Novel surfactant mesostructural topologies: between lamellae and columnar (hexagonal) forms

Recent developments in theoretical and experimental studies of amphiphilic lyotropic ‘intermediate’ mesophase formation are summarized. For the purposes of the review, we consider intermediate mesophases to be self-assemblies with novel geometries and topologies, excluding lamellar, bicontinuous sponge, columnar (hexagonal) and micellar mesophases. Intermediates include novel branched bilayer topologies, enclosing multiple interwoven channel systems and inclined rod packings, and punctured bilayer morphologies, including mesh phases and bicontinuous monolayers.     

Lyotropic liquid crystalline phase behavior of a polymeric amphiphile polymerized via their hydrophilic ends

The reaction of the nonionic low molecular mass surfactant 3, 6, 9, 12, 15, 18, 21, 24-octaoxaoctatriacontane-1-ol (CH₃(CH₂)₁₃(OCH₂CH₂)₈OH, C₁₄E₈) with acryloyl chloride yielded the monomeric amphiphile II (CH₃(CH₂)₁₃(OCH₂CH₂)₈O₂C-(CH:CH₂) with the polymerizable group located at the hydrophilic end of the molecule. Using radical polymerization, the polymeric surfactant III is obtained. These three surfactant water systems exhibit lyotropic liquid crystalline phases. The binary phase diagrams are compared with each other. In changing from the monomer-water to the polymer-water system a stabilization of the lyotropic mesophases is observed with amphiphiles which are connected via their hydrophilic ends; it is known for the surfactants to be connected via their hydrophobic ends. The appearance of the inverse mesophases, as expected from the molecular geometry of the polymer, is not observed.     

Polymerisation in lyotropic liquid-crystalline phases of dioctadecyldimethylammonium bromide

The polymerisation of styrene in lyotropic liquid-crystalline (LC) phases of dioctadecyldimethylammonium bromide (DODAB) in water is explored. Amphiphile concentrations between 20 and 50 wt % are employed. The study is set out as a model study for polymerisation reactions in nonstabilised, nonfunctional bilayer systems. X-ray characterisation was used to assess the phase behaviour of the lyotropic mesophases before, during and after polymerisation. The DODAB/water system forms the lamellar phase within the concentration range considered. Addition of styrene to the lamellar phase of DODAB at an equimolar ratio induces a phase shift to a bicontinuous cubic phase at elevated temperatures near the phase-transition temperature. Upon polymerisation within this cubic phase, the phase structure is maintained if the system is kept at constant temperature; however, if the polymer/amphiphile phase is cooled, the lamellar phase, being typical of the DODAB/water system, is restored. It is concluded that, as a result of phase separation between the polymer and the amphiphile phase, the polymerisation in lyotropic LC phases does not provide a stable copy of the templating amphiphile phase. This is in analogy to the observations for polymerisations in other lyotropic phases. Received: 16 March 2000 Accepted: 1 July 2000     

Lyotropic Liquid Crystal to Soft Mesocrystal Transformation in Hydrated Salt–Surfactant Mixtures

Hydrated CaCl₂, LiI, and MgCl₂ salts induce self‐assembly in nonionic surfactants (such as C₁₂H₂₅(OCH₂CH₂)₁₀OH) to form lyotropic liquid‐crystalline (LLC) mesophases that undergo a phase transition to a new type of soft mesocrystal (SMC) under ambient conditions. The SMC samples can be obtained by aging the LLC samples, which were prepared as thin films by spin‐coating, dip‐coating, or drop‐casting of a clear homogenized solution of water, salt, and surfactant over a substrate surface. The LLC mesophase exists up to a salt/surfactant mole ratio of 8, 10, and 4 (corresponding to 59, 68, and 40 wt % salt/surfactant) in the CaCl₂, LiI, and MgCl₂ mesophases, respectively. The SMC phase can transform back to a LLC mesophase at a higher relative humidity. The phase transformations have been monitored using powder X‐ray diffraction (PXRD), polarized optical microscopy (POM), and FTIR techniques. The LLC mesophases only diffract at small angles, but the SMCs diffract at both small and wide angles. The broad surfactant features in the FTIR spectra of the LLC mesophases become sharp and well resolved upon SMC formation. The unit cell of the mesophases expands upon SMC transformation, in which the expansion is largest in the MgCl₂ and smallest in the CaCl₂ systems. The POM images of the SMCs display birefringent textures with well‐defined edges, similar to crystals. However, the surface of the crystals is highly patterned, like buckling patterns, which indicates that these crystals are quite soft. This unusual phase behavior could be beneficial in designing new soft materials in the fields of phase‐changing materials and mesostructured materials, and it demonstrates the richness of the phase behavior in the salt–surfactant mesophases.     

Structures and crystal chemistry of the double perovskites Ba2LnB′O6 (Ln=lanthanide and B′=Nb, Ta):: Part II—Temperature dependence of the structures of Ba2LnB′O6

The structures of eight members of the series of double perovskites of the type Ba₂LnB′O₆ (Ln=La³⁺-Sm³⁺ and Y³⁺ and B′=Nb⁵⁺ and Ta⁵⁺) were examined both above and below room temperature using synchrotron X-ray powder diffraction. The La³⁺ and Pr³⁺ containing compounds had an intermediate rhombohedral phase whereas the other tantalates and niobates studied have a tetragonal intermediate. This difference in symmetry appears to be a consequence of the larger size of the La³⁺ and Pr³⁺ cations compared to the other lanthanides. The temperature range over which the intermediate symmetry is stable is reduced in those compounds near the point where the preferred intermediate symmetry changes from tetragonal to rhombohedral. In such compounds the transition to the cubic phase involves higher order terms in the Landau expression. This suggests that in this region the stability of the two intermediate phases is similar.     

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.     

Influence of glycerol on the formation of lyotropic mesophases —microscopic texture observations for determining preliminary phase diagrams of binary K-soap/glycerol systems

Analogously to aqueous K-soap/water systems already examined, the glycerol-containing systems KC _n /G (KC _n ;n=12, 14, 16, 18, 22; G=glycerol) are also able to build up hexagonal, lamellar, optically isotropic, gel-like and crystalline phases. These preliminary phases have been identified by texture observations of contact samples and singular concentrations with a polarizing microscope. The appertaining phase regions have been plotted in the binary phase diagrams.Correspondences and differences between these systems have been elucidared by drawing a comparison. Mosaic texture and oily streaks are typical of the lamellar phase. Spherulites are mainly found in the heterogeneous two-phase region lamellar/isotropic. The textures of the hexagonal phase are of fan-like morphology. The appearance of the gel phase texture resembles globular or curd-like structures.The influences exerted by the increasing chain lengths of the K-soaps (KC _n ,n=12–22) on the phase regions in the binary systems (KC _n /G) can be described as follows. The concentrations required for forming the hexagonal and the lamellar phase respectively are shifted toward lower K-soap concentrations. The concentration range in which the hexagonal phase is stable is diminished. The temperature range in which the hexagonal phase is stable becomes larger. The upper temperature limit of the lamellar phase region is lowered.Binary aqueous and glycerol-containing K-soap systems have the following common features: The hexagonal phase is built up at low soap concentrations. The lamellar phase is formed at high soap concentrations. The lamellar phase is formed at high soap concentrations. An optically isotropic region is inserved between the lamellar and the hexagonal phase in aqueous and glycerol-containing systems of the types KC₁₄, KC₁₆ and KC₁₈. The temperature of the transition hexagonalisotropic phase (HS) runs through a maximum value. On increasing the chain length the formation of the hexagonal phase is shifted in the direction of lower soap concentrations.Aqueous and glycerol-containing K-soap mixtures differ in the following essential points: The lyotropic mesophases (H, L, I) of aqueous systems are formed at considerably lower soap concentrations than the corresponding phases of glycerol-containing systems. The lamellar phases of aqueous systems reach the regions of very low soap concentrations. The lyotropic mesophases of aqueous systems are built up at temperatures lower than the corresponding ones of glycerol-containing mixtures. In aqueous systems the concentration range of the lamellar phase increases with increasing chain length, in contrast to glycerol-containing systems where it is diminished.     

Phase behaviour of n-alkyl- and bi-alkylbenzenesulphonates. Nematic lyotropics from double chain surfactants

The lyotropic mesophases in binary systems of surfactants in water: n-alkylbenzenesulphonates (C₈-C₁₂), two chain C₁₂-surfactants, and dodecyl-benzenesulphonic acid, were investigated. The micellar properties were examined by conductometry and viscosimetry. The phase diagrams were determined using crossed polarizers, ²H NMR spectroscopy and polarization microscopy. Besides lamellar and inverse cubic phases, new nematic lyotropic phases have been found, presenting precursors for the lamellar phases, and exhibiting very fast alignment in a magnetic field.     

The binary system composed of a bent-core compound forming a B7 phase and a nematogenic calamitic compound

The isobaric phase diagram for a binary system of liquid crystals is presented. One mixing component is a bent-core mesogen forming a B₇ phase and the other one is a nematogenic calamitic compound. The occurring mesophases have been identified by their optical textures as well as by X-ray investigations. The B₇ phase exists down to about 60 mol% of the bent-core compound A / 40 mol% of the calamitic compound B. Two additional mesophases are induced in the mixed phase region. At medium concentrations (around 50 mol%) an oblique columnar phase appears which shows a similar X-ray pattern to the B₇ phase but an utterly different nucleation on cooling the isotropic liquid and a completely dissimilar texture. At concentrations below 35 mol% A, a further phase is induced which possesses an irregularly modulated layer structure. This phase can be regarded as an intermediate state between the regularly modulated Col_r (B₁) phase and the intercalated B₆ phase. It transforms on cooling into the phase with a regularly modulated structure.     

Characterization and flow properties of lyotropic ultrahigh-molar-mass polysaccharide mesophases

The occurrence of lyotropic mesophases in solutions of various polysaccharides, such as non-ionic schizophyllan and anionic xanthan, was demonstrated by means of polarizing microscopy. In contrast to synthetic polymers where the formation of liquid-crystalline phases has been attributed to the presence of mesogenic groups in the main- or side-chain, here a helical structure is a prerequisite for the formation of mesophases. It was then shown that the stability of the helix is dependent on the chemical structure and the arrangement of the side groups. Apart from their optical anisotropy, some lyotropic mesophases are distinguished by extraordinary viscous and elastic properties (e.g. maximum behaviour of viscosity). The viscoelastic material functions were determined by rheological methods. A precise characterization of the chemical and steric microstructure should provide information on the ability of polysaccharides to form mesophases. Determination of the chemical microstructure (quaternary polymer) was carried out by ¹H NMR spectroscopy after ultrasonic degradation. Low- and multi-angle laser light scattering were employed for the determination of the steric microstructure which indicates an expanded semi-flexible structure. The experimental results were compared with those from molecular modelling.     

The liquid-crystalline properties of selected cellulose derivatives

The liquid-crystalline properties of three cellulose esters, phenylacetoxy cellulose (PAC), 4-methoxyphenylacetoxy cellulose (4MPAC), and p-tolylacetoxy cellulose (TAC) and two cellulose silyl ethers, trimethyl silyl cellulose (TMSC) and t-butyldimethylsilyl cellulose (TBDMSC), are reported. Hot-stage polarized light microscopy provided evidence regarding the formation of thermotropic mesophases in the PAC, 4MPAC, TAC, and TMSC in bulk form upon heating. The concomitant DSC data showed further evidence of the thermotropic nature of these materials. PAC, 4MPAC, TAC, and TMSC formed lyotropic mesophases at 44, 48, 50, and 27 wt%, respectively in CH₂Cl₂. The presence of fingerprint patterns in wholly anisotropic solutions in conjunction with optical rotation measurements confirmed the cholesteric nature of these liquid crystalline solutions. TBDMSC formed neither a lyotropic nor a thermotropic liquid-crystalline phase due to the low degree of substitution (DS 0.68) of this derivative. The hydroxyl substituents of PAC, 4MPAC, TAC, and TMSC may be readily removed under mild conditions to regenerate cellulose.     

The Self-Assembly of a Lipophilic Deoxyguanosine Derivative and the Formation of a Liquid-Crystalline Phase in Hydrocarbon Solvents

The lipophilic 3′,5′-di-O-decanoyl-2′-deoxyguanosine ( 1 ) in CHCl₃ undergoes extensive self-assembly, mediated by H-bonding between the guanine bases, to give ribbon-like aggregates. X-Ray investigation of the platelets obtained from CHCl₃ reveals a disordered fibre-like structure consisting of stacks of the ribbon-like aggregates. The aggregates are completely different from the columnar structures, based on G-quartets, which are the building blocks of the mesophases formed by deoxyguanosine oligonucleotides in H₂O. In pure hydrocarbons or in CHCl₃/hydrocarbons, 1 forms a lyotropic liquid-crystalline phase.     

Structure of mesh phases in a cationic surfactant system with strongly bound counterions

We report the observation of an intermediate mesh phase with rhombohedral symmetry, corresponding to the space group Rm, in a mixed surfactant system formed by the cationic surfactant cetyltrimethylammonium bromide (CTAB) and the organic salt 3-sodium-2-hydroxy naphthoate (SHN). It occurs between a random mesh phase (L(alpha)(D)) and a lamellar phase (L(alpha)) at low temperatures; at higher temperatures, the (L(alpha)(D)) phase transforms continuously into the (L(alpha)) phase with an increasing surfactant concentration (phi(s)). To separate the effects of salt and phi(s) on the phase behavior, the ternary system consisting of cetyltrimethylammonium 3-hydroxy-naphthalene-2-carboxylate (CTAHN), sodium bromide (NaBr), and water was studied. The intermediate mesh phase is found in this system at high NaBr concentrations. The micellar aggregates, both in the intermediate and random mesh phases, are found to be made up of a two-dimensional network of rod-like segments, with three rods meeting at each node. The average mesh size increases with phi(s), and the transition from the random mesh phase to the intermediate phase is found to occur when it is approximately 1.5 times the lamellar periodicity. The intermediate mesh phase is absent in the equimolar dodecyltrimethylammonium bromide (DTAB)-SHN system, indicating the role of the surfactant chain length in the formation of this phase. This system exhibits a random mesh phase over a very wide range of water content, with the average mesh size decreasing upon an increasing phi(s), contrary to the trend seen in the CTAB-SHN system.     

Order and disorder in Ca2ND0.90H0.10-A structural and thermal study

The structure of calcium nitride hydride and its deuterided form has been re-examined at room temperature and studied at high temperature using neutron powder diffraction and thermal analysis. When synthesised at 600 °C, a mixture of both ordered and disordered Ca₂ND_0.90H_0.10 phases results. The disordered phase is the minor component and has a primitive rocksalt structure (spacegroup Fm3m) with no ordering of D/N on the anion sites and the ordered phase is best described using the rhombohedral spacegroup R-3m with D and N arranged in alternate layers in (111) planes. This mixture of ordered and disordered phases exists up to 580 °C, at which the loss of deuterium yields Ca₂ND_0.85 with the disappearance of the disordered phase. In the new ordered phase there exists a similar content of vacancies on both anion sites; to achieve this balance, a little N transfers onto the D site, whereas there is no indication of D transferring onto the N-sites. These observations are thought to indicate that the D/N ordering is difficult to achieve with fully occupied anion sites. It has previously been reported that Ca₂ND has an ordered cubic cell with alternating D and N sites in the [100] directions [1]; however, for the samples studied herein, there were clearly two coexisting phases with apparent broadening/splitting of the primitive peaks but not for the ordered peaks. The rhombohedral phase was in fact metrically cubic; however, all the observed peaks were consistent with the rhombohedral unit cell with no peaks requiring the larger ordered cubic unit cell to be utilised. Furthermore this rhombohedral cell displays the same form of N-D ordering as the Sr and Ba analogues, which are metrically rhombohedral.     

Tyrosine‐Based Ionic Liquid Crystals: Switching from a Smectic A to a Columnar Mesophase by Exchange of the Spherical Counterion

Synthetic strategies were developed to prepare l ‐tyrosine‐based ionic liquid crystals with structural variations at the carboxylic and phenolic OH groups as well as the amino functionality. Salt metathesis additionally led to counterion variation. The liquid‐crystalline properties were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X‐ray diffraction (WAXS, SAXS). The symmetrical ILC chlorides bearing the same alkyl chain at both the ester and ether but either an acyclic or cyclic guanidinium group displayed enantiotropic SmA₂ mesophases with phase widths of 31–88 K irrespective of the head group. It was particularly the replacement of chloride in the acyclic guanidinium ILC by hexafluorophosphate that induced a phase change from SmA₂ to Col_r. This phase change was attributed to a higher curvature of the interface due to the larger anion, which increased the effective head group cross‐sectional area of the amphiphilic ILC. The unsymmetrical acyclic guanidinium chlorides, bearing a constant C₁₄ ester and variable alkyl chains on the phenolic position, formed enantiotropic SmA₂ phases. The derivative with the largest difference in chain lengths, however, displayed a Col_r phase, resulting from discoid aggregates of the cone‐shaped guanidinium chloride. The results are discussed in terms of the packing parameters, which indicate that the phase behaviour of the thermotropic tyrosine‐based ILCs shows analogies to those of lyotropic liquid crystals.     

Mesophases II

In the continuation of a review of the classification, properties and applications of mesophases, the general features of thermodynamic data of thermotropic liquid–crystalline phase transitions are surveyed. The orientation of molecules in liquid–crystalline mesophases is discussed in relation to the electrical properties. Some applications of mesophases are outlined. After surveys of both the structural classes of lyotropic mesophases and the properties of plastic crystals in cubic phases, the thermodynamic, structural and other properties of all mesophases-are summarily considered in relation to the present state of the knowledge in this field.     

The rz structure of 1,2,5-selenadiazole partially oriented in ordered mesophases as determined by PMR spectra including 13C and 77Se satellites

The proton magnetic resonance spectra of 1,2,5-selenadiazole together with the natural abundance ¹³C and ⁷⁷Se satellites have been obtained and analysed in two lyotropic mesophases and in a thermotropic mesophase. The r_z structure of the molecule has been obtained.     

Structural studies of a new series of biforked mesogens derived from 3,4 dialkoxy cinnamic acid and 3-(3,4 dialkoxy-phenyl) propanoic acid

Structural studies of selected homologues of some new series of biforked mesogens have been performed by X-ray diffraction methods. These series exhibit a thermotropic mesomorphism which shows some similarities with lyotropics. We have identified three different mesophases with large three dimensional lattice cells (i.e. body centred cubic, hexagonal and rhombohedral). The occurrence of such mesophases is related to the core flexibility; moreover, the chain to core length ratio is one of the main parameters that drive the thermotropic polymorphism, playing a role similar to that of the solvent concentration in a lyotropic system. However the symmetries as well as the lattice constants, in units of molecular size, appear to be different in the two cases owing to differences in their chemical architecture.     

Effect of the surfactant alkyl chain length on the stabilisation of lyotropic nematic phases

Lyotropic quaternary mixtures of potassium alkanoates (KCx) and sodium alkyl sulphates (NaCxS), where x is the number of carbon atoms in their alkyl chains, were prepared to investigate the effect of the surfactant alkyl chain length on the stabilisation of lyotropic nematic phases. The lyotropic mixtures investigated were formed by the dissolution of KCx (NaCxS) surfactants in the mixture of Rb₂SO₄/1-decanol/water (Na₂SO₄/1-decanol/water), separately. The uniaxial-to-biaxial nematic phase transitions were identified from the temperature dependence of the birefringences of the nematic phases by means of laser conoscopy. The micelle dimensions were obtained from small-angle X-ray scattering measurements. It was observed that the increase in the surfactant alkyl chain length causes the micellar growth in the plane perpendicular to the main amphiphile bilayer. The surfactant alkyl chain length plays a key role on the shape anisotropy of micelles, which triggers the orientational fluctuations that are responsible for the stabilisation of the different lyotropic nematic phases.     

Vanadium Pentoxide Sol and Gel Mesophases

Colloidal suspensions of V₂O₅ ribbon-like particles display optical textures typical of lyotropic nematic phases. Tactoids (small nematic droplets) and then isotropic phases are formed as these systems are diluted. Nematic suspensions can be oriented by applying a magnetic or an electric field. Such a liquid crystal behavior is mainly due to the highly anisotropic shape of vanadium oxide colloidal particles. Acid dissociation at the oxide/water interface gives rise to surface electrical charges and electrostatic repulsion should also be responsible for the stabilization of the nematic phases. Anisotropic xerogel layers are formed when these gels are deposited and dried onto flat substrates. X-ray diffraction patterns of such coatings exhibit a series of 00l harmonics due to the turbostratic stacking of the oxide particles. Dehydration is reversible and fluid mesophases are again obtained via a swelling process when water is added to the xerogel.