Liquid crystals and life

The molecules of living systems invariably exhibit both thermotropic and/or lyotropic liquid crystalline properties. In some cases the mesophases formed by bio-materials have lamellar structures, whereas in other situations they form columnar phases. Many liquid crystal biomaterials are found in cell membranes, indicating that such structures have properties that are dependent on liquid crystallinity for their behaviour of a variety of bio-materials is discussed. function. In this article the mesomorphic     

Electron and light microscopical investigation of defect structures in mesophases of pharmaceutical substances

 Transmission electron microscopy of freeze fractured and replicated samples (TEM) and polarizing light microscopy (PLM) are used to investigate the defect structures of the thermotropic and lyotropic mesophases of the non-steroidal antiinflammatory drug fenoprofen sodium and of the thermotropic mesophase of the nonionic surfactant sucrose oleate (O1570). All mesophases have a layered, smectic structure. The thermotropic liquid crystal of feno-profen sodium is an interdigitated smectic A phase (smectic Ad) having the highest viscosity of the investigated samples. The thermotropic mesophase of the sugar ester is also of the type smectic A, likely to be of subtype smectic A2 (bilayered smectic structure). The lyotropic mesophase is of lamellar liquid crystalline nature and has a much lower viscosity than the thermotropic mesophases. In the PLM the lyotropic fenoprofen mesophase has a strong tendency to form a pseudoisotropic texture, indicating a strong tendency to form undisturbed layered structures. Other textures exhibited in the PLM are fan-shaped texture and maltese-cross texture. Confocal domains, cylinders, pits and peaks as well as screw dislocations are found in great number in the TEM. However, no greater regions of undisturbed lamellar arrangement in the lyotropic mesophase could be detected. The only texture of the thermotropic fenoprofen mesophase visible in the PLM is the fan-shaped texture, indicating confocal domains as predominant structural elements. However, no confocal domains (tori or Dupin cyclides) are found in the TEM. In the PLM the sugar–ester mesophase exhibited a fan-shaped texture, maltese crosses and oily streaks as dominant textures. In the TEM only a few +π and −π disclinations and imperfect confocal domains could be detected. The discrepancies in the appearance of defect structures and textures between the mesophases as well as the discrepancies in the findings in the PLM and in the TEM investigations are caused by the different sample preparation and the different viscosities of the mesophases. Received: 28 May 1997 Accepted: 2 September 1997     

Synthesis and mesomorphic behaviour of comb-like polymers based on lipopeptides with two hydrophobic chains

Polymerizable lipopeptides with two hydrophobic chains were synthesized and transformed into comb-like polymers by radical polymerization. The structure of dry polymerizable lipopeptides and comb-like polymers and of their aqueous solutions was determined by X-ray diffraction. Comb-like polymers exhibit both thermotropic and lyotropic properties. Three types of mesomorphic structure were resolved: smectic B, smectic A and cylindrical hexagonal. The domains of stability of the mesophases and the values of their structural parameters were established.     

Main chain liquid crystalline ionic polymers with thermotropic and lyotropic mesophases

An ionogenic main chain liquid crystalline polymer was synthesized. In contrast to previous studies the charged sites were incorporated into the flexible spacer and not into the mesogenic group. This was done through quaternization of 1,2-bis(4-pyridylethane) with a biphenyl-4,4′-nonanoxytoluenesulphonate. The polymer displayed thermotropic and lyotropic me-sophases. The thermotropic mesophase was smectic. Organic counterions such as meth-ylsulfonates and p-toluenesulfonates were found to be favorable to the development of mesophases, due to the increased solubility and lower isotropisation temperatures, when compared to bromide counterion containing polymers. Easy supercooling, dependence on thermal history, and the development of batonnet textures on cooling from the melt were also observed. © 1995 John Wiley & Sons, Inc.     

The effects of substituent size and molecular weight on the liquid crystalline properties of poly(2-alkyl-1,4-phenylene terephthalate)s

A series of low molecular weight, thermotropic poly(2-alkyl-1,4-phenylene terephthalate)s was prepared by the solution polycondensation reaction of terephthaloyl chloride and alkylhydroquinones containing n-alkyl substituents of increasing size from methyl to dodecyl. Samples of the low molecular weight polymers so obtained were also further polycondensed in the solid state to obtain high molecular weight polymers. The liquid crystalline phase behaviors and textures were determined, and the effects of polymer structure and molecular weight on these properties are discussed. All of the polymers obtained formed thermotropic, nematic mesophases, which were less stable for the lower molecular weight polymers, as expected, than were the mesophases formed by the higher molecular weight polymers. © 1994 John Wiley & Sons, Inc.     

Synthesis and mesomorphic behaviour of comb-like polymers based on lipopeptides with two hydrophobic chains

Abstract

Polymerizable lipopeptides with two hydrophobic chains were synthesized and transformed into comb-like polymers by radical polymerization. The structure of dry polymerizable lipopeptides and comb-like polymers and of their aqueous solutions was determined by X-ray diffraction. Comb-like polymers exhibit both thermotropic and lyotropic properties. Three types of mesomorphic structure were resolved: smectic B, smectic A and cylindrical hexagonal. The domains of stability of the mesophases and the values of their structural parameters were established.     

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.     

Liquid-Crystalline Behaviour in the n-Alkyl Gluconamides and Other Related Carbohydrates

Many alkyl derivatives of carbohydrates are used as detergents for cell wall membranes. This study describes the liquid-crystalline properties of a number of these systems. The combination of a hydrophilic carbohydrate moiety and a hydrophobic aliphatic substituent leads to the formation of both thermotropic and lyotropic liquid-crystal mesophases. Materials with this structural combination are suspected to form interdigitated bilayer smectic A phases. The central core region of the layer is held together by dynamic hydrogen-bonding between the neighbouring carbohydrate moieties, whereas the terminal aliphatic chains create fluidity between layers.     

2H NMR studies on two-homopolypeptide lyotropic enantiodiscriminating mesophases: experimental quantification of solute-fiber affinities

The analytical potential and enantioselective properties of lyotropic mesophases made by mixing two chemically different chiral polypeptides are described. Here we examine the case of a mixture of poly-gamma-benzyl-L-glutamate (PBLG) and poly-epsilon-carbobenzyloxy-L-lysine (PCBLL). We demonstrate that 2H NMR spectroscopy on these chiral oriented mixtures can discriminate both enantiomers and enantiotopic directions in prochiral molecules. Moreover, in such systems, degree of enantiodiscrimination, resolution, and sensitivity can be conjointly optimized by changing the relative proportion of the two polypeptides. Therefore, these new enantiodiscriminating media provide a favorable alternative to single-polypeptide mesophases with respect to stereochemical applications. At a more fundamental level, the present work points out that solute distribution in the vicinity of each polypeptide partly governs the degree of enantiodiscrimination and NMR relaxation rates. To this end, the experimental trends of solute NMR observables (Delta nu Q, T1) versus the fraction of peptide units of each polymer were analyzed by using a "mean-field" model derived from that proposed for mixtures of thermotropic nematic solvents, and based on the separation of intermolecular interactions between the solute and both polypeptides. This approach allows the relative solute-fiber affinities in these lyotropic systems to be determined. To identify the factors controlling solute-polypeptide affinities, we investigated various solutes (polar/apolar, rigid/flexible, achiral/prochiral/chiral molecules) using 2H NMR at natural abundance or on isotopically enriched solutes.     

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.     

Liquid-Crystalline Behaviour in the n-Alkyl Gluconamides and Other Related Carbohydrates

Abstract

Many alkyl derivatives of carbohydrates are used as detergents for cell wall membranes. This study describes the liquid-crystalline properties of a number of these systems. The combination of a hydrophilic carbohydrate moiety and a hydrophobic aliphatic substituent leads to the formation of both thermotropic and lyotropic liquid-crystal mesophases. Materials with this structural combination are suspected to form interdigitated bilayer smectic A phases. The central core region of the layer is held together by dynamic hydrogen-bonding between the neighbouring carbohydrate moieties, whereas the terminal aliphatic chains create fluidity between layers.     

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.     

Substitution effects on the liquid crystalline properties of D,L-xylitol amphiphiles

In this article we describe the self-assembling properties of alkyl substituted xylitols in relation to both thermotropic and lyotropic liquid crystalline mesophases. Three series of substituted xylitols were prepared where aliphatic chains of varying length were attached to a xylitol moiety via ether, thioether and ester linking groups. The thermotropic properties were investigated by thermal polarized light microscopy and differential scanning calorimetry, and evaluated as a function of chain length and linking group. The lyotropic phase behaviour was investigated via the addition of water to each material at room temperature. The efficiency for forming thermotropic phases was found to be reversed for the lyotropic phases in respect of the three series, i.e. as a function of the linking unit.     

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.     

Liquid-crystalline polymers: Past, present, and future

The main steps of the evolution in studies related to the design and investigation of the structure and properties of thermotropic LC polymers containing mesogenic groups are discussed. The principal attention is focused on the results of experiments performed at the Laboratory of Chemical Transformations of Polymers, Faculty of Chemistry, Moscow State University, which was established and guided by Academician N.A. Platé from 1966 to 1985 and then supervised by V.P. Shibaev, the author of this review. Historical evidence is presented to demonstrate the contribution of Russian scientists to the development of approaches to the synthesis and study of chiral and electro- and photocontrollable comb-shaped LC polymers and related composites. The concept of preparing multifunctional LC copolymers and LC networks containing mesogenic, chiral, photochromic, and functional (including ionophoric) groups that can undergo hydrogen bonding, form complexes with metal ions, and interact with nanoparticles is scrutinized. Specific features of the structural organization of polymer mesophases are covered. The data on multifunctional comb-shaped LC polymers, LC ionomers, and LC dendrimers are examined, and the problems concerning the design of light-controllable LC copolymers and polymer photochromic composites and networks are reviewed. Some applied aspects of using LC polymers are considered: specifically, approaches to creation of lasers based on cholesterics and photo- and electroactive media in optics and photonics, systems for data recording and storage, holography, display technology, and other fields.     

A self-diffusion study in aqueous solution and lyotropic mesophases of amphiphilic block copolymers

 Water-soluble poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PPO) triblock copolymers are high-molecular-weight nonionic copolymers and form micellar solutions and liquid-crystalline mesophases in water. We studied the temperature dependence of polymer and water self-diffusion in solutions and lyotropic mesophases of the PEO₁₃ PPO₃₀ PEO₁₃/water and PEO₂₁ PPO₄₇ PEO₂₁/water binary systems. The self-diffusion measurements were performed by means of the pulsed field gradient spin-echo NMR method. The analysis of the water mobility was realised using “the obstruction factor” and “the two-site model”, which consider the reduction of the water self-diffusion due to the microstructure of the lyotropic aggregates and to the presence of one part of the solvent bound to the polymer aggregate surfaces. We calculated the water obstruction factors and the hydration numbers as a function both of the polymer composition and of the temperature. The results are compared with the data obtained in mesophases formed by classical surfactants. Received: 16 September 1999 Accepted in revised form: 24 November 1999     

Luminescent Metallacycle-Cored Liquid Crystals Induced by Metal Coordination

Two rhomboidal metallacycles based on metal-coordination-driven self-assembly are presented. Because metal-coordination interactions restrict the rotation of phenyl groups on tetraphenylethene units, these metallacycles were emissive both in solution and in solid state, and their aggregation-induced emission properties were well-retained. Moreover, the rhomboidal metallacyclic structures offer a platform for intermolecular packing beneficial for the formation of liquid crystalline phases. Therefore, although neither of building blocks shows mesogenic properties, both thermotropic and lyotropic (in DMF) mesophases were observed in one of metallacycles, indicating that mesophases could be induced by metal-coordination interactions. This study not only reveals the mechanism for the formation of cavity-cored liquid crystals, but also provides a convenient approach to preparing supramolecular luminescent liquid crystals, which will serve as good candidates for chemo sensors and liquid crystal displays.     

Functional liquid-crystalline polyesters based on twin nonamethylene spaced p-oxybenzoate dyads and dithiols

A new series of thermotropic liquid-crystalline poly-(ester-β-sulphide)s 9Sn was prepared by reacting the mesogenic nona-methylene bis[4-(4-acryloyloxybenzoyloxy)benzoate] 1 with α,ω-alka-nedithiols of varying length. The polymers exhibit nematic and smectic mesophases, which are enantiotropic or monotropic in character, depending on the number n of methylene units in the dithiol precursor (n = 2–10). The phase transition parameters were determined and compared with those of closely related poly(ester-β-sulphide)s 6Sn. It is suggested that these systems may be suitable model polymers to test current theory of the existence of highly anisotropic or weakly anisotropic mesophases in polymers.     

Synthesis and Characterization of Liquid Crystalline Alkylammonium Polyacrylates

Two monomers, 2‐acryloyloxyethyl(didodecyl)methylammonium iodide and 2‐acryloyloxyethyl(didecyl)methylammonium iodide, were synthesized and characterized. Radical polymerization of both monomers was carried out to form comb‐like ionic polyacrylates as analogous amphiphilic derivatives of polysoaps. Thermal and mesogenic properties were evaluated by means of differential scanning calorimetry and polarizing microscopy. The polymers exhibited well‐defined thermotropic smectic mesophases only upon cooling.     

Luminescent Metallacycle‐Cored Liquid Crystals Induced by Metal Coordination

Two rhomboidal metallacycles based on metal‐coordination‐driven self‐assembly are presented. Because metal‐coordination interactions restrict the rotation of phenyl groups on tetraphenylethene units, these metallacycles were emissive both in solution and in solid state, and their aggregation‐induced emission properties were well‐retained. Moreover, the rhomboidal metallacyclic structures offer a platform for intermolecular packing beneficial for the formation of liquid crystalline phases. Therefore, although neither of building blocks shows mesogenic properties, both thermotropic and lyotropic (in DMF) mesophases were observed in one of metallacycles, indicating that mesophases could be induced by metal‐coordination interactions. This study not only reveals the mechanism for the formation of cavity‐cored liquid crystals, but also provides a convenient approach to preparing supramolecular luminescent liquid crystals, which will serve as good candidates for chemo sensors and liquid crystal displays.