“Bands” and “Torsads” Textures in Films and Threads of Hydroxypropyl Cellulose

The present paper deals with films and threads of a mesomorphic cholesteric polymer: the hydroxypropyl cellulose. The steady flow behaviour and the shear induced textures (observed by optical microscopy under crossed polars) of films of lyotropic solutions of this polymer have been studied. A detailed analysis of the banded structures, of either the sheared solutions or the dried films obtained by solvent evaporation, is reported. We point out the existence of transverse striated patterns—“torsads”—superposed on the main banded structures, which are associated with the rewinding of the cholesteric structure following the cessation of the shear stress. The torsads, also observed in some threads, originate from the same relaxation phenomena and are discussed in the last part of the paper.     

New chiral liquid crystal materials based on menthol: Synthesis and phase behavior

To study structure-mesomorphism relationships of chiral materials based on menthol, a series of chiral compounds containing menthyl group were synthesized. Their chemical structures, formula, and the purity were characterized by Fourier transform infrared (FTIR), proton nuclear magnetic resonance (¹H NMR), and elemental analyses. The corresponding phase behavior was investigated with differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). The effect of the mesogenic core, flexible spacer, and terminal groups on the mesophase formation and type was discussed. The compound 4-menthyloxyacetoxybenzoyloxy-4′- (6-bromohexyloxy)biphenyl showed the smectic A (S_A) and cholesteric phases on heating cycle, and a cubic Blue Phase, chiral smectic C (S_C^*), S_A and cholesteric phases on cooling cycle. However, the compound 4-menthyloxyacetoxybenzoyloxy-4′-(4-bromobutoxy)biphenyl showed enantiotropic S_C^*, S_A and cholesteric phases, moreover, the platelet texture of a cubic Blue Phase was also observed on cooling cycle. The methacrylate monomer with six flexible methylene units and three phenyl rings as mesogenic core only showed cholesteric phase, while the methacrylate monomer with four methylene unit and three phenyl rings showed the S_C^* and cholesteric phases. However, when the terminal methacryloyloxy groups in the monomers were substituted by thiophenylacryloyloxy groups, the corresponding monomers all show no mesophase. With increasing the rigidity of mesogenic core or decreasing the flexible methylene spacer length, the corresponding melting temperature (T_m) or isotropic temperature (T_i) increased.     

Investigation of a Twisted Phase between the Cholesteric and the Smectic A Phase

In a ternary mixture of two liquid crystals and a non-mesomorphic chiral dopant an intermediate state with an unusual texture was found between the cholesteric and the S_A phase which could be identified as a separate twisted mesophase. The reflection wavelength of this mesophase does not change with temperature whereas the transmission of unpolarized light decreases from 50 to 20%. The experimental findings point to the existence of a twisted grain boundary phase.     

The Orientational Order in Cholesteric Liquid Crystals

The investigation of the orientational order in the mesophase of steroidal cholesterogens has been all but neglected by experimentalists, possibly because of the lack of an appropriate technique. However electron resonance spectroscopy can be used to determine the order parameter of a spin probe dissolved in a cholesteric mesophase. In addition the structure of the spin probe may be made to resemble that of the cholesteric solvent. Here this technique is employed to determine the orientational order for cholesteryl and cholestanyl benzoate, as a function of temperature. The results of these experiments yield order parameters which are comparable, or slightly smaller, than those typically observed for nematics. A comparison of these values with mean field theories suggests that the low order parameters of steroidal cholesterogens stems from deviation of the constituent molecules from cylindrical symmetry.     

Topology of a Surface of the Phase Diagram of the Cholesteric Lyotropic Mesophase: Potassium Laurate/1-Decanol/Water/I-N-Lauroyl Potassium Alaninate

A surface of the phase diagram of the lyotropic cholesteric mesophase of potassium laurate/1-decanol/H₂O/l-N-lauroyl potassium alaninate (l-LAK) is studied by optical microscopy and X-ray diffraction as a function of the relative molar concentration of l-LAK and temperature. Cholesteric discotic and calamitic phases are observed and also a large domain of biaxial cholesteric phase. The inverse pitch as a function of the l-LAK relative molar concentration presents a linear behavior in the doping range studied. The l-LAK doping and its influence in favoring cholesteric calamitic phase formation are discussed in terms of the packing of the l-LAK amphiphile in the bilayer and the orientational fluctuations of the intrinsically biaxial correlation volumes.     

Synthesis and Liquid Crystal Properties of Some 3-Arylcholest-2 enes and 3-Arylcholest-3,5-dienes

Abstract

A series of mesogenic 3-arylcholest-2-enes and 3-arylcholest-3,5-dienes were prepared. All members of the monoene and diene steroid series exhibited enantiotropic cholesteric mesophases. The broadest mesophase range was 90°, found for para-methoxyphenylcholest-2-ene.     

High-frequency acoustic domains in liquid crystals

A mechanism for the formation of one-and two-dimensional domains in planar nematic and cholesteric liquid crystal samples in an ultrasonic field is discussed. A new approach to the analysis of this phenomenon based on the concepts of nonequilibrium hydrodynamics and taking into account the relaxation properties of the mesophase is experimentally substantiated.     

A Polyester Forming a Thermotropic Cholesteric Phase

Mesomorphic polyesters were synthesized from 4, 4′-dihydroxy-α-methylstilbene and adipic acid (P-6) or (+)-3-methyl adipic acid (P-6M). P-6 forms a thermotropic nematic phase and P6-M a thermotropic cholesteric phase. The nematic phase of P-6 could easily be identified by optical microscopy. For both polymers we observed a biphasic region in which the isotropic and liquid crystalline phases coexist. Bright colors were obtained by increasing the pitch of P6-M by admixture with either a low molecular weight nematogen or with polymer P-6, and also by synthesizing a copolymer containing the two dibasic acids. The copolymeric cholesteric phase, which is stable between 199 and 282[ddot]C, had a predominately planar texture, and these features could be retained in the solid state by quenching to produce a film having a deep blue color at room temperature. The role of the degree of polymerization upon the development of organization, and parameters, of the mesophase is discussed.     

Liquid-Crystalline State of Cholesterol-Containing Monomers

A series of cholesterol-containing monomers was synthesized: cholesteryl esters of N-acryloyl-ω-aminocarboxylic acids, N-methacryloyl-ω-aminocarboxylic acids, ω-acryloyloxycarboxylic acids and ω-methacryloyloxycarboxylic acids. The mesomorphic properties, temperatures and heats of transitions of monomers were investigated in comparison with the cholesteryl alkanoates. The temperature range of cholesteric mesophase of monomers—derivatives of oxycarboxylic acids was shown to be wide. Such monomers can be used in thermographic composites and for synthesis of the liquid-crystalline polymers.     

Liquid-Crystalline Solvents as Mechanistic Probes. 10. Dynamics of Intramolecular Quenching of Pyrenyl Fluorescence in the Liquid-Crystalline and Isotropic Phases of a Cholesteric Solvent1

Abstract

The effect of cholesteric order in a 59.5/15.6/24.9 (w/w/w) mixture of cholesteryl oleate/cholesteryl nonanoate/cholesteryl chloride (CM) on the intramolecular fluorescence quenching of l,3-bis(l-pyrenyl) propane (P3P) has been explored. A comparison with fluorescence quenching of N,N-dimethyl-4-[3-(l-pyrenyl)propyl]aniline (P3D) in CM is made. From the Arrhenius activation parameters for quenching in the cholesteric and isotropic phases, it is concluded that the motions which take the ground state conformers of P3P to their quenching transition state are nearly impervious to macroscopic CM mesophase order: in the cholesteric phase, E'_a = 10.5±0.4 kcal mol^?1 and ΔS^? = 1 ± 1 eu; in the isotropic phase, E'_a = 10.0 ± 0.2 kcal mol^?1 and ΔS^? = 0 ± 0.5 eu. An explanation of these results is advanced.     

High Pressure Studies on Mesomorphic and Polymesomorphic Transitions

The paper presents the following results: (1) pressure induced mesomorphism in p-p'-n-butylazobenzene and biphenyl p-ethyl benzoate. (2) the monotropic nematic-isotropic transition in trans-p-n-propoxy-x-methyl cyanophenyl cinnamate becoming enantiotropic under pressure, (3) suppression of the cholesteric mesophase in cholesteryl nonanoate and the location of a solid-cholesteric-isotropic triple point at ～ 2.85 kbar. confirming an earlier observation of Keyes. Weston and Daniels on the same compound, (4) a measurement of dT/dp for the solid-smectic A, smectic A-cholesteric and cholesteric-isotropic transitions in cholesteryl myristate and a comparison with the values evaluated from the Clausius-Clapeyron equation using the known latent heat and volumetric data.     

Synthesis and Mesomorphic Characteristics of Fluoroaniline Derivatives with Different Lateral Groups

Two new homologous series of liquid crystals viz. 4-(4'-n-alkoxybenzoyloxy)-2-chlorophenylazo-4”-fluorobenzenes(I) and 4-(4'-n-alkoxybenzoyloxy)-2-methylphenyl azo-4”-fluorobenzenes(II) with terminal fluoro, lateral chloro(I) and methyl(II) group and central ester and azo linkages are synthesized and their mesomorphic properties are studied. Both the series are similar in molecular structure with the difference in their lateral substitutions; series I has chloro group and series II has methyl group as laterally substituted groups. All the twelve homologues of each of the series are mesogenic in nature. Series I shows nematic mesophase from the first C₁ to the last C₁₆ derivative synthesized; smectic mesophase is exhibited by last two viz. C₁₄ and C₁₆ derivative, where as all the members from C₁ to C₁₆ of series II only show nematic mesophase. The nematic mesophase shows marble texture and the smectic mesophase shows Schlirene texture of the Smectic C variety. Both the series are compared with structurally related series.     

Cholesteric Pitch Near the Smectic-C Phase

The temperature dependence of the cholesteric pitch of the chiral ester 4-n-hexyloxyphenyl-4'-(2”-methylbutyl)biphenyl-4-carboxylate has been measured in detail using the method of selective reflection. This compound has a cholesteric to smectic-C transition at 79°C. Because of the first-order nature of the transition, the pretransitional unwinding of the pitch is considerably less pronounced than that in cholesteryl esters near the smectic-A transition. The wavelength of maximum reflection increases from 440 nm at 110°C to 560 nm at the transition. When fitted to a power-law temperature dependence, the data imply an exponent of 0.82 ± 0.15, which is consistent with de Gennes’ theory in the meanfield approximation.     

Synthesis and Liquid Crystal Behavior of a Novel Ester Homologous Series

A novel ester homologous series of 4-[4’-n-alkoxy cinnamoyloxy] benzyl benzoates has been synthesized. The series consists of 12 homologues. Liquid crystal properties commence from the sixth member to the last member of the series with the exhibition of an enantiotropic nematic phase without the exhibition of any smectogenic mesophase. The remaining homologues do not exhibit liquid crystal behavior. The texture of the nematic phase is of the threaded or Schlieren type. The solid-nematic or isotropic transition curve adopts a zigzag path and the nematic-isotropic transition curve steeply rises and then falls in the phase diagram and behaves in normal manner. An odd–even effect is absent in the nematic-isotropic transition curve with an alteration of transition temperatures. The average thermal stability for the nematic mesophase is 153.1°C, and the nematogenic temperature ranges vary from 12°C to 50°C. Analytical data confirm the molecular structures of the homologues. The Liquid Crystal properties and transition temperatures were observed through an optical polarizing microscope, equipped with a heating stage. The mesomorphic characteristics of the novel ester series are compared with other, known and structurally similar series. The novel series is predominantly nematogenic with the absence of any smectogenic character, with relatively short mesophase temperature ranges and of the middle ordered melting type.     

New chiral metal-mesogenic nanosystems “silver - thiocholesterol” and their adsorption properties

ABSTRACT

New chiral matrices for thin film chromatography were obtained using hybrid metal-mesogenic nanosystems «silver – thiocholesterol» with different metal to ligand ratio, immobilized on silica gel particles. It was shown, that heteroatomic derivative of cholesterol – thiocholesterol and its composition with small silver nanoparticles formed in the system by the chemical reduction of silver ions possess liquid crystalline cholesteric mesophase. Molar ratio between thiocholesterol ligand molecules (L) and silver (Ag) insignificantly influenced on the size of silver nanoparticles formed in the system: for molar ratio Ag : L = 1:5 the main diameter of nanoparticles was equal to (2,7 ± 0,4) nm, for molar ratio Ag : L = 1:2 – (2, 2 ± 0,4) nm, for molar ratio Ag : L = 1:0,5 – (2,1 ± 0,6) nm. The new chiral matrices for thin film chromatography possess enantioselectivity related to optical isomers of 2,2′-diamino-1,1′-binaphtol (DABN) and trifluoroantranylethanol (TFAE). We have succeeded to select optical isomers of TFAE with selecting factor equal to 1,56.     

Cholesteric liquid Crystals: Physical Properties and Molecular-Statistical Theories

It seems certain now that cholesteric liquid crystals (cholesterics, or CLC, for short) have been the first examples of mesomorphic state of matter known to humankind. Apart from the well-known discovery of the two-stage melting of cholesteryl benzoate made by Reinitzer in 1888¹ and cited in almost all the textbooks, one may recall some other papers where the authors, quite unaware of the real significance of their observations, presented undeniable evidence of the liquid crystalline state of matter. E.g., Professor Planer from the Lvov University as early as in 1861 did observe, putting it in the presentday terms, selective reflection from the planar texture of cholesteryl chloride forming a monotropic cholesteric mesophase on cooling.² One should also note that the works of Fergason^3,4 outlining the prospects of practical applications for CLC, did, in fact, precede similar endeavors by Heilmeier in the field of nematics. From the viewpoint of organic chemistry, a number of mesogenic cholesterol derivatives had been already synthesized and thoroughly studied⁵ by the time the name of MBBA (p-methoxybenzylidene-p′-n-butylaniline), to say nothing about cyanobiphenyls, was not yet known to anybody. The mere listing of CLC prospective applications^6,7. seems so impressive that, keeping in mind the above-described historical background, one should expect to find cholesterics in a key position in the field of liquid crystal science.     

Synthesis and Mesomorphic Phase Behavior of Laterally Substituted Novel Azoesters

A novel homologous series of 4(4′-n-alkoxy benzoyloxy)phenylazo 2′′-chloro-3′′-methyl benzenes was synthesized and studied for mesophase behavior dependence on molecular structure. The nematogenic mesophase is exhibited from the first to the last member and the smectogenic mesophase from the hexyloxy to the tetradecyloxy member of the series. The nematic mesophase is of a threaded or Schlieren type, and the smectic mesophase is of a focal conic fan of the type A or C. Mesomorphic properties of the present novel homologous series are compared with other structurally similar homologous series.     

Steroid motor: dynamics of cholesteric helix induction in the nematic droplet

A nematic liquid crystal can be converted into a cholesteric phase by a chiral dopant, and the cholesteric pitch can be changed by its photochemical transformations [1]. For the first time we investigate the dynamics of the cholesteric phase induction using seven steroids (vitamin D isomers and related compounds) as chiral dopants. Here we report the new effect of rotation of a rod-like steroid crystal (0.1-1 mm length) when it is placed at the surface of a nematic drop and its dissolution course was followed with a polarizing microscope. For all the compounds univocal correspondence was noticed between the crystal rotation direction, the helicity of the molecular steroid ring system [2] and the sign of the cholesteric macrohelix determined by the Cano-Grandjean method [3]. No rotation was observed in the isotropic phase.     

Phase Diagrams of Cholesteric and Nematic Thermotropic Liquid-Crystalline Polymers

Linear mesogenic polyesters with flexible spacers (molecular weight ranging from 9,000 to 20,000) are studied by polarized microscopy. The nematic and cholesteric mesophases are identified by means of the contact method. Two enantiomers form perfect solid, cholesteric and liquid solutions. The sign of the twist of the cholesteric phases are determines.