Lyotropic liquid-crystalline mesophases and a novel,solid physical form of some water-soluble,reactive dyes

Abstract

A novel, solid physical form has been observed when some water-soluble, reactive dyes are isolated from aqueous solution, as sodium salts, by the addition of sodium chloride. This quasi-crystalline form has a fibrous morphology, is birefringent but is not crystalline. Dyes of this type are known to form lyotropic liquid-crystalline mesophases in water. Preliminary X-ray diffraction investigations, reported here, for the mesophases formed by two such dyes indicate that they have columnar structures of the type first proposed for the lyotropic mesophases of the disodium chromglycate/water system and subsequently for other drug and dye molecules. X-ray and electron diffraction studies of the quasi-crystalline form show that it has a closely related columnar structure. The quasi-crystalline form is postulated to result from the formation and subsequent precipitation of columnar dye aggregates, as sodium chloride is added to the aqueous dye solution.     

The influence of sodium chloride and urea on chromonic liquid crystals formed by CI Acid Red 266

Chromonic liquid crystals are currently receiving renewed interest with particular attention on the Edicol Sunset Yellow (ESY)/water system, which forms columnar nematic and hexagonal phases. CI Acid red 266 is structurally fairly similar to ESY and also forms columnar nematic and hexagonal phases but at much lower concentrations (>1%). In this study, we have examined the influence of sodium chloride and urea on chromonic liquid crystals formed by CI acid red 266. The techniques employed were polarising microscopy, X-ray diffraction and ²H NMR. Sodium chloride moves the concentration at which mesophases form to higher values. Once formed, the mesophases are stable to slightly higher temperatures. Screening of the interstack electrostatic repulsions by added electrolyte appears to be responsible for the changes. Urea can be added in fairly large concentrations (up to 25 wt%) without significant changes in mesophase stability. X-ray diffraction measurements show that there is little change in the aggregate structure with added urea. NMR measurements on urea and water ordering show that urea has much larger order parameters than water. Both order parameters are much smaller than values reported for ESY, but this is simply because of the lower dye concentrations. The larger order parameters for urea appear to arise from some intercalation of urea into the acid red 266 stacks. There is no evidence for changes in ‘water structure’ by the addition of urea.     

Chromonic liquid crystal formation by Edicol Sunset Yellow

The solution and liquid crystalline phases formed by dissolution of the dye Edicol Sunset Yellow (ESY) in water have been examined using optical microscopy, multinuclear NMR (1H, 2H, 13C, 23Na), and X-ray diffraction. From the solution 1H and 13C spectra (particularly 13C), it is clear that the tautomeric form present in all these phases is the hydrazone, NH, structure, not the usually given azo, OH, form. Two chromonic mesophases occur: a nematic (N) phase at approximately 30-40 wt % and a hexagonal (M) phase at approximately 40-45 wt %. X-ray diffraction data show that the aggregates in the mesophases are single molecule stacks, with a typical spacing of approximately 3.5 angstroms, as expected for these systems. The NMR quadrupole splittings (2H2O, 23Na) are similar to those observed for surfactant lyotropic mesophases, suggesting that there are no water molecules or counter ions that are tightly bound to the ESY aggregates. An unusual feature of the X-ray diffraction pattern of the mesophases is the occurrence of diffuse off-axis reflections at approximately 6.8 angstroms. It is proposed that these arise from a head-to-tail packing of the molecules within the stacks.     

Chromonic liquid crystals formed by CI Acid Red 266 and related structures

Chromonic liquid crystals are currently receiving increased attention because they have applications in a wide range of products. In this study, we have compared the chromonic mesophase behaviour of four azo dyes with similar chemical structures. Our objective is to determine if there is an obvious link between mesophase formation and dye chemical structure. Orange G does not form mesophases over the concentration range examined (saturated solution > ~20–30 wt%). The other three compounds all form nematic (N) and hexagonal (H) mesophases, but over very different concentration ranges. X-ray diffraction shows that the ordered Edicol Sunset Yellow (ESY) aggregates present in the mesophases have a single molecule cross section, while those of CI Acid Red have a cross section equivalent to six to eight molecules, probably organised in a ‘water-filled pipes’ structure. NMR quadrupole splittings of ²H₂O demonstrate that water binding to the aggregates is similar to that found for surfactant lyotropic mesophases. The sodium (²³Na) quadrupole splittings for Orange II and CI Acid Red are similar to the values found for surfactant hexagonal phases, suggesting that most sodium ions are ‘bound’ to the aggregates. This is unlike the behaviour of ESY where only one of the two sodium ions is bound.     

Liquid-crystalline comb copolymers with lipoamino acid side chains Synthesis and structure study

In order to obtain liquid-crystalline polymers without using classical mesogenic groups, comb copolymers consisting of a polyacrylamide main chain and lipoamino acid side chains have been synthesized. These copolymers were obtained by the polymerization of lipoamino acid macromonomers. These macromonomers were obtained from, α,ω-aliphatic amino acids by linking a polymerizable group at the amino end and an α-amino acid at the carboxyl end. The macromonomers were then transformed into comb copolymers by free-radical polymerization. These comb copolymers exhibit mesophases both in aqueous solution and in the anhydrous state. The range of stability and the structures of the mesophases were determined by X-ray diffraction. Two types of structures were found, corresponding to the lyotropic lamellar and hexagonal mesophases. The influences of the nature of the amino acid and the water concentration on the domain of stability and the geometrical parameters of the mesomorphic structures were investigated.     

Elliptical diffusion of dye in hexagonal columnar polycatenar mesophases

We have studied polycatenar compounds which exhibit hexagonal columnar mesophases. In the planar orientation of these mesophases, the elliptical diffusion of the dissolved dyes is visualized by taking several pictures of the sample. The diffusion ratio D// /D is deduced for these columnar mesophases. Furthermore, using a classical optical absorption technique, we present measurements of dye diffusion in the same mesophases. The diffusion constants are measured in two geometries, along and perpendicular to the columns. The diffusion anisotropy ratios are in agreement with those deduced from the ellipse axes. The structure of these new columnar mesophases exhibited by rod-like mesogens is compared with that of disk-like mesogens.     

Elliptical diffusion of dye in hexagonal columnar polycatenar mesophases

We have studied polycatenar compounds which exhibit hexagonal columnar mesophases. In the planar orientation of these mesophases, the elliptical diffusion of the dissolved dyes is visualized by taking several pictures of the sample. The diffusion ratio D// /D is deduced for these columnar mesophases. Furthermore, using a classical optical absorption technique, we present measurements of dye diffusion in the same mesophases. The diffusion constants are measured in two geometries, along and perpendicular to the columns. The diffusion anisotropy ratios are in agreement with those deduced from the ellipse axes. The structure of these new columnar mesophases exhibited by rod-like mesogens is compared with that of disk-like mesogens.     

Studies on the aggregation behaviour of some direct dyes in aqueous solutions

Summary Physicochemical properties of the two direct dyes ChrysophenineG and Chlorazol Sky Blue FF in aqueous solutions, have been studied using solubility and electrical conductivity methods. The results indicate that in aqueous solutions, both dyes in the presence of added sodium chloride start forming aggregates at a critical dye concentration. This critical concentration is a function of the temperature and the concentration of added sodium chloride. An analysis of the conductivity data shows that in all solutions containing dye aggregates the concentration of single dye ions is constant and equal to the critical cocentration. Since the solubility of ChrysophenineG unlike that of Chlorazol Sky Blue FF, is very small in the presence of added sodium chloride, the solubility product principle has been used to experimentally determine mean ionic activity coefficients for the dye ions. These values have been compared with activity coefficients calculated using a suitable form of theDebye-Hückel expression. The results indicate that ChrysophenineG in aqueous solutions behaves as a strong unaggregated 12 valence type electrolyte in dilute solutions below the critical concentration for aggregate formation.Finally, a close correlation has been shown to exist between the critical dye concentrations for aggregate formation and the equilibrium dye bath concentrations at which the aqueous solution adsorption isotherms for these dyes on cotton, viscose and cuprammonium rayon fibres show a marked change in slope leading to the formation of a flat plateau region.     

Polymer gel/organic dye complexes in aqueous salt solutions

The present work is devoted to the study of the complex formation of polymer gel with organic dye and their properties in the aqueous salt solutions. Two systems were studied: 1) polyelectrolyte gel based on poly(diallyldimethylammonium chloride) and water soluble oppositely charged organic dyes (alizarin red S and catechol violet) and 2) organogel based on poly(N-vinylcaprolactam) and dithizone. The collapse of the polyelectrolyte gels in the presence of oppositely charged dyes together with the effective absorption of dyes was observed. The shrinking degree and the dye absorption by the gel depends on the dye concentration. In the case of PVCa gel in organic media the dye absorption takes place. The main attention has been concentrated on the study of the behaviour of gel/dye complex immersed in the salt solution if dye is the chelating ligand for metal ions. It was shown that polyelectrolyte gels generally form stable complexes with oppositely charged dyes. The behaviour of PVCa-dithizone-chloroform system was studied in AgNO₃ aqueous solution. The release of dithizone to the external aqueous solution of AgNO₃ reservoir is completely suppressed. Absorption spectra of gel/dye and gel/dye/metal ion systems were studied. It was shown that metal ions penetrate inside the gel phase and the dye/metal ion complexes form within the gel. The dependence of the optical density for the systems of gel/dye/metal ion on the salt concentration is observed.     

Amphotropic liquid crystallinity of N,N'-diundecenoylbenzene-1,4-diamine (DUBDA)

N,N'-diundecenoylbenzene-1,4-diamine (DUBDA), an amide with long symmetric aliphatic chains, is shown to exhibit monotropic thermotropic liquid crystallinity as well as lyotropic liquid crystallinity in highly polar solvents on the basis of differential scanning calorimetry, polarized optical microscopy, temperature-variable FTIR, and X-ray diffraction analysis. There are obvious differences between the two mesophases in terms of molecular stacking and driving force, although the two mesophases originate from the same molecule. In addition, a possible lamellar model for the lyotropic mesophase is proposed.     

Synthesis and characterization of tris-methacrylated 3,4,5-tris

The synthesis of liquid crystalline 3,4,5-tris(11-methacryloylundecyl-1-oxybenzyloxy)benzoic acid, 2-methyl-(1,4,7,10,13-pentaoxacyclopentadecane)-3,4,5-tris[4-(11-methacryloylundecyl-1-oxy)benzyloxy] benzoate and its 1:1 complex with sodium triflate is described. The observed mesophases were identified, by polarized optical microscopy and contact preparation techniques, to be of hexagonal columnar disordered structure. The amphiphiles form lyotropic columnar phases in concentrated methacrylate solvents, while at low solute contents supramolecular organogels emerge.     

The effect of shear on ordered block copolymer solutions

Block copolymers are extensively used in solution, especially aqueous solution, because of their amphiphilic character. This leads to the formation of lyotropic mesophases under given conditions of concentration and temperature. In many applications, block copolymer solutions are subjected to shear during processing (for example in drug delivery or when washing in detergent solutions) and thus it is of considerable interest to understand how shear affects the mesophase structure. Recent research has focussed on probing shear-induced structural transformations in lamellar, hexagonal and cubic-packed micellar phases using small-angle X-ray and neutron scattering.     

A study of the self-assembly of 2-deoxyguanosine 3 5-cyclic monophosphate, d(cGp), by CD and X-ray diffraction

2-Deoxyguanosine 3 5-cyclic monophosphate forms in water cholesteric and hexagonal columnar mesophases. The polymorphic behaviour and the structural building blocks of the liquid crystalline phases, as determined by optical microscopy, CD spectroscopy and X-ray diffraction, are comparable to those found with all the deoxyguanylates investigated so far (in particular with deoxuguanosine 5- and 3-monophosphate). The present results show that the formation of a stacked array of planar G-tetramers, a necessary condition for the existence of the columnar mesophases, occurs even in the absence of hydrogen bonding groups linking the molecules along the length of the columns.     

Synthesis and phase characterization of a double-tailed pyrrole-containing surfactant: a novel tecton for the production of functional nanostructured materials

A double-tailed polymerizable (pyrrolylalkyl) ammonium amphiphile has been synthesized, and its interfacial properties and aqueous phase behavior have been studied by polarized optical microscopy and X-ray diffraction. The Krafft temperature is about 27 degrees C, and the critical micelle concentration at 40 degrees C is about 1 mM, as obtained from surface tension measurements, potentiometry, and isothermal titration calorimetry. The lyotropic behavior of the surfactant is found to be of a complex nature. At concentrations higher than the micellar (L1) region, two mesophases have been identified: a second isotropic (L2) phase, which is probably micellar but not fully miscible with water, and a lamellar (L(alpha)) phase, showing interesting alignment properties. Small-angle X-ray scattering analysis of the mesophases has been evaluated in terms of a model of spherical micelles, which describes a mutual arrangement by a structure factor derived from a hard-sphere potential (Percus-Yevick, "PY", approach). Interest in the comprehensive phase behavior of the polymerizable surfactant is based on the desire to integrate the system into a composite material to obtain potentially conducting self-assembled hybrid mesostructures.     

Oriented monolayers prepared from lyotropic chromonic liquid crystal

We use a layer-by layer electrostatic self-assembly technique to obtain in-plane oriented aggregates of mesogenic dye molecules cast from lyotropic chromonic liquid crystals (LCLCs) on mica substrates. The aqueous solutions of dye used for deposition are in the nematic phase. Atomic force microscopy and X-ray photoelectron spectroscopy of the dried film reveal that the LCLC molecules adsorb at the charged substrate preserving ordered aggregates of elongated shape characteristic of the nematic phase in the aqueous solution. These elongated aggregates of LCLC molecules form films with in-plane orientational order and are compositionally distinct from the substrate.     

Self-alignment of dye molecules in micelles and lamellae for three-dimensional imaging of lyotropic liquid crystals

We report alignment of anisotropic amphiphilic dye molecules within oblate and prolate anisotropic micelles and lamellae, the basic building blocks of surfactant-based lyotropic liquid crystals. Absorption and fluorescence transition dipole moments of these dye molecules orient either parallel or orthogonal to the liquid crystal director. This alignment enables three-dimensional visualization of director structures and defects in different lyotropic mesophases by means of fluorescence confocal polarizing microscopy and two-photon excitation fluorescence polarizing microscopy. The studied structures include nematic tactoids, Schlieren texture with disclinations in the calamitic nematic phase, oily streaks in the lamellar phase, developable domains in the columnar hexagonal phase, and various types of line defects in the discotic cholesteric phase. Orientational three-dimensional imaging of structures in the lyotropic cholesterics reveals large Burgers vector dislocations in cholesteric layering with singular disclinations in the dislocation cores that are not common for their thermotropic counterparts.     

Lyotropic liquid-crystalline phase composed of aliphatic amino stearates and water

Polarization microscopy, differential calorimetry D.S.C. and X-ray diffraction have been used to examine the lyotropic mesophases which occur in solutions of amino salts in water. The following systems were investigated: methylamino, n-propylamino, n-butylamino, isobutyl-amino and n-hexylamino stearates as one component of the system and water as the other. The types of lyotropic phase and the range in which they occur were determined as functions of concentration and temperature.     

Effect of degree of acetylation and solvent on the chiroptical properties of lyotropic (acetyl) (ethyl) cellulose solutions

(Acetyl) (ethyl) cellulose (AEC) polymers with an ethyl degree of substitution (DS) of 2.5 and acetyl DS ranging from 0 to 0.5 dissolve readily in a wide range of organic solvents and form chiral nematic liquid crystalline phases in concentrated solution. The chiroptical properties of these liquid crystals are strongly influenced by the acetyl content and solvent. In dichloromethane, dibromomethane, chloroform, bromoform, m-cresol, acetic acid, and aqueous phenol, the AEC lyotropic mesophases all show a handedness inversion as the acetyl DS of the polymers is increased, changing from left- to right-handed supermolecular helicoidal structures. The temperature dependence of the pitch for these mesophases is also reversed from negative to positive with increasing acetyl DS in all the above solvents except aqueous phenol, in which the corresponding AEC mesophases change from positive to negative. The optical microscopic, optical diffraction, and ORD evidence provide a unique indication that the reversal of the handedness and temperature dependence for the AEC mesophases occurs at a compensated degree of acetylation, DA^*. The corresponding compensated mesophases show an infinite pitch and behave optically like nematic mesophases. The value of the DA^* is dependent on solvent. In dichloroacetic acid, AEC liquid crystals remain right-handed, independent of the acetyl DS. At given concentration and temperature, the long pitch samples flow much more readily than short pitch samples. © 1994 John Wiley & Sons, Inc.     

A new lyotropic liquid crystalline phase formed in hydrocarbon solvents by a deoxyguanosine derivative through extensive hydrogen bonding

Lipophilic deoxyguanosine 1 in pure hydrocarbons or in mixed CHCl3-hydrocarbon solvents forms a new lyotropic liquid crystalline phase characterized by a two dimensional square packing. The structural elements of the phase are ribbon-like assembled species which are completely different from the columnar structures, based on G-quartets, which are the building blocks of the mesophases formed by deoxyguanosine oligonucleotides in water.     

Synthesis and Characterization of Liquid-Crystalline Tetraoxapentacene Derivatives Exhibiting Aggregation-Induced Emission

A series of new tetrakis(dialkoxyphenyl) dicyanotetraoxapentacene derivatives ( 1 a – c ) were prepared by reaction of the appropriate terphenyl diols with tetrafluoroterephthalonitrile in good yields. Compounds 1 b and 1 c , which bear hexyloxy and decyloxy side chains, exhibited columnar hexagonal mesophases, as shown by polarized optical microscopy, variable-temperature powder X-ray diffraction, and differential scanning calorimetry. Single-crystal X-ray diffraction of methoxy-substituted 1 a revealed that the dicyanotetraoxapentacene core is highly planar, consistent with the notion that these molecules are able to stack in columnar mesophases. A detailed photophysical characterization showed that these compounds exhibit aggregation-induced emission in solution, emission in nonpolar solvents, weak emission in polar solvents, and strong emission in the solid state both as powder and in thin films. These observations are consistent with a weakly emissive charge-transfer state in polar solvents and a more highly emissive locally excited state in nonpolar solvents.