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New hockey stick-shaped mesogens with a lateral methyl group inserted between the m-alkyloxy-chain and the azomethine connecting group, 4-(3-n-alkyloxy-2-methyl-phenyliminomethyl) phenyl-4-n-alkyloxycinnamates have been synthesised. The interesting feature of these hockey stick-shaped mesogens is the appearance of the nematic phase in addition to two polymorphic tilted smectic phases - the synclinic smectic C (SmCs) and the anticlinic SmCa phase. Physical characterisation of these mesogens has been carried out using polarising optical microscopy, differential scanning calorimetry, optical birefringence, X-ray diffraction (XRD), electro-optical and dielectric spectroscopy measurements. The SmCs-SmCa phase transition is accompanied by only a small calorimetric signal but causes a pronounced change in the optical textures. Orientational order parameters determined from the birefringence measurements have been compared with those estimated from XRD patterns. Dielectric measurements point to the formation of small 'soft' ferroelectric clusters responsible for a low frequency absorption range. [ABSTRACT FROM AUTHOR]

Three new homologous bent-shaped mesogens with terminal octyloxy P8, decyloxy P10 and dodecyloxy P12 groups were synthesized. Calorimetric, X-ray and electro-optic investigations prove the existence of two mesophases of the SmCPA type for compound P10 but only one SmCPA phase for the homologues P8 and P12. The static dielectric permittivities of compound P12 and that of the low-temperature phase of substance P10 are in the order of 30 and agree with results on bent-core mesogens published before. Surprisingly, the dielectric permittivities of P8 and of the high-temperature phase of P10 are of about 1000. We explain this extremely high dielectric response with the soft reaction of ferroelectric units in the external electrical field. [ABSTRACT FROM AUTHOR]

The physical behaviour, especially the dielectric properties, of two series of isomeric compounds formed by banana-shaped molecules is reported. The feature of all liquid crystalline substances investigated is the formation of a ferroelectric short range order. In one layer of the SmCPA phase the spontaneous polarisation shows in one direction and in the following in the opposite resulting in an antiferroelectric behaviour. It is demonstrated that the molecular origin of the polarization is connected with the perpendicular dipole moments. From the two relaxation modes seen the first results from ferroelectric units and the second from the reorientation of the molecules about the long axes. The collective character of both motions is demonstrated. The same mechanisms appear in the columnar phase, but they behave in a different way due to the different structure. Strong changes of the dielectric properties are observed at the transition from the isotropic in the liquid crystalline phase, but astonishingly not between both mesophases. [ABSTRACT FROM AUTHOR]

Three homologous achiral five-ring bent-core mesogens are presented where 4-chlororesorcinol is the central core and the aromatic rings are linked by ester groups. These compounds form smectic phases with a tilted arrangement of the molecules (tilt angle ≈ 45°). On cooling the isotropic liquid this phase adopts a fan-like texture which shows for two homologues at relatively high electric fields ( 25-35V μm^-1) an antiferroelectric electro-optical response based on the collective rotation of the molecules around their long axes. At lower temperature the application of a sufficiently high electric field leads to a continuous transition into a non-birefringent texture which exhibits randomly distributed domains of opposite handedness. These domains can be reversibly switched into a state of opposite chirality by reversal of the field polarity. This switching is bistable and shows a current response typical for a ferroelectric ground state. The possible mechanism of the field-induced phase transition, of the ferroelectric switching and of the field-induced inversion of the chirality is discussed on the base of XRD, 13C- and 1H-NMR investigations, dielectric and electro-optical measurements. [ABSTRACT FROM AUTHOR]

Dielectric measurements on a binary system of two liquid crystalline diols were carried out. These show a SmA and a cubic phase. In the middle concentration range of the system, a columnar phase is induced. The self assembly of the molecules giving different liquid crystalline phases is clearly seen in the dielectric spectrum, and therefore details of this process may be discussed. All the samples show a high frequency dielectric absorption which is related to the dynamics of the network of hydrogen bonds. In the columnar phase an additional low frequency mechanism is seen which may be caused by the internal dynamics in the columns. [ABSTRACT FROM AUTHOR]

Investigations on the phase diagrams of two bi-component mixtures of liquid crystals are presented. Whereas in one of the bi-component systems, smectic A (SmA) phase is seen to be induced, in the other case the so-called nematic “island” has been observed. The dielectric properties of magnetically oriented sample forming nematic phase and induced smectic phase in one of the mixtures, and a nematic “island” and SmA phase in the other mixture, were measured in the frequency range from 1  Hz to 10  MHz at different temperatures. The transition temperatures obtained from the polarizing microscope and differential scanning calorimeter measurements agree well with the dielectric relaxation data. [ABSTRACT FROM AUTHOR]

Two tin-containing homopolymers, one liquid crystalline and the other non-mesomorphic, were synthesized and characterized by different relaxation methods (dielectric, calorimetric, NMR). The results prove the existence of two glass transition temperatures related to the dynamics of the main chain and of the liquid crystalline side group, respectively. The reason for this effect is based on a phase separation on nanometer scale. [ABSTRACT FROM AUTHOR]

N-p-Cyano-phenyl maleimide PCPMI was prepared and copolymerized with ethyl and butyl methacrylate in order to study the effect of introducing a strong dipole along the polymer backbone. The copolymer composition was determined by elemental analysis and 1H NMR spectroscopy. The molecular mass of the copolymers was determined by GPC. The glass transition temperature was measured and it was found to correlate well with the chemical structure, and increases with the increase of the maleimide content. The dielectric behavior of the homo methacrylate polymers and the copolymers was measured in the frequency range of 0.01 Hz to 10 MHz at different temperatures. The dielectric data were compared with the two Cole–Cole parameters equation. The glass transition temperature obtained from DSC measurements agreed well with the dielectric relaxation data. [ABSTRACT FROM AUTHOR]

A smectic hexatic phase with tilted molecules is assumed to be confined between two plane boundaries. At a finite boundary distance two dielectric modes are excited by an a.c. external electric field. Using the elastic continuum theory, equations for the relaxation times and the corresponding dielectric susceptibilities are derived and discussed in the limit of high boundary distances and for different material parameters. [ABSTRACT FROM AUTHOR]

It was found that doping of tiny ferroelectric particles to a nematic liquid crystal(LC)strongly affects dielectric properties of the system. The doping increases dielectric response of the LC due to interaction between LC molecules and particles, which possess large dipole moment and high polarisability. The suspension reveals high dielectric response on either side of the Curie temperature, TCurie, and peculiarity at the vicinity of TCurie. This result points at retention of dipole ordering above Curie temperature that may be a result of a memory effect. [ABSTRACT FROM AUTHOR]

It was found that doping a nematic liquid crystal (LC) with a small amount of ferroelectric nanoparticles strongly affects the dielectric properties of the system. In particular, adding the ferroelectric particles results in a shift of the absorption bands corresponding to the rotation of liquid crystal molecules around their short axes to lower frequencies and in an increase of the amplitude and with of the absorption bands. This suggests that strong interactions occur between the LC molecules and the particles, caused by the large dipole moment and high polarizability of the ferro-particles. The ferroelectric particles affect not only dielectric losses, but also dielectric permittivity of the system. Specifically, the static dielectric permittivity and the dielectric anisotropy of the suspension are more than twice that of the pure LC. [ABSTRACT FROM AUTHOR]

A new series of five-ring banana-shaped mesogens derived from isophthalaldehyde was synthesized and investigated. Some of the compounds exhibit a B 2 -B 4 dimorphism. The mesophases were characterized alternatively by optical methods, X-ray studies, and dielectric and electro-optical measurements. [ABSTRACT FROM AUTHOR]

New meta -substituted homologous three-ring mesogens, the 4-(3- n -decyloxyphenyliminomethyl) phenyl 4- n -alkyloxybenzoates, have been synthesized, which are non-linear due only to the attachment of one of the alkyloxy groups in a meta -position. The mesophases were studied by optical microscopy, differential scanning calorimetry, NMR spectroscopy, X-ray diffraction, and electro-optical and dielectric measurements. Unusual phase behaviour was observed on varying the length of the terminal chain. The most interesting finding is the occurrence of two polymorphic tilted smectic phases designated as SmC 1 and SmC 2 . The existence of these phases was revealed by calorimetric studies and also from the pronounced difference in optical textures. It was shown from NMR measurements that the molecular orientation changes from a synclinic to an anticlinic arrangement in the SmC 1 to SmC 2 phase transition. It has also been shown, using NMR, that the SmC 1 → SmC 2 phase transition in these compounds is accompanied by a conformational change in the molecular fragment containing the aromatic ring with the meta -substituted terminal alkyloxy chain. This conformational change is linked to a change in the shape of the molecules and leads to a different packing of the molecules within the layers of the SmC 2 phase. From dielectric measurements an increase by a factor of two was detected in the molecular mobility at the transition into the low temperature SmC 2 phase. This finding supports a change in the packing as result of conformational changes. [ABSTRACT FROM AUTHOR]

Dielectric investigations on a magnetically oriented sample forming N, SmA, SmC and B[sub 2] phases were carried out. The sample shows a negative dielectric anisotropy in the N state and a strong increase of the static dielectric constants perpendicular to the director in the ensuring 'classical' phases. This proves directly the strong and continuous increase of the positive dipole correlation in the lateral direction due to the steric interactions of the bent-shape molecules. From a dynamical point of view, the SmA and SmC phases of this sample show deviations from the classical phases of rod-like molecules. Crystallization did not allow us to extend the dielectric measurements into the B[sub 2] state. [ABSTRACT FROM AUTHOR]

A new achiral banana-shaped five-ring 2-methylresorcinol derivative fluorinated on the outer rings has been synthesized. This compound exhibits four antiferroelectric smectic phases characteristic for bent-core molecules (B[sub 2], B′[sub 2], B′′[sub 2], B[sub 5]). In addition, a highly viscous solid-like phase has been detected which also shows electro-optical switching. This is the first switchable highly ordered B phase. The characterization of the mesophases was made by X-ray diffraction, electro-optical measurements and dielectric spectroscopy. [ABSTRACT FROM AUTHOR]

The first clear experimental evidence of a dielectric relaxation in the B[sub 7] phase is given. The associated molecular process is probably the reorientation of the bent-shaped molecules about the long molecular axis. It is also shown that the dielectric constant strongly increases at the phase transition I-B[sub 7] pointing to a co-operative motion of ferroelectric clusters. Furthermore, a phase transition B[sub 7]-B[sub X] is observed. The values of about 10 for the high frequency limit of the dielectric constants of the B[sub 7] and B[sub X] phases and the static dielectric constants of the isotropic phase are in agreement. Thus, in all the phases the main dipoles can reorient faster than 10[sup -8]s, i.e. the experimental limit. Only in the supercooled B[sub X] phase were the dynamics of the transversal dipoles measured. Using atomic force microscopy, focal-conic domains modulated by parallel lines have been observed at room temperature. [ABSTRACT FROM AUTHOR]

Dielectric measurements on four samples composed of bent-shaped molecules with the same basic structure were carried out. They differ only in the position of one fluorine atom in the central core. Two relaxation ranges were detected: the fast reorientation about the long axes and a slow collective process. In three cases, evidence for a positive dipole correlation in the isotropic phase near to the transition to the B[sub 2] phase was found. All samples show a tendency to give a glass transition. The dielectric constants are discussed in relation to the position of the fluorine atoms. [ABSTRACT FROM AUTHOR]

Banana-shaped five-ring mesogens derived from either isophthalic acid or 4-bromoisophthalic acid have been synthesized. It is shown that the melting and clearing points of the bromine-substituted compounds are markedly decreased in comparison with the analogous unsubstituted compounds. On the basis of X-ray diffraction studies and NMR measurements, as well as dielectric and electro-optical investigations, the mesophase of these compounds could be identified as a B[sub 2] phase. [ABSTRACT FROM AUTHOR]

Dielectric measurements on a sample consisting of banana-shaped molecules were carried out in a frequency range between 0.1 Hz and 10 MHz. The sample exhibited B[sub 2] and B[sub 4] phases. As usual, two ranges of relaxation were detected in the B[sub 2] phase, the fast reorientation about the long axes of the molecules and a slow collective process. In the B[sub 4] phase, only one dielectric active process at low frequencies was found; this does not differ from the low frequency relaxation of the B[sub 2] modification. This relaxation is probably related to the dynamics of superstructures. Crystallization could be observed after keeping the sample for a longer time at higher temperature. Thus, it was possible to differentiate clearly between the crystalline and the B[sub 4] phases. AFM investigations prove the existence of focal-conic domains and periodic superstructures in the B[sub 4] phase; then do not appear in the crystalline state. For this reason the B[sub 4] phase is regarded as different from a classical crystalline phase. [ABSTRACT FROM AUTHOR]

Background: The small chondroitin/dermatan sulphate proteoglycans decorin and biglycan participate in organizing the network of collagen fibrils and interact with non-collagenous matrix proteins. In addition, via interactions with cytokines they are directly or indirectly involved in signalling, growth and cell differentiation. We aimed to analyse their expression in normal gastric tissue and during gastric ulcer healing. Methods: Proteoglycan expression was studied by immunohistochemistry and in situ hybridization in acetic acid-induced gastric ulcers in rat during early phases and during chronic ulceration. The effects of treatment with an acid stable mutein of FGF-2 (bFGF) were also studied. Results: In normal gastric tissue, both proteoglycans were most strongly expressed in the submucosal layer. However, some epithelial cells were positive for biglycan and, surprisingly, also for decorin. In the early phase after ulcer induction exclusively decorin became induced in the muscularis mucosae, while biglycan became detectable in this layer only after 2 weeks. There was no up-regulation of either proteoglycan in other layers, nor could an effect of FGF-2 treatment be seen. Conclusions: The expression of decorin could be observed for the first time in epithelial cells. Decorin, but not biglycan, appears as an early phase reactant in the muscularis mucosae in accordance with its putative role during angiogenesis and the prevention of apoptosis. [ABSTRACT FROM AUTHOR]

Dielectric measurements on two samples formed from banana-shaped molecules with terminal alkyl or alkyloxy groups were carried out in a frequency range between 10[sup -3] Hz and 10 MHz. Both samples exhibit B[sub 2] and B[sub 3] phases; one of them has a B[sub 4] state as well. As usual, two ranges of relaxation were detected in the B[sub 2] phase, the fast reorientation about the long axes of the molecules and a slow collective process. Only one dielectrically active low frequency process could be separated in the B[sub 3] and B[sub 4] phases; this is probably related to the dynamics of superstructures. The high frequency limit of the dielectric constants gives a hint that neither phase is a classical solid. A quite strong increase in the conductivity at the transition into the B[sub 3] phase is critically discussed. [ABSTRACT FROM AUTHOR]

Dielectric measurements in the frequency range 0.01 Hz to 10 MHz on a liquid crystal material with SmB/N dimorphism confined to randomly oriented and interconnected mesoporous (pore diameter 2-10 nm) and macroporous glasses (pore diameter 86 nm) were carried out. In the macroporous glasses the liquid crystal behaves similarly to the bulk phase, but the phase transition temperature SmB-N is suppressed. In the mesoporous glass the transition SmB-N is completely suppressed. [ABSTRACT FROM AUTHOR]

Dielectric measurements on two different samples formed by banana-shaped molecules and showing a B[sub 1] phase were carried out. Three relaxation ranges were detected: a very fast intramolecular motion, the fast reorientation about the long axes and a slow collective process. The data are discussed in relation to known X-ray investigations and dielectric results for homologous samples showing the B2 state. The main difference between B[sub 1] and B[sub 2] is that in B[sub 1] no evidence for ferroelectric order in the short range was detected. [ABSTRACT FROM AUTHOR]

Atomic force microscopy (AFM) images reveal that the liquid crystalline B[sub 2] phase has no helical superstructure, in contrast to the B[sub 7] phase. This is demonstrated on comparing the AFM images of focal-conic domains in the smectic A, cholesteric, B[sub 2] and B[sub 7] phases. The B[sub 2] and B[sub 7] phases are phases formed by banana-shaped molecules. The results point to the existence of ferroelectric clusters with a random size distribution which also cause the low frequency dielectric relaxation. [ABSTRACT FROM AUTHOR]

A new achiral five-ring banana-shaped mesogen is presented which has a cyano substituent in the 4-position of the central core. Microscopical, X-ray, dielectric and electro-optical investigations give evidence for the unusual phase sequence B[sub 2], SmC, SmA. The B[sub 2] phase shows an antiferroelectric switching behaviour; the spontaneous polarization was found to be 330 nCcm[sup -2]. [ABSTRACT FROM AUTHOR]

Two samples consisting of banana-shaped molecules with terminal alkyloxy or terminal alkyl groups were investigated. Dielectric measurements prove the existence of two absorption ranges up to 10 MHz. The high frequency process is related to the reorientation of the bulky rigid core characterized by a strong positive dipole correlation in the B[sub 2] phase. The sample with the alkyloxy groups should show a third absorption range at higher frequencies due to the fast reorientation of the end groups. The low frequency process seen only in the B[sub 2] phase is explained by the dynamics of ferroelectric clusters. [ABSTRACT FROM AUTHOR]

AFM investigations of a glassy heterogeneous system consisting of an oligomeric cholesteric liquid crystal and the hydrophobic aerosil R812 were carried out. With increasing aerosil concentration, a suppression of the characteristic cholesteric surface pattern was observed. Typical separated aerosil aggregates appear in the samples. Their size and form change from small lumps through bigger rod-like entities to large crystallite-like aggregates of aerosil particles. This matches with observations of light scattering of systems with low molecular mass liquid crystals and of the memory effect. The pitch of the cholesteric fingerprint pattern slightly decreases with increase in the aerosil concentration. [ABSTRACT FROM AUTHOR]

Two strongly polar 4-(4-cyanobenzyloxy)benzylidene 4- n -alkylanilines were synthesized for the first time and mixed with the hydrophilic aerosil A 300. The compounds, showing a rich polymorphism, and the mixtures were investigated by calorimetric and dielectric methods. Phase transitions of first and second order were detected. Neither the phase transition temperatures nor dielectric relaxation times are strongly influenced by addition of aerosil up to 20%. [ABSTRACT FROM AUTHOR]

Six members of a new homologous series of achiral banana-shaped molecules have been synthesized and studied by optical microscopy, differential scanning calorimetry, NMR spectroscopy and X-ray diffraction. According to X-ray diffraction measurements on oriented samples, four homologues form an XB2 phase behaviour. From electro-optical studies the spontaneous polarization and the tilt angle could be measured. An orientational order parameter of 0.8 was determined by 13C NMR and this is nearly independent of the temperature. NMR investigations also give information about the real conformation of the molecules in the XB2 phase. Dielectric measurements indicate that the rotation around the molecular long axis is clearly hindered because of the packing of the bent molecules within the smectic layers. which exhibits antiferroelectric switching. [ABSTRACT FROM AUTHOR]

The small proteoglycan decorin had been localized previously at the d-band in the gap zone of collagen fibrils in nonmineralizing tissues. In bone matrix this zone is proteoglycan free and is at least in some species the place where mineralization along collagen fibrils starts. To study the metabolism of the small proteoglycans decorin and biglycan under mineralizing conditions, osteoblasts from human nasal bone were cultured for several weeks in the presence or absence of β-glycerophosphate and ascorbate. An immediate consequence of the treatment was a reduced expression of decorin, as judged by immune precipitation, whereas the biosynthesis of biglycan was not affected. Pulse-chase experiments were performed with osteoblasts embedded in floating type I collagen gels. In the presence of β-glycerophosphate and ascorbate, a more rapid turnover of both proteoglycans was noted; the one of biglycan reached statistical significance. Indirect evidence for an enhanced rate of proteoglycan endocytosis was obtained. This effect was not seen in cultured skin fibroblasts. Thus, osteoblasts respond rapidly to mineralizing conditions with alterations of small proteoglycan biosynthesis and turnover. [ABSTRACT FROM AUTHOR]

Heterotopic ossification is a metabolically active process which shares several properties of orthotopic bone formation and, therefore, represents an excellent model for studying bone matrix components. Immunohistochemical methods were used to investigate the distribution pattern of the small proteoglycans decorin and proteoglycan-100 during different stages of heterotopic ossification of pressure sores of paraplegic patients. Decorin and proteoglycan-100 exhibited a substantially divergent distribution pattern. Decorin was detectable in the perivascular matrix of granulation tissue as well as in the stroma of heterotopic ossification. The ossification zone was stained most strongly. In contrast, proteoglycan-100 was predominantly detectable in fibroblasts and preosteoblasts in early areas of osteogenesis. In more mature forms of heterotopic ossification immunostaining was markedly reduced in osteoblasts and osteocytes and even absent in so-called bone-lining cells. However, at least some osteoclasts were strongly positive. These results suggest indicate that decorin and proteoglycan-100 are important components during the formal pathogenesis of heterotopic ossification. The expression of the small proteoglycans, especially of proteoglycan-100, correlates with different phases during heterotopic ossification, showing a maximum for proteoglycan-100 in matrix-forming cells in early phases of bone formation, but in osteoclasts in mature bone. [ABSTRACT FROM AUTHOR]

Phase diagrams of different substituted acids with 1-heptyl-4-(4-pyridyl)pyridinium bromide were investigated. The formation of ionic hydrogen-bonded 1 :1 and 1:2 associates can be detected in the solid state. In some cases thermodynamically stable smectic A phases are observed. The maximum phase stability in the liquid crystalline state can differ considerably from the expected value for the 1 :1 associates. The layer thickness of the smectic layers measured by X-ray methods is smaller than the value calculated from molecular models. This indicates a complicated packing behaviour of the molecular building units in the SmA layers. [ABSTRACT FROM AUTHOR]

Dielectric measurements on four diols showing columnar hexagonal and micellar cubic phases were carried out. Besides the known fast local reorientation in theGHz-range, a new absorption in theMHz region was detected. This mechanism was interpreted as a collective motion of the molecules inside the micelles or cylindrical aggregates. The absorption was also found in the isotropic phase. Based upon the interpretation given, the molecular aggregates should also exist in the isotropic state. The electrical conductivity strongly supports the classification as inverse phases. [ABSTRACT FROM AUTHOR]