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1.
Yilmaz Y 《The Journal of chemical physics》2007,126(22):224501
Transition between collapsed state phases and discontinuous volume phase transition for a hydrogen bonding gel, poly(methacrylic acid-co-dimethyl acrylamide), were observed by using both the volume measurements and fluorescence intensity of the pyranine fluoroprobe (8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt) bonded to the gel by means of electrostatic interactions. In the collapsed state, while there is no appreciable change in the volume of the gel, a considerable variation in the fluorescence intensity occurred around 30 degrees C signaling a second order phase transition between collapsed state phases, from relatively frozen to a fluctuating phase. Our analysis of the data around 30 degrees C indicates that the critical point of gel volume transition belongs to the so-called mean-field universality class, as predicted in Onuki [Phys. Rev. A 38, 2192 (1988)] and by Golubovic and Lubensky [Phys. Rev. Lett. 63, 1082 (1989)]. The relaxation time for the equilibrium swelling critically depends on the temperature and diverges near 60 degrees C, where both fluorescence intensity and the volume of the gel change drastically and indicate the discontinuous volume phase transition. The swelling kinetics of the critical gel during the discontinuous volume phase transition can be modeled best with the first term in the expansion of the Li-Tanaka equation for a long initial period of the swelling time. 相似文献
2.
Bezner S Krueger M Hamplová V Glogarová M Giesselmann F 《The Journal of chemical physics》2007,126(5):054902
The smectic layer spacing of two homologous series of ferroelectric liquid crystal compounds was characterized by small-angle x-ray diffraction and different degrees of smectic layer shrinkage on cooling from the SmA* into the SmC* phase were observed. The smectic A*-smectic C* phase transition was further studied by measuring the thermal and electric field effects on the optical tilt angle and the electric polarization. With decreasing length of the alkyl terminal chain the phase transition changes from tricritical exhibiting high layer shrinkage to a pure second-order transition with almost no layer shrinkage. This is explained by the increased one-dimensional translational order of the smectic layers, which seems to promote the "de Vries"-type [Mol. Cryst. Liq. Cryst. 41, 27 (1977)] smectic A*-C* phase transition with no or little layer shrinkage. 相似文献
3.
MesomorphicCharacteristicsofInducedChiralNematicPhaseof[SmecticLCP,PS(4BC/DM)/NematicLC,E7/ChiralDopant,CB┐15]┐TernaryComposi... 相似文献
4.
Xiaohua He Hailiang Zhang Deyue Yan Xiayu Wang 《Journal of polymer science. Part A, Polymer chemistry》2003,41(18):2854-2864
A series of side‐chain liquid‐crystalline (LC) homopolymers of poly[6‐(4‐methoxy‐4′‐oxy‐azobenzene) hexyl methacrylate] with different degrees of polymerization were synthesized by atom transfer radical polymerization (ATRP), which were prepared with a wide range of number‐average molecular weights from 5.1 × 103 to 20.6 × 103 with narrow polydispersities of around 1.17. Thermal investigation showed that the homopolymers exhibit two mesophases, a smectic phase, and a nematic phase, and the phase‐transition temperatures of the homopolymers increase clearly with increasing molecular weights. A series of novel LC coil triblock copolymers with narrow polydispersities was synthesized by ATRP, and their thermotropic phase behavior was investigated with differential scanning calorimetry and polarized optical microscopy. The LC coil triblocks were designed to have an LC conformation of poly[6‐(4‐methoxy‐4′‐oxy‐azobenzene) hexyl methacrylate] with a wide range of molecular weights from 3.5 × 103 to 1.7 × 104 and the coil conformation of poly(ethylene glycol) (PEG) (number‐average molecular weight: 6000 or 12,000) segment. Their characterization was investigated with 1H NMR, Fourier transform infrared spectra, and gel permeation chromatography. Triblock copolymers exhibited a crystalline phase, a smectic phase, and a nematic phase. The phase‐transition temperatures from the smectic to nematic phase and from the nematic to isotropic phase increased, and the crystallization of PEG depressed with increasing molecular weight of the LC block. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2854–2864, 2003 相似文献
5.
Liquid crystalline α-[bis(2-hydroxyethyl)amino]- ω -(4′-methoxybiphenyl-4-oxy)alkane hydrochlorides with different spacer lengths (6, 8, 10 methylene units) have been synthesized and characterized by NMR, DSC, polarizing optical microscopy and X-ray diffraction. The melting temperatures of the hydrochlorides decrease with increasing number of methylene units in the spacer. Highly ordered and very viscous liquid crystalline (LC1) smectic phases are formed on melting. Upon further heating these phases are transformed into a less viscous smectic C phase (LC2). The temperature of the LC1-LC2 transition decreases and the temperature of the LC2 to isotropic phase transition (LC2-I transition) increases with increasing number of methylene units in the spacer. 相似文献
6.
《中国化学快报》2022,33(8):3973-3976
Amphiphilic molecules adsorbed at the interface could control the orientation of liquid crystals (LCs) while LCs in turn could influence the distributions of amphiphilic molecules. The studies on the interactions between liquid crystals and amphiphilic molecules at the interface are important for the development of molecular sensors. In this paper, we demonstrate that the development of smectic LC ordering from isotropic at the LC/water interface could induce local high-density distributions of amphiphilic phospholipids. Mixtures of liquid crystals and phospholipids in chloroform are first emulsified in water. By fluorescently labeling the phospholipids adsorbed at the interface, their distributions are visualized under fluorescent confocal microscope. Interestingly, local high-density distributions of phospholipids showing a high fluorescent intensity are observed on the surface of LC droplets. Investigations on the correlation between phospholipid density, surface tension and smectic LC ordering suggest that when domains of smectic LC layers nucleate and grow from isotropic at the LC/water interface as chloroform slowly evaporates at room temperature, phospholipids transition from liquid-expanded to liquid-condensed phases in response to the smectic ordering, which induces a higher surface tension at the interface. The results will provide an important insight into the interactions between liquid crystals and amphiphilic molecules at the interface. 相似文献
7.
Kunlun Wang Prabin Rai Ashani Fernando Tibor Szilvási Huaizhe Yu Nicholas L. Abbott 《Liquid crystals》2020,47(1):3-16
ABSTRACTA series of fluorine tail-terminated alkoxy and alkyl cyanobiphenyl compounds and some cyano-p-terphenyl derivatives were synthesised and mesogenic properties described. Comparison with the non-fluorinated K series and M series indicates that the terminal fluorine atom generally decreases the transition temperatures and, more interestingly, depresses the formation of a smectic phase. Several binary LC mixtures formed by the fluorine tail-terminated compounds were found exhibiting promising room temperature nematic phases with wide ranges. The mixture F7OCB and F8OCB shows homeotropic ordering at the metal salts-decorated surfaces and planar ordering at the free surface, which may have potential application in designing a more sensitive and faster LC system to targeted analytes. 相似文献
8.
S. Lakshminarayana C. R. Prabhu D. M. Potukuchi N. V. S. Rao V. G. K. M. Pisipati D. Saran 《Liquid crystals》2013,40(6):909-914
Abstract The temperature dependence of density in terephthalylidene-bis-p-n-alkylanilines (TBAA5 and 6) is studied to investigate the phase transitions, associated volume jumps, order of the transitions, estimated pressure dependence of transition temperatures, and pretransitional effects. The compounds exhibit nematic, smectic A, smectic C, smectic F, smectic G and smectic H phases with higher clearing temperatures. The smectic A to smectic C transition, which is a fluctuation induced first order transition in TBAA5, is found to be a second order transition in TBAA5 and 6. The results are discussed in the light of other experimental reports. The estimated pressure dependence of transition temperatures along with the reported experimental P[sbnd]T data are discussed. The N[sbnd]SA transition is first order in TBAA5 and 6. The studies across other transitions are also discussed. 相似文献
9.
Tan LN Orler VJ Abbott NL 《Langmuir : the ACS journal of surfaces and colloids》2012,28(15):6364-6376
We report that specific binding of ligand-functionalized (biotinylated) phospholipid vesicles (diameter = 120 ± 19 nm) to a monolayer of proteins (streptavidin or anti-biotin antibody) adsorbed at an interface between an aqueous phase and an immiscible film of a thermotropic liquid crystal (LC) [nematic 4'-pentyl-4-cyanobiphenyl (5CB)] triggers a continuous orientational ordering transition (continuous change in the tilt) in the LC. Results presented in this paper indicate that, following the capture of the vesicles at the LC interface via the specific binding interaction, phospholipids are transferred from the vesicles onto the LC interface to form a monolayer, reorganizing and partially displacing proteins from the LC interface. The dynamics of this process are accelerated substantially by the specific binding event relative to a protein-decorated interface of a LC that does not bind the ligands presented by the vesicles. The observation of the continuous change in the ordering of the LC, when combined with other results presented in this paper, is significant, as it is consistent with the presence of suboptical domains of proteins and phospholipids on the LC interface. An additional significant hypothesis that emerges from the work reported in this paper is that the ordering transition of the LC is strongly influenced by the bound state of the protein adsorbed on the LC interface, as evidenced by the influence on the LC of (i) "crowding" of the protein within a monolayer formed at the LC interface and (ii) aging of the proteins on the LC interface. Overall, these results demonstrate that ordering transitions in LCs can be used to provide fundamental insights into the competitive adsorption of proteins and lipids at oil-water interfaces and that LC ordering transitions have the potential to be useful for reporting specific binding events involving vesicles and proteins. 相似文献
10.
M. Rössle L. Braun D. Schollmeyer R. Zentel Corresponding author J. P. F. Lagerwall F. Giesselmann 《Liquid crystals》2013,40(5):533-538
This paper compares smectic phases formed from LC‐homo‐ and LC‐co‐polysiloxanes. In the homopolysiloxane, each repeating unit of the polymer chain is substituted with a mesogen, whereas in the copolysiloxanes mesogenic repeating units are separated by dimethylsiloxane units. Despite a rather similiar phase sequence of the homo‐ and co‐polysiloxanes—higher ordered smectic, smectic C* (SmC*), smectic A (SmA) and isotropic—the nature of their phases differs strongly. For the copolymers the phase transition SmC* to SmA is second order and of the ‘de Vries’ type with a very small thickness change of the smectic layers. Inside the SmA phase, however, the smectic thickness decreases strongly on approaching the isotropic phase. For the homopolymer the phase transition SmC* to SmA is first order with a significant thickness change, indicating that this phase is not of the ‘de Vries’ type. This difference in the nature of the smectic phases is probably a consequence of microphase separation in the copolymer, which facilitates a loss of the tilt angle correlation between different smectic layers. This has consequences for the mechanical properties of LC‐elastomers formed from homo‐ and co‐polymers. For the elastomers from homopolymers the smectic layer compression seems to be rather high, while it seems to be rather small for the copolymers. 相似文献
11.
Density measurements as a function of temperature for four homologues of the 5-n-alkyl-2-(4-n-alkyloxy-phenyl)-pyrimidines (PYP nOm) which exhibit nematic, smectic A and smectic C phases are reported. Furthermore 1-butyl-c-4-(4'-octyl-biphenyl-4-yl)-r-cyclo-hexan- carbonitrile (NCB84) is studied; this has additionally a smectic G phase. From these data the thermal expansion coefficients are calculated. Comparing PYP 907 and PYP 709, differing in their exchanged alkyl chains, we observe in the smectic A and the smectic C phase a distinctly lower density for PYP 709 whereas their densities nearly agree in the isotropic phase. The pyrimidines PYP 709 and PYP 808 exhibit a continuous volume change on crossing the smectic A-smectic C transition which differs dramatically from PYP 909 which shows a small volume jump. Furthermore a binary mixture of PYP 708 and PYP 706 is analysed which shows only a nematic and a smectic C phase. The associated phase transition is probably first order revealing nearly no pretransitional behaviour. The smectic A-smectic C transition of NCB84 seems to be second order exhibiting a continuous change of volume across the transition whereas the smectic C-smectic G transition shows a volume discontinuity and is first order. In order to induce ferroelectric smectic C* phases all smectic C materials were doped with a chiral pyrimidine dopant. Astonishingly the thermal expansion coefficient across the smectic A-smectic C* transition is influenced by the dopant in a very different way. 相似文献
12.
Pradip K. Bhowmik Xiaobin Wang Haesook Han 《Journal of polymer science. Part A, Polymer chemistry》2003,41(9):1282-1295
A series of main‐chain, thermotropic, liquid‐crystalline (LC), hydrogen‐bonded polymers or self‐assembled structures based on 4,4′‐bipyridyl as a hydrogen‐bond acceptor and aliphatic dicarboxylic acids, such as adipic and sebacic acids, as hydrogen‐bond donors were prepared by a slow evaporation technique from a pyridine solution and were characterized for their thermotropic, LC properties with a number of experimental techniques. The homopolymer of 4,4′‐bipyridyl with adipic acid exhibited high‐order and low‐order smectic phases, and that with sebacic acid exhibited only a high‐order smectic phase. Like the homopolymer with adipic acid, the two copolymers of 4,4′‐bipyridyl with adipic and sebacic acids (75/25 and 25/75) also exhibited two types of smectic phases. In contrast, the copolymer of 4,4′‐bipyridyl with adipic and sebacic acids (50/50), like the homopolymer with sebacic acid, exhibited only one high‐order smectic phase. Each of them, including the copolymers, had a broad temperature range of LC phases (36–51 °C). The effect of copolymerization for these hydrogen‐bonded polymers on the thermotropic properties was examined. Generally, copolymerization increased the temperature range of LC phases for these polymers, as expected, with a larger decrease in the crystal‐to‐LC transition than in the LC‐to‐isotropic transition. Additionally, it neither suppressed the formation of smectic phases nor promoted the formation of a nematic phase in these hydrogen‐bonded polymers, as usually observed in many thermotropic LC polymers. The thermal transitions for all of them, measured by differential scanning calorimetry, were well below their decomposition temperatures, as measured by thermogravimetric analysis, which were in the temperature range of 193–210 °C. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1282–1295, 2003 相似文献
13.
采用示差扫描量热法(DSC)、一维(1D)、二维(2D)广角X-射线衍射(WAXD)和偏光显微镜(PLM)等研究手段对聚{11-[(4′-正庚氧基-4-联苯基)羰基]氧-1-十一炔}(PA-9,7)的本体相转变和相结构进行研究,并采用分子动力学方法对相结构进行模拟.结果表明,样品的相转变为近晶B相(SmB)近晶A相(SmA)各向同性态(Iso).在近晶B相中,侧链在层状结构中排列成具有六次对称性的准长程有序结构。 相似文献
14.
To develop viable polymer stabilized liquid crystal systems, it is crucial to understand the factors that affect polymer nanostructure evolution. This work examines the influence of the photopolymerization of aliphatic and fluorinated monoacrylate monomer within a room temperature smectic liquid crystal (LC). Additionally, the effect of LC order on polymerization kinetics, monomer and polymer organization, and the effect of the polymer on LC properties have been examined. Through this work, insight has been gained regarding the impact that the introduction of a fluorinated monoacrylate monomer has on polymerization kinetics, LC organization, and monomer/polymer segregation and organization within a polymer/LC system. Fluorinated moieties lower the surface energy of the monomer to enhance segregation between the smectic layers of the LC as compared with an analogous aliphatic monomer. Additionally, the enhanced segregation significantly increases the polymerization rate in the smectic phase and drives the continued segregation of the fluorinated polymer during and after polymerization. Fluorination also leads to the formation of an ordered polymer nanostructure if polymerized in ordered LC phases. This ordering is particularly evident when the fluorinated monomer is polymerized in the smectic phase in which the monomer is organized between the smectic layers of the LC. In addition, the ordered polymer structure found with the fluorinated monomer in the smectic phase leads to continued birefringence above the clearing point of the LC due to surface interactions between the LC and the ordered fluorinated polymer. The continued birefringence offers an exceptional opportunity to examine how factors such as polymer molecular mass and UV light intensity affect the overall polymer morphology of these polymer/LC systems. As the initiator concentration and UV light intensity are decreased, longer polymer chains form lattice-type morphologies; whereas, shorter polymer chains form smoother morphologies that more closely mirror the texture of the LC smectic phase. 相似文献
15.
To develop viable polymer stabilized liquid crystal systems, it is crucial to understand the factors that affect polymer nanostructure evolution. This work examines the influence of the photopolymerization of aliphatic and fluorinated monoacrylate monomer within a room temperature smectic liquid crystal (LC). Additionally, the effect of LC order on polymerization kinetics, monomer and polymer organization, and the effect of the polymer on LC properties have been examined. Through this work, insight has been gained regarding the impact that the introduction of a fluorinated monoacrylate monomer has on polymerization kinetics, LC organization, and monomer/polymer segregation and organization within a polymer/LC system. Fluorinated moieties lower the surface energy of the monomer to enhance segregation between the smectic layers of the LC as compared with an analogous aliphatic monomer. Additionally, the enhanced segregation significantly increases the polymerization rate in the smectic phase and drives the continued segregation of the fluorinated polymer during and after polymerization. Fluorination also leads to the formation of an ordered polymer nanostructure if polymerized in ordered LC phases. This ordering is particularly evident when the fluorinated monomer is polymerized in the smectic phase in which the monomer is organized between the smectic layers of the LC. In addition, the ordered polymer structure found with the fluorinated monomer in the smectic phase leads to continued birefringence above the clearing point of the LC due to surface interactions between the LC and the ordered fluorinated polymer. The continued birefringence offers an exceptional opportunity to examine how factors such as polymer molecular mass and UV light intensity affect the overall polymer morphology of these polymer/LC systems. As the initiator concentration and UV light intensity are decreased, longer polymer chains form lattice-type morphologies; whereas, shorter polymer chains form smoother morphologies that more closely mirror the texture of the LC smectic phase. 相似文献
16.
Czarnik-Matusewicz B Pajak J Rospenk M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(1-3):157-163
The FT-IR spectra of a thin layer of pure 4-chloro-2'-hydroxy-4'-pentyloxyazobenzene (CHPAB) were studied as a function of temperature. A detailed analysis of the intensity variations was performed by a method based on principal component analysis (PCA). It was shown that the phase transition temperatures obtained by means of PCA and those determined by differential scanning calorimetry (DSC), the most widely used technique in the field, were nearly identical. The PCA results revealed that the transition from solid to a liquid crystalline (LC) phase (smectic A) is more drastic phase transition in terms of infrared absorption changes. The nematic to isotropic phase transition is much less infrared sensitive. Very much smaller absorption changes are associated with the transition between the smectic and nematic mesophases. The pattern of the intensity changes strictly is correlated with the orientation of the CHPAB molecules towards the surface windows due to the surface-induced homeotropic alignment of LC molecules. The important role of hydrogen bonding interaction on the observed transition is disclosed. 相似文献
17.
Deuterium NMR measurements of the molecular orientational ordering (nematic order) are reported for a reentrant binary mixture of some alkoxy-eyanobiphenyls (nOCB) to which small amounts of perdeuterated p-xylene have been added. The results indicate that the degree of orientational order is enhanced at the smectic A to reentrant nematic phase transition. This effect is shown to be in agreement with the predictions of a Landau-type theory of the reentrant phase transition where-by this phase transition is explained as the result of a coupling between the smectic and the nematic order parameters. 相似文献
18.
We study the orientation and order parameter of a liquid crystalline random side chain copolymer by 13C NMR. Evidence has previously been presented that this material forms a de Vries smectic A phase. The NMR data show that the molecular tilt angle in the smectic A phase is very small or zero and the smectic A–smectic C* transition is attributed predominantly to a change of the molecular tilt rather than azimuthal ordering. We discuss the NMR results in the context of earlier X‐ray and elastic characterizations of structurally similar materials. 相似文献
19.
P. Schiller 《Liquid crystals》1994,17(5):667-679
In smectic phases molecules can reorientate around their long and short axes. The motion of a molecule around its long axis is non-cooperative and influenced by both stochastic and deterministic forces exerted by neighbouring molecules. Solving the Smoluchovsky equation for such a reorientation process, two-time correlation functions are calculated which are related to frequency-dependent susceptibilities. The results are used for investigating how deterministic forces in higher ordered smectic phases have an effect on microwave spectra. It can be concluded that the quadrupolar ordering produces a splitting of the relaxation frequency. This splitting, which should occur at the transition from the smectic A to the smectic C phase, is only weakly influenced by an additional dipolar (ferroelectric) ordering. 相似文献
20.
Yang Y Liu X Nakamura A Binnemans K Liu J 《The journal of physical chemistry. B》2008,112(17):5291-5295
The effect of pressure on the phase behavior of the liquid crystalline complex [Eu(bta)(3)L(2)] (bta is benzoyltrifluoroacetonate, and L is the Schiff base 2-hydroxy-N-octadecyl-4-tetradecyloxybenzaldimine) was studied by X-ray diffraction, Raman spectroscopy, and luminescence spectroscopy. The pressure was varied between ambient pressure and 8.0 GPa. [Eu(bta)(3)L(2)] exhibits a smectic A (SmA) phase at room temperature. The complex undergoes a transition from the SmA phase to a solid lamellar structure around 0.22 GPa and another transition from the solid lamellar phase to an amorphous state from 1.6 to 3.5 GPa. At low pressures, the smectic layer spacing increases, and the intermolecular distance decreases. Above 3.5 GPa, both the interlamellar and the intermolecular spacings hardly change, but the intensity of X-ray reflections exhibits a remarkable decrease and eventually vanishes. An interpretation of the changes in the molecular structure is given. It was found that less interdigitation of the alkyl chains situated in adjacent layers and/or a full extension of the alkyl chains occurred at low pressures and that the second phase transition was accompanied by a transfer of the hydrogen atom from the nitrogen atom of the imine group to the oxygen atom of the Schiff base ligand. The effect of applying pressure equals that of the lanthanide contraction on the phase behavior. 相似文献