X‐ray diffraction from the uniaxial and biaxial nematic phases of bent‐core mesogens

X‐ray diffraction patterns for the uniaxial and biaxial nematic phases exhibited by rigid bent‐core mesogens were calculated using a simple model for the molecular form factor and a modified Lorentzian structure factor. The X‐ray diffraction patterns depend strongly on the extent of the alignment of the molecular axes as well as the orientation of molecular planes. The X‐ray diffraction can be unequivocally used to identify the biaxial nematic phase, study the uniaxial–biaxial phase transition, and estimate the order parameters of the nematic phase.     

Bimodal form distribution from modelling biaxial lyotropic liquid crystal solutions through a polydisperse Maier–Saupe model

Biaxial nematic phases have been the subject of a long list of studies. In particular, they were found for a few lyotropic micellar solutions. There is a debate in the literature on whether the micellar aggregates should be biaxial, or if biaxiality could be the result of perpendicular alignment of uniaxial particles of cylinder-like and disc-like geometry in a mixture. Based on recent studies on the phase stability of such mixtures, we have investigated a polydisperse distribution of uniaxial particles interacting through a Maier–Saupe potential. Our calculations were developed for a general distribution of micellar anisometries. The distribution was obtained from the fitting of our results to the experimental data of Yu and Saupe’s well-known 1980 paper, near the Landau point, yielding a bimodal distribution, with the presence of two quadrupoles referred to objects of opposite symmetry, that is to prolate and oblate micelles. This result lends support to the rationalization of the biaxial phase for lyotropic systems in terms of a polydisperse mixture of rod-like and disc-like micelles.     

Biaxial phase and coexistence of the two uniaxial nematic phases in the system sodium dodecyl sulphate–decanol–D2O

The system sodium dodecyl sulphate (SDS)/decanol (DeOH)/water presents, with temperature increase, an unusual phase transition between a stable biaxial phase and a coexistence region of the two uniaxial nematic phases (discotic N_D + cylindrical N_C). This has been detected previously by several methods for a sample with water/SDS molar ratio M_w = 36. Here, this system is investigated changing the ratio M_w to 32, where previously the coexistence region was reported after a discotic N_D phase, without the biaxial phase. We report now the existence of a biaxial N_B in the temperature range of ~2°C, defining for both values of M_w and the phase sequence as N_B – (N_D + N_C) – N_C. The change in temperature is followed by conoscopic and orthoscopic optical techniques and also analysed through the curve obtained by the technique of digital image processing of the textures, which reveals a continuous transition N_D – N_B – (N_D + N_C). While the biaxial phase is stable for at least 10 hours, in a reproducible way, the coexistence region evolves with time, and drops of the discotic phase grow immersed in a N_C matrix. Results are explained in terms of recent theories dealing with stabilisation of mixtures of cylinders and discs.     

Solvent–solute and solute–solute interactions from NMR in nematic phases

Abstract

The use of NMR spectroscopy of molecules oriented in liquid-crystalline media to study solvent–solute and solute–solute interactions in π-systems such as benzene–chloroform and in charge transfer complexes, for example pyridineiodine, is illustrated. Changes in molecular order and chemical shifts as a result of complexation are employed in such studies. The extraordinary symmetry of C₆₀ has also been investigated by using a mixture of liquid crystals of opposite diamagnetic anisotropies indicating, thereby, negligible solvent–solute/solute–solute interactions.     

X-ray investigation of the nematic and reentrant nematic phases of N-[(4-n-octyloxybenzoyloxy)-salicilidene]-4′-cyanoaniline

We have performed an X-ray scattering study of the nematic-smectic A and reentrant nematic-smectic A phase transitions in N-[(4-n-octyloxybenzoyloxy)-salicilidene]-4′-cyanoaniline (OOBOSCA). A diffractometer with a linear position sensitive detector was used. The results show that the smectic phase in OOBOSCA is of the A_d type with an interlayer spacing incommensurate with the molecular length L; d ∽ 1·2L. In the reentrant nematic phase two types of fluctuation modes were found. One of them corresponds to the monolayer wavevector q ₁ ∽ 2π/L, and the other is due to the partial bilayer fluctuations with the wavevector q ₂ ∽ 0·8q ₁. The temperature dependences of the interlayer spacing, X-ray scattering intensity and longitudinal correlation length for both types of layering in the reentrant nematic phase are presented. The change of the fluctuation regime from S_Ad, to S_Cd type with decreasing temperature in the reentrant nematic phase of OOBOSCA was found. The results are discussed on the basis of models with competing order parameters. The influence of alkyl chain flexibility on the stability of a partial bilayer smectic phase is also considered.     

Selectivity and thermodynamics of the dissolution of structural isomers in the stationary phases based on nematic 4-ethyloxy-4′-(ω-hydroxyalkoxy)azo- and azoxybenzenes

Gas chromatography was used to study of the retention of xylene, methylanisole, and lutidine on stationary phases based on nematic 4-ehtyloxy-4′-(6-hydroxyhexyloxy)azobenzene, 4-ethyloxy-4′(3-hydroxypropyloxy)azobenzene, and 4-ethyloxy-4′-(6-hydroxyhexyloxy)azobenzene. A thermodynamic explanation of the structural selectivity of the liquid-crystalline phases of the considered compounds is proposed.     

On the balance between nematic and smectic phases in 2′,3′-difluoro-4,4″-dialkyl-p-terphenyls

ABSTRACT

The full homologous series of 2?,3?-difluoro-4,4″-dialkyl-p-terphenyls, where alkyl chains are from methyl to nonyl length, have been synthesised and mesomorphic properties, phase transition temperatures and enthalpies were measured. The influence of the terminal chain length on thermal mesophase range, phase sequence has been analysed and discussed. The odd–even and symmetric–non-symmetric effects have also been studied and its influence on smectic to nematic balance was analysed.     

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.     

Pure face-centered-cubic (fcc) and hexagonal-close-packed (hcp) nickel phases obtained in air atmosphere sol–gel process and fcc nickel phase obtained in N2 protected sol–gel process

Air atmosphere sol–gel process is often applied to prepare metallic oxide materials. Here we show that metallic nickel phase can also be obtained by citric acid (CA) based air atmosphere sol–gel process in appropriate procedure. Pure fcc or hcp phases of nickel can be obtained in air atmosphere by using CA, nickel (II) acetylacetone, organic solvents and organic surfactants such as oleylamine (OAM), hexadecylamine. However, only NiO can be prepared by aqueous CA based sol–gel process. Oleic acid and OAM can also be used in organic solution mediated sol–gel process to prepare nickel nanoparticles in N₂ atmosphere with pure fcc phase at appropriate calcination temperature when 1-hexyl alcohol has been used as solvent. Impurities, such as hcp Ni or Ni₃N phase, do not occur in this experimental condition. Our results provide a new and facile way in preparation of metallic nanoparticles.     

EPR on bis(1,2-dithiosquarato)cuprate(II) in the bis(1,2-dithiosquarato)nickelate(II) host lattice — structure and spectroscopy‡

EPR spectroscopy is a well suited analytical tool to monitor the electronic situation around paramagnetic metal centres as copper(II) and therefore the structural influences on the paramagnetic ion. 1,2-Dithiosquaratometalates are available by direct synthesis from metal salts with dipotassium-1,2-dithiosquarate and the appropriate counter cations. Synthesis and characterisation of bis(benzyltributylammonium)1,2-dithiosquaratonickelate(II), (BzlBu₃N)₂[Ni(dtsq)₂], and bis(benzyltributylammonium)1,2-dithiosquaratocuprate(II), (BzlBu₃N)₂[Cu(dtsq)₂], with benzyltributylammonium as the counter ion is reported and the X-ray structures of two complexes, (BzlBu₃N)₂[Ni(dtsq)₂] and (BzlBu₃N)₂[Cu(dtsq)₂], are presented. Both complexes, crystallising in the monoclinic space group P2₁/c, are isostructural with only small differences in the coordination sphere due to the different metal ions. The diamagnetic nickel complex is therefore well suited as a host lattice for the paramagnetic Cu(II) complex to measure EPR for additional structural information.     

Critical behaviour of optical birefringence in the vicinity of nematic–isotropic and smectic A–isotropic phase transitions of the eight members of alkyloxy-cyanobiphenyls

We report the measurements of birefringence (Δn) as a function of the temperature of a homologous series of alkyloxy-cyanobiphenyls (nOCB) liquid crystalline compounds by means of high-resolution optical transmission method. The temperature dependence of the birefringence has been determined from the transmitted intensity data for two different wavelengths. The order parameter critical exponent β, obtained by using a four-parameter fitting procedure consistent with the mean-field theory for a weakly first order transition, is found to be in good agreement with the theoretically predicted tricritical value. A weak birefringence has been found to develop on approaching the clearing temperature, which is tentatively attributed to the formation of a small mesophase domain within the isotropic phase. This striking behaviour leads to a further quantification of the critical fluctuation close to the transition. Finally, the order character of the nematic–isotropic (N–I) and smectic A–isotropic (SmA–I) phase transitions have been assessed by using the birefringence data. The critical exponent α (usually assigned to the heat capacity) extracted from Δn data describes the critical nature of N–I and SmA–I transitions and strongly supports the tricritical nature of the same.     

Structural topology and dimensional reduction in uranyl oxysalts: eight novel phases in the methylamine–(UO2)(NO3)2–H2SeO4–H2O system

Single crystals of eight novel uranyl selenates, (CH₃NH₃)₂[(UO₂)(SeO₄)₂(H₂O)](H₂O) (I) and (CH₃NH₃)₂[(UO₂)(SeO₄)₂(H₂O)] (II), (CH₃NH₃)₂[(UO₂)₂(SeO₄)₃] (III) and (CH₃NH₃)(H₃O)[(UO₂)₂(SeO₄)₃(H₂O)](H₂O) (IV), (CH₃NH₃)₄[(UO₂)₃(SeO₄)₅](H₂O)₄ (V) and (CH₃NH₃)(H₅O₂)(H₃O)₂[(UO₂)₃(SeO₄)₅](H₂O)₄ (VI), (CH₃NH₃)₄(H₃O)₂[(UO₂)₅(SeO₄)₈(H₂O)](H₂O)₄ (VII), and (CH₃NH₃)_1.5(H₅O₂)_1.5(H₃O)₃[(UO₂)₅(SeO₄)₈(H₂O)](H₂SeO₄)_2.6(H₂O)₃ (VIII), have been prepared by isothermal evaporation from aqueous solutions and structurally characterized. The observed structural topologies of uranyl selenate units have been investigated using graph theory. The principle of dimensional reduction has been used for analysis of the uranyl oxysalts with general chemical formula A _n (UO₂) _p (TO₄) _q (H₂O) _r (A = monovalent cation, and T = S, Se, Cr, Mo), which allowed to construct three-component composition-structure diagram with separate dimensionality fields for different chemical compositions.     

Thermodynamic properties of water in the lattice gas model with сonsideration of the vibrational motions of molecules

A molecular model developed earlier for a polar fluid within the lattice gas model is supplemented by considering the vibrational motions of molecules using water as an example. A combination of point dipole and Lennard-Jones potentials from SPC parametrization is chosen as the force field model for the molecule. The main thermodynamic properties of liquid water (density, internal energy, and entropy) are studied as functions of temperature. There is qualitative agreement between the calculation results and the experimental data. Ways of refining the molecular theory are discussed.     

Colloid–chemical regression model in analyzing the relationship between dynamic surface tension and the content of total protein and albumins in blood

Mathematical statistics methods in chemistry and biology make it possible to apply certain analytical methods, e.g., interphase tensiometry, in diagnosing physiological states of humans and animals. This study is the first to use the regression method for modeling the relationship between the biochemical parameters of blood serum and dynamic surface tension (DST). We also demonstrate how the regression model can be used to determine the contents of total protein and albumins in blood serum from the known DST values at the liquid/air interface. As a result of constructing the regression model, we propose the regression equations characterizing the relationship between the DST values and the content of protein components in blood serum of animals.     

Electroclinic effect in the chiral smectic A and cholesteric phases at the proximity of a N*–SmA–SmC* multicritical point

We studied the electro-optic and dielectric properties of three pure ferroelectric liquid crystal materials (C10, C11 and C12) of the same series exhibiting cholesteric (N*), smectic A (SmA) and chiral smectic C (SmC*) phases. From electro-optic investigations, the tilt angle and spontaneous polarisation were determined as a function of temperature. In the dielectric measurements carried out without a dc bias field, we studied the soft-mode relaxation in the SmA phase. From experimental data and using the results of a Landau model, we evaluated the soft-mode rotational viscosity and the electroclinic coefficient in the SmA phase. A soft-mode like mechanism was also observed in the N* phase for compounds with shorter chains (C10 and C11). This relaxation process is not detected for the homologue with a longer chain (C12). The observation of this mechanism is related to smectic order fluctuations within N* phase whose amplitude is increased when approaching the SmC*–SmA–N* multicritical point.     

Speciation in the Vanadium(III)–Carnosine System

Speciation in the aqueous V(III)–carnosine system has been determined from potentiometric and spectroscopic (UV-Vis absorption and CD) data. Application of the Hyperquad program to the experimental potentiometric data indicates that under our experimental conditions (I=0.5 mol⋅L⁻¹ NaClO₄, pH=2 to 6.5, and L/M>5) only ML₂H₄, ML₂H₃, ML₂H₂ and ML₂H form. These potentiometric results prove that stable complexes form and, with use of the spectroscopic methods, the binding sites are identified.     

The conformations adopted by α,δ-bis(phenoxy)ethane in isotropic and nematic solutions

Abstract

Errors in the calculations of Cheung and Emsley (Liquid Crystals, 13, 265 (1993)) used to derive the populations of α,δ-bis(phenoxy)ethane dissolved in isotropic and nematic liquid crystalline solvents have been corrected, and the results are compared with those obtained on the same molecule by Abe, Iizumi and Kimura (Liquid Crystals, 16, 655 (1994)). The principal difference between these two calculations is that Abe et al., obtain 0·80 as the population of the tg ± t conformers, and they find this to be independent of temperature, whereas the present calculations obtain 0·42 to 0·58 depending upon solvent and temperature.     

Thermodynamic stability of solid phases in the system Cu–O–Al2O3 by means of the EMF and DSC-TGA techniques

Journal of Solid State Electrochemistry - Thermodynamic properties of solid phases in the Cu–O–Al2O3 system were measured by means of the EMF method with oxygen concentration galvanic...     

Relationship between the c(4×2) and the (√3×√3)R30° phases in alkanethiol self-assembled monolayers on Au(111)

Transformation between the two well-known phases of alkanethiol monolayers on Au(111), c(4×2) and (√3×√3)R30°, has been studied using scanning tunneling microscopy in ultra-high vacuum. Among the many versions of the c(4×2) phases observed, one particular structure where a lateral shift of adsorbate by as much as 0.17 nm within the unit cell is found. This lateral shift along the [112[combining macron]] direction corresponds to the movement of one adsorbed unit, towards its nearest neighbour from one hollow site to another (fcc to hcp, or hcp to fcc).