Volume 61, Issue 2
August 2003, pages 187-481
pp 187-187 August 2003
pp 189-198 August 2003
The liquid crystalline and selected physical properties of some vanadyl and manganese(III)-porphyrin-TCNE complexes are discussed. These materials form linear chains from a magnetic point of view and columnar discotic LC phases. Some of the manganese complexes exhibit a bulk magnetic phase below ∼20 K. The discussed materials are studied by means of DSC, X-ray powder diffraction, dielectric spectroscopy, reversal current characterization and magnetic susceptibility measurements. A broader view on some physical properties of columnar paramagnetic metallomesogens is given.
pp 199-203 August 2003
Connecting two columnar phase forming discotic mesogens via a short rigid spacer leads to the formation of a π-conjugated discotic dimer snowing discotic nematic (ND) phase. Attaching branched-alkyl chains directly to the core in hexaalkynylbenzene resulted in the stabilisation of ND phase at ambient temperature. Pentalkynylbenzene derivatives possessing a combination of normal- and branched-alkoxy chains display a very broad ND, phase which is stable well below and above the room temperature.
pp 205-218 August 2003
We present in this work a review concerning wide frequency rangeT1 proton NMR relaxation studies performed in compounds exhibiting columnar mesophases, namely the Colho mesophase in the case of a liquid crystal of discotic molecules and the øh mesophase in the case of a liquid crystal of biforked molecules. These NMR relaxation studies were performed combining conventional and fast field cycling NMR techniques in a frequency range between 100 Hz and 300 MHz. The possibility of probing such a large frequency range has provided a way to effectively distinguish the influence, on theT1 relaxation profiles, of the different molecular movements observed in this type of mesophases. In addition, we present a comparison between the molecular dynamics in columnar (øh) and lamellar (SmC) mesophases exhibited by the same biforked compound.
pp 219-229 August 2003
The synthesis and characterization of some polycatenar ligands which exhibit hexagonal columnar and cubic phases are reported. A pentacatenar with only four phenyl rings in the core and exhibiting a mesophase is also reported. A few copper (II) and palladium (II) complexes have been synthesized using these ligands and the mesomorphic properties exhibited by them are described. The hexagonal columnar phase exhibited by some of the complexes can be cooled down to room temperature. The mesophases have been characterized using a combination of polarized light microscopy, differential scanning calorimetry and X-ray diffraction methods.
pp 231-237 August 2003
The biaxial nematic liquid crystalline phase was predicted several decades ago. Several vigorous attempts to find it in various systems resulted in mis-identifications. The results of X-ray diffraction and optical texture studies of the phases exhibited by rigid bent-core molecules derived from 2,5-bis-(p-hydroxyphenyl)-l,3,4-oxadiazole reveal that the biaxial nematic phase is formed by three compounds of this type. X-ray diffraction studies reveal that the nematic phase of these compounds has the achiral symmetry D2h, in which the overall long axes of the molecules are oriented parallel to each other to define the major axis of the biaxial phase. The apex of the bent-cores defines the minor axis of this phase along which the planes containing the bent-cores of neighboring molecules are oriented parallel to each other.
pp 239-248 August 2003
3,5-Disubstituted 1,2,4-oxadiazoles are a new type of liquid crystalline (LC) compounds with asymmetrical five-membered heterocycle as a central unit. They have a bent shape and are very convenient model-compounds for studying the dependence of the LC properties on the molecular design. We have also synthesized and investigated ‘banana-shaped’ 1,2,4-oxadiazoles using the ester groups as the linkage units. The new compounds exhibit spontaneous polarization in the smectic phase, even if there is no chiral group in the molecules. Preliminary experimental data suggest the presence of spontaneous polarization in the nematic phase as well. In order to study the structural properties of the LC phases, X-ray diffraction (XRD) measurements on powder samples have been carried out. Based on the XRD data, a model of the structural arrangement of the bent molecules in the smectic phase is provided, which accounts for the macroscopic spontaneous polarization as well as the ferroelectric switching behavior.
pp 249-262 August 2003
The measurement of dipolar couplings between nuclei is a convenient way of obtatining directly liquid crystalline ordering through NMR since the coupling is dependent on the average orientation of the dipolar vector in the magnetic field which also aligns the liquid crystal. However, measurement of the dipolar coupling between a pair of selected nuclei is beset with problems that require special solutions. In this article the use of cross polarization for measuring dipolar couplings in liquid crystals is illustrated. Transient oscillations observed during cross polarization provide the dipolar couplings between essentially isolated nearest neighbour spins which can be extracted for several sites simultaneously by employing two-dimensional NMR techniques. The use of the method for obtaining heteronuclear dipolar couplings and hence the order parameters of liquid crystals is presented. Several modifications to the basic experiment are considered and their utility illustrated. A method for obtaining proton-proton dipolar couplings, by utilizing cross polarization from the dipolar reservoir, is also presented.
pp 263-275 August 2003
We present the results of optical studies on the instabilities in a substrate-free nematic 8CB film, subject to an in-plane electric field. The initial director field involves a −1/2 strength disclination loop, separating the central pseudoisotropic zone from the splay-bend (SB) birefringent boundary. Three regimes of sample thickness are distinguishable on the basis of field-induced instabilities. Thick (∼75 μm) films display growth of SB zones (independently of disclination movement), wall-formation, and reversible transition between walls and disclinations. Moderately thick films, a few μm in the central part, exhibit distinctive undulations at the border of advancing SB layers. Submicron thin films, with smectic-like homeotropic central plateau, show spectacular isotropic vortex-pairs at either end of this plateau. Further, the end regions of the birefringent zone exhibit both electro-convective flows and reorientational effects. The latter are associated with the formation of open and closed walls, and loop-wall emission. The final high field instability involves jet-like flows at the two ends of the film.
pp 277-283 August 2003
We predict the existence of a new defect-lattice phase near the nematic-smectic-C(NC) transition. This tilt-analogue of the blue phase is a lattice of double-tilt cylinders which are disclination lines in the smectic layer normal as well as the c-field. We discuss the structure and stability of the cone phase. We suggest that many ‘nematics’ exhibiting short range layering and tilt order may in fact be in the molten cone phase, which is a line liquid.
pp 285-295 August 2003
Combining layered positional order as smectic order and chirality can generate complex architectures since twist parallel to the layers is not allowed. This paper will review some new experimental results on different phases resulting from the competition between smectic positional order and twist orientational order. It concerns the TGBA and the NL*, that is the liquid line phase as well as the SmQ phase. Chiral effects in the isotropic phase will also be discussed.
pp 297-312 August 2003
Viscoelastic properties of liquid crystals are very important for applications like display technology. However, there are not many direct techniques to study them. In this review, we describe our studies on the viscoelastic modes of some chiral liquid crystals using dynamic light scattering. We discuss viscoelastic modes corresponding to the C director fluctuations in the chiral smectic C phase and the behaviour of the Goldstone-mode near the chiral smectic C-smectic A phase transition. In cholesteric liquid crystals, we consider the director fluctuations in a wavevector range comparable to the inverse pitch of the cholesteric. Here, the study of the scattered light in the vicinity of the Bragg reflection using a novel geometry will be presented.
pp 313-329 August 2003
Quality of image in a display depends on the contrast, colour, resolution and the number of gray shades. A large number of gray shades is necessary to display images without any contour lines. These contours are due to limited number of gray shades in the display causing abrupt changes in grayness of the image, while the original image has a gradual change in brightness. Amplitude modulation has the capability to display a large number of gray shades with minimum number of time intervals [1,2]. This paper will cover the underlying principle of amplitude modulation, some variants and its extension to multi-line addressing. Other techniques for displaying gray shades in passive matrix displays are reviewed for the sake of comparison.
pp 331-343 August 2003
Biomolecular electronics is rapidly evolving from physics, chemistry, biology, electronics and information technology. Organic materials such as proteins, pigments and conducting polymers have been considered as alternatives for carrying out the functions that are presently being performed by semiconductor silicon. Conducting polymers such as polypyrroles, polythiophenes and polyanilines have been projected for applications for a wide range of biomolecular electronic devices such as optical, electronic, drug-delivery, memory and biosensing devices. Our group has been actively working towards the application of conducting polymers to Schottky diodes, metal-insulator-semiconductor (MIS) devices and biosensors for the past 10 years. This paper is a review of some of the results obtained at our laboratory in the area of conducting polymer biomolecular electronics.
pp 345-352 August 2003
Double stranded DNA chain is known to have non-trivial elasticity. We study the effect of this elasticity on the denaturation profile of DNA oligomer by constraining one base pair at one end of the oligomer to remain in unstretched (or intact) state. The effect of this constraint on the denaturation profile of the oligomer has been calculated using the Peyrard-Bishop Hamiltonian. The denaturation profile is found to be very different from the free (i.e. without the constraint) oligomer. We have also examined how this constraint affects the denaturation profile of the oligomer having a segment of defect sites located at different parts of the chain.
pp 353-360 August 2003
We study the elastic responses of double-(ds) and single-stranded (ss) DNA at external force fields. A double-strand-polymer elastic model is constructed and solved by path integral methods and Monte Carlo simulations to understand the entropic elasticity, cooperative extensibility, and supercoiling property of dsDNA. The good agreement with experiments indicates that short-ranged base-pair stacking interaction is crucial for the stability and the high deformability of dsDNA. Hairpin-coil transition in ssDNA is studied with generating function method. A threshold force is needed to pull the ssDNA hairpin patterns, stabilized by base pairing and base-pair stacking, into random coils. This phase transition is predicted to be of first order for stacking potential higher than some critical level, in accordance with experimental observations.
pp 361-371 August 2003
During the course of our investigation of the electron transfer properties of some redox species through highly hydrophobic long chain alkanethiol molecules on gold in aqueous and non-aqueous solvents, we obtained some intriguing results such as unusually low interfacial capacitance, very high values of impedance and film resistance, all of which pointed to the possible existence of a nanometer size interfacial gap between the hydrophobic monolayer and aqueous electrolyte. We explain this phenomenon by a model for the alkanethiol monolayer—aqueous electrolyte interface, in which the extremely hydrophobic alkanethiol film repels water molecules adjacent to it and in the process creates a shield between the monolayer film and water. This effectively increases the overall thickness of the dielectric layer that is manifested as an abnormally low value of interfacial capacitance. This behaviour is very much akin to the ‘drying transition’ proposed by Lum, Chandler and Weeks in their theory of length scale dependent hydrophobicity. For small hydrophobic units consisting of apolar solutes, the water molecules can reorganize around them without sacrificing their hydrogen bonds. Since for an extended hydrophobic unit, the existence of hydrogen bonded water structure close to it is geometrically unfavourable, there is a net depletion of water molecules in the vicinity leading to the possible creation of a hydrophobic interfacial gap.
pp 373-384 August 2003
Much of the modern understanding of orientational order in liquid crystals (LCs) is based on polarizing microscopy (PM). A PM image bears only two-dimensional (2D) information, integrating the 3D pattern of optical birefringence over the path of light. Recently, we proposed a technique to image 3D director patterns by fluorescence confocal polarizing microscopy (FCPM). The technique employs the property of LC to orient the fluorescent dye molecules of anisometric shape, added in small quantities to the LC. In LC, smooth director deformations do not alter mass density of the material. Thus the density of dye is also uniform across the sample, except, perhaps, near the surfaces or at the cores of topological defects. In polarized light, the measured fluorescence signal is determined by the spatial orientation of the molecules rather than by dye concentration (as in regular biological samples stained with tissue-specific dyes). The contrast is enhanced when both excitation and detection of fluorescence light are performed in polarized light. This short review describes the essence of FCPM technique and illustrates some of its applications, including imaging of Frederiks electric-field induced effect in a nematic LC and defects such as dislocations in cholesteric LCs.
pp 385-393 August 2003
In the last decade, it has been experimentally found that in certain conditions a periodic domain pattern arises in ferroelectric liquid crystals (FLC) in bookshelf geometry. Such a periodic texture appears after switching-off an external electric field, even in strong anchoring conditions. It has a static character and is bidimensional, being dependent on directions normal to both the smectic planes and the cell plates. Here a new model explaining this phenomenon is proposed, valid in the case of FLC with strong anchoring. The model is based on the coupling between the spontaneous polarization field in the first semi-period of its modulation along the cell plates and the same field in the second semi-period. This coupling competes with the FLC medium elasticity and is trapped by the anchoring. According to our model, in the ferroelectric state the biperiodic texture is favored by increasing the values of spontaneous polarization. The critical value of the spontaneous polarization for which the undeformed state becomes unstable is found. It is shown to be proportional to the square root of the ratio between the FLC elastic constant and the cell thickness. Moreover, it is inversely proportional to the sinus of the pre-tilt angle with respect to the cell walls.
pp 395-404 August 2003
In this paper we present a review of five-rings banana-shaped molecules derived from isophthalic acids. This study deals with about a hundred compounds and most of them have not been published. By a combination of several linking groups and different selected substituents either on the outer rings or on the central core, several mesophases with switching properties are induced. The study of homologous series underlines the importance of the length and nature of the terminal chains. X-ray analysis reveals several new structures.
pp 405-415 August 2003
In most homologous series of compounds made of bent-core (BC) molecules, the B2 B1 and B6 phases occur as the chain length decreases. We have studied binary mixtures of the compound 1,3-phenylene bis[4-(3-methylbenzoyloxy)]4-n-dodecylbiphenyl 4’-carboxylate (BC12) which exhibits the B2 phase with the compound 4-biphenylyl 4’-n-undecyloxybenzoate (BO11) made of rod-like (R) molecules. We find the above sequence of occurrence of the B phases with increasing concentration of BOH. In this paper we describe the physical origin for the formation of these phases in both pure compounds and in the mixtures. We have also found the occurrence of the biaxial smectic A phase when the BO11 concentration is increased to 87–95.5 mol%. We also report on another binary system composed of BC12 and 4-n-octyloxy 4’- cyanobiphenyl (8OCB) made of R molecules. This system exhibits the biaxial smectic A phase down to 30°C. Using polarized infrared spectroscopy we find that the mutual orientation of the R and BC molecules in the SmAdb liquid crystal is such that the arrow axes of the BC molecules are along the layer normal of the partial bilayer smectic structure formed by the rods. We also describe unusual growth patterns obtained when the nematic phase transforms to the SmAdb phase in a mixture with 24 mol% of BC12.
pp 417-423 August 2003
Induction and stabilization of liquid crystallinity through hydrogen bonding (HB) are now well-established. Interesting observations made on the influence of HB on LC behaviour of amido diol-based poly(esteramide)s, poly(esteramide)s containing nitro groups and azobenzene mesogen-based polyacrylates will be discussed. The use of amido diol as an important precursor for the synthesis of novel PEAs containing inbuilt di-amide linkage enabled generation of extensive hydrogen bondings between the amide-amide and amide-ester groups which stabilized the mesophase structures of the PEAs. The contributions of hydrogen bonding to the generation and stabilization of mesophase structures were plainly evident from the observation of liquid crystallinity even in PEAs prepared from fully aliphatic amido diols. Replacement of terephthaloyl units by isophthaloyl moiety totally vanquished liquid crystalline phases while biphenylene and naphthalene units did only reduce the transition temperatures as expected. The occurrence of the smectic phases in some of the polymers indicated possibly self-assembly through the formation of hetero intermolecular hydrogen bonded networks. A smectic polymorphism and in addition, a smectic-to-nematic transition, were observed in the monomers and polymers based on 1,4-phenylene[bis-(3-nitroanthranilidic acid)] containing nitro groups. A smectic polymorphism was also observed as a combined effect of hydrogen bonded carboxyl groups and laterally substituted alkyl side chains in the case of azobenzene mesogen containing side chain polyacrylates. It was further shown that the presence of the mesophase enhances the non-linear optical (NLO) response of these polymers.
pp 425-434 August 2003
Segmented conjugated polymers, wherein the conjugation is randomly truncated by varying lengths of non-conjugated segments, form an interesting class of polymers as they not only represent systems of varying stiffness, but also ones where the backbone can be construed as being made up of chromophores of varying excitation energies. The latter feature, especially when the chromophores are fluorescent, like in MEHPPV, makes these systems particularly interesting from the photophysics point of view. Segmented MEHPPV-x samples, wherex represents the mole fraction of conjugated segments, were prepared by a novel approach that utilizes a suitable precursor wherein selective elimination of one of the two eliminatable groups is affected; the uneliminated units serve as conjugation truncations. Control of the compositionx of the precursor therefore permits one to prepare segmented MEHPPV-x samples with varying levels of conjugation (elimination). Using fluorescence spectroscopy, we have seen that even in single isolated polymer chains, energy migration from the shorter (higher energy) chromophores to longer (lower energy) ones occurs — the extent of which depends on the level of conjugation. Further, by varying the solvent composition, it is seen that the extent of energy transfer and the formation of poorly emissive inter-chromophore excitons are greatly enhanced with increasing amounts of non-solvent. A typical S-shaped curve represents the variation of emission yields as a function of composition suggestive of a cooperative collapse of the polymer coil, reminiscent of conformational transitions seen in biological macromolecules.
pp 435-445 August 2003
It is suggested that liquid crystal—polymer interfaces are coupled systems, in which the components mutually influence the orientational state of each other. The photo-orientation process at liquid crystal-polymer interfaces provides a striking example of such a coupling. Experiments show that the anisotropic structure generated by polarised light at a polymer surface is strongly affected by the phase of the liquid crystal covering the polymer. Photo-orientation is significantly more efficient when the liquid crystal is in the isotropic phase than when it exhibits orientational order. The observations are interpreted by assuming that in the smectic and nematic phases the liquid crystal stabilises to a large extent polymer chain-segments aligned parallel to the director, while it blocks the photo-induced formation of chain-segments in the perpendicular direction. Other situations, in which the coupling between the liquid crystal and the polymer can be important, are also discussed briefly.
pp 447-454 August 2003
Structures of complexes formed in aqueous solutions by some anionic polyelectrolytes (double and single stranded (ds and ss) DNA, poly(vinyl sulfonate) (PVS), and poly(styrene sulfonate) (PSS)) with a cationic surfactant system consisting of cetyltrimethylammonium bromide (CTAB) and sodium 3-hydroxy-2-naphthoate (SHN) have been determined using small angle X-ray diffraction. All complexes are found to have a two-dimensional (2-D) hexagonal structure at low SHN concentrations. Analysis of the diffraction data shows that the ds DNA—CTAB complex has an intercalated structure, with each DNA strand surrounded by three cylindrical micelles. On increasing SHN concentration, DNA—CTAB—SHN complexes exhibit a hexagonal-to-lamellar transition, whereas PVS complexes show a hexagonal → centered rectangular → lamellar transition. PSS complexes show yet another sequence of structures. These results indicate the significant influence of the chemical nature of the polyelectrolyte on the structure of the complexes.
pp 455-481 August 2003
This contribution gives an overview of ferroelectric switching liquid crystalline phases formed by bent-core molecules. First a description of some general principles behind the mesophase formation within bent-core systems will be given, followed by a short review of the mesophase structures formed by such molecules. Then, different classes of ferroelectric switching bent-core mesogens will be described. This type of switching behaviour has been reported for several subtypes of polar smectic phases (B2, B5, B7 and SmCG) and recently for columnar mesophases. In this discussion particular attention will be made to polyphilic bent-core molecules, composed of three incompatible units, a bent aromatic core, alkyl chains and an oligosiloxane unit. The importance of the decoupling of the layers into microsegregated sublayers for the ferroelectric organisation is discussed. Many of the ferroelectric switching mesophases show dark textures with distinct regions of opposite chirality in their ground states. It is discussed that this might be due to a helical superstructure formed as a result of an escape from macroscopic polar order. Hence, the materials themselves are not ferroelectric in the ground state, but upon alignment within an electric field in the measuring cells the ferroelectric states are stabilised by surface interactions, leading to a ferroelectric switching system. The designing principle was extended to mesogenic dimers with bent-core structural units. For these compounds, depending on the number of dimethylsiloxane units in the spacer either ferroelectric or antiferroelectric switching was observed, whereby the effect of parity is reversed to that observed for conventional calamitic dimesogens. Finally, a carbosilane-based first generation dendrimer is reported. It shows a ferroelectric switching phase, for which a non-correlated organisation of tilted polar smectic layers is proposed (SmCPR).
Volume 93 | Issue 5
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