCs), were performed. The latter consists of four cyanoparaphenylenes, i.e. 4-cyano-4?-n-pentyl-biphenyl (5CB), 4-cyano-4?-n-heptyl-biphenyl (7CB), 4-cyano-4?-n-oxyoctyl-biphenyl (8OCB) and 4-cyano-4?’-n-pentyl-p-biphenyl (5CT). Thermal properties of the poly-2EHA/E7 system were studied by differential scanning calorimetry and the sample morphologies were investigated by optical microscopy. Phase diagram analysis revealed an increase of the nematic–isotropic transition temperature when E7 was added to poly-2EHA, compared to pure E7. This effect, related to a preferential miscibility phenomenon of E7 components towards poly-2EHA, was evidenced by gas chromatography analysis coupled to mass spectrometry, allowing to qualify and quantify the content of phase separated LC domains. Thermograms of model LC mixtures including 5CB, 7CB, 8OCB and 5CT, which correspond to their composition in segregated LC domains of poly-2EHA/E7, present strong deviations from eutectic behaviour. In order to access the impact of such variations for practical applications, such a model LC mixture was introduced in photochemically crosslinked 2-EHA (polycross-2EHA). Surprisingly, the electro-optical response of the obtained polycross-2EHA/LC films was considerably improved compared to the original polycross-2EHA/E7 system.     

Simultaneous determination of E-2-nonenal and beta-damascenone in beer by reversed-phase liquid chromatography with UV detection

A method for the simultaneous determination of E-2-nonenal and beta-damascenone in beer by reversed-phase liquid chromatography using UV detection is presented. The method consists of beer steam distillation, followed by an extraction/concentration step using Sep-Pak Plus C18 RP cartridges and determination by HPLC at 226 nm UV-absorption maximum. The identity of the compounds was confirmed by GC analysis with MS detection of the isolated fractions. A recovery factor of approximately 80% was obtained for beta-damascenone with a R.S.D. of 3%. E-2-Nonenal and beta-damascenone were monitored in a comparative study of fresh and either naturally and forced aged beer. The results obtained show that both compounds have a similar behaviour through an extended storage of beer and consequently can be used as good analytical markers of beer ageing. Nevertheless, the use of beta-damascenone seems to be more convenient because this compound appears in beer in higher concentrations than E-2-nonenal, thus making it easier to measure.     

NMR studies on dimethyl selenide and dimethyl telluride oriented in the nematic phase of a liquid crystal

¹H NMR spectra of dimethyl selenide with ¹³C and ⁷⁷Se satellites and of dimethyl telluride with ¹³C, ¹²³Te and ¹²⁵Te satellites have been investigated. The structural information has been derived and is found to be in good agreement with microwave results for dimethyl selenide. For dimethyl telluride our results disagree with earlier data obtained by extrapolation from similar molecules.     

Electro-optic behaviour of a non-polar nematic liquid crystal and its mixtures

In this work we report preliminary results on the properties of a non-polar bicyclohexane nematic liquid crystal. Moreover, its binary mixtures both with a low viscosity phenylcyclohexane and with a normal polar nematic liquid have been investigated. The elastic, viscous and electro-optical properties of these compounds are presented. The non-polar compound, and its mixture with a low percentage of the well known liquid crystal MBBA, exhibit an electrohydrodynamic behaviour in which the conducting regime is absent, while the dielectric regime spreads to low frequencies. Additionally, at higher frequencies of the applied electric field, a regime whose thresholds are linear in frequency is observed. On the other hand, the mixture formed by 50 wt % of the non-polar compound with MBBA exhibits at low frequencies the usual behaviour, followed at higher frequencies by the linear regime.     

Electro-optic behaviour of a non-polar nematic liquid crystal and its mixtures

In this work we report preliminary results on the properties of a non-polar bicyclohexane nematic liquid crystal. Moreover, its binary mixtures both with a low viscosity phenylcyclohexane and with a normal polar nematic liquid have been investigated. The elastic, viscous and electro-optical properties of these compounds are presented. The non-polar compound, and its mixture with a low percentage of the well known liquid crystal MBBA, exhibit an electrohydrodynamic behaviour in which the conducting regime is absent, while the dielectric regime spreads to low frequencies. Additionally, at higher frequencies of the applied electric field, a regime whose thresholds are linear in frequency is observed. On the other hand, the mixture formed by 50 wt % of the non-polar compound with MBBA exhibits at low frequencies the usual behaviour, followed at higher frequencies by the linear regime.     

Characterization and design of liquid phase flow-through detector systems

Characterization of liquid phase flow-through detection systems as used in column liquid chromatography and flow injection analysis is discussed. Linear range, selectivity, peak broadening and detection limit are the most important characteristics. Peak broadening is treated with the aid of the concepts of systems analysis. The total peak broadening effect is given as the sum of contributions from connecting tubes or reactors, measuring volume and time constants in electronics and transducers. The influence of noise and signal frequency content on the precision of analytical results is treated qualitatively. The detection limit of a flow-through detection system is defined, taking these effects into account qualitatively. These characteristics are related to the performance of the whole analytical system with regard to concentration detection limit, absolute detection limit and maximum sample frequency.     

Retention behaviour of crown ethers and actinomycin D in reversed-phase HPLC

Summary Retention of crown ethers in reverse-phase HPLC has been determined by their bonding ability with cations present in the eluent. The dependence of retention of crown ethers on cation concentration exhibits an inflection and makes it possible to calculate stability constant for the crown ether-cation complex. It is shown that in 75% MeOH retention of antitumor antibiotic, actinomycin D, depends on [Na⁺] and not on [K⁺] at concentrations of K⁺ from 5×10^–7 to 10^–1 mol l^–1. Hence, actinomycin D may be classified as an ionophore-antibiotic.     

Optimising reversed-phase liquid chromatographic separation of an acidic mixture on a monolithic stationary phase with the aid of response surface methodology and experimental design

An optimization strategy for the separation of an acidic mixture by employing a monolithic stationary phase is presented, with the aid of experimental design and response surface methodology (RSM). An orthogonal array design (OAD) OA(16) (2(15)) was used to choose the significant parameters for the optimization. The significant factors were optimized by using a central composite design (CCD) and the quadratic models between the dependent and the independent parameters were built. The mathematical models were tested on a number of simulated data set and had a coefficient of R(2) > 0.97 (n = 16). On applying the optimization strategy, the factor effects were visualized as three-dimensional (3D) response surfaces and contour plots. The optimal condition was achieved in less than 40 min by using the monolithic packing with the mobile phase of methanol/20 mM phosphate buffer pH 2.7 (25.5/74.5, v/v). The method showed good agreement between the experimental data and predictive value throughout the studied parameter space and were suitable for optimization studies on the monolithic stationary phase for acidic compounds.