• Archives of Pharmacal Research
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• v.9 no.2
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• pp.75-79
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• 1986

The effect of phenothiazine derivatives on the thermotropic transition of liposomal lipid bilayer made of dipalmitoyl phosphatidylchline and dipalmitoyl phosphatidic acid was investigated with differential scanning calorimetry. The thermograms of the liposomal bilayer incorporated with levomepromazine, chlopromazine, prochloperazine, perphenazine and fluphenazine were obtained and the size of cooperative unit of the transition were calculated from the ratio of the van't Hoff enthalpy change to the calculated enthalpy change of the transition. The results showed that incorporation of phenothiazine derivatives into the liposomal bilayer reduced the transition temperature at which the transition from solid state to liquid-crystalline state occurs, and broadened the thermogram peaks. Phenothiazine derivatives also significantly reduced the size of cooperative unit of the transition. The effect of the drugs was proportional to the concentration of the drug in the bilayer. This means that phenothiazine derivatives might have significant fluidizing effects on the biomembrane. The sizes of cooperative unit were successfully corrlated with phar-macological activities of the drugs and the surface pressure increases of lipid monolayer by these drugs. These correlations might be ascribed to a possible hydrophobic nature of interaction between the biomembrane and the drugs involved in their pharmacology.

• The Korean Journal of Pharmacology
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• v.26 no.1
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• pp.77-82
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• 1990

The effects of phenothiazine derivatives and calcium on the thermotropic phase transition of bilayers in dipalmitoyl phosphatidylcholine (DPPC) and dipalmitoyl phosphatidic acid (DPPA) liposomes were investigated with differential scanning calorimeter (DSC). Bilayers underwent an abrupt organizational changes at a characteristic temperature when heated. Such temperature-dependent transition was particularly striking and sharp in the bilayers prepared from pure phospholipids. The ability of phenothiazine derivatives to modify the phase transition of phospholipids liposomes was measured by a broadening of the phase transition profile, that transition began to appear at lower temperature than which occurs in untreated liposomes. Calcium ion caused a large upward shift in the transition temperature of DPPC:DPPA (34:66mol%) liposomes. When the liposomes were first incubated with calcium ion followed by phenothiazine derivatives, disappearance of the broad curve centering at $73^{\circ}C$ indicated displacement of calcium ion by phenothiazine derivatives at the anionic site. It is supposed that calcium ion and phenothiazine derivatives might compete with each other on the head group of acidic phospholipid.

• Macromolecular Research
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• v.17 no.5
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• pp.313-318
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• 2009

The side chain liquid crystal triblock copolymers (TBCs), which underwent phase transitions below their decomposition temperature, were prepared by copolymerization of poly(n-butyl acrylate) and a comonomer containing the mesogenic azobenzene group. The physical properties of TBCs in the distinctive transition temperature ranges were investigated in terms of the liquid crystal (LC) content in the copolymers. The phase transition temperatures traced optically, thermally and rheologically were well coincided one another and clearly exhibited the phase transition of smectic-nematic-isotropic with increasing temperature. In the smectic phase, increasing temperature made the liquid crystal system more elastic, but viscosity (${\eta}'$) remained almost constant. In the nematic phase, increasing temperature abruptly decreased ${\eta}'$ and G', ultimately leading to isotropic phase. Both smectic and nematic phases exhibited Bingham viscosity behavior but the former gave much greater yield stress at the same LC content.

• Journal of Life Science
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• v.10 no.2
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• pp.27-32
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• 2000

To understand the effects of the fraction from Chrysanthemum coronarium L. (CC), we prepared five different types of samples, denoted here as CCMM, CCMH, CCMEA, CCMB and CCMA. We studied the effects of these samples on the phase transition of liposomal membranes by high-sensitivity differential scanning calorimetry (nano-DSC). We used dipalmitoylphosphatidylcholine (DPPC) bilayers which make most stable liposomes among the other phosphatidylcholines. When the samples were added to the bilayers, the phase transition temperatures of DPPC liposomes incorporated with CCMH and CCMEA were decreased by 1.5 and 2^{\circ}C$, while the other three fractions showed less tendencies. The CCMH and CCMEA fractions markedly affected the thermotropic properties of DPPC liposomes, broadened and shifted the thermograms of DSC. It also significantly reduced the size of cooperative unit of the transition. In all cases, there was no change in enthalpy of transition within the concentration range of the CC fractions studied. We concluded that the incorporation of the CCMH and CCMEA into DPPC liposomes was preferentially located in the hydrophobic core of DPPC bilayers compared to the other three fractions CCMM, CCMB and CCMA. These results suggest that certain substances in CCMH and CCMEA fractions might have biologically significant effects on the fluidity of biological membrane.

• Bulletin of the Korean Chemical Society
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• v.11 no.6
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• pp.508-511
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• 1990

The simple binary mixtures of pure phospholipids such as DPPC:DSPC and DPPC:DPPA were investigated with differential scanning calorimeter. The thermotropic properties of DPPC and DSPC mixtures did not deviate much from the ideal curves that was obtained on varying either the temperature or the relative proportions of phospholipids. This means that the two phospholipids are completely miscible in the liquid and solid phase. But the thermotropic properties of DPPC and DPPA mixture deviated much from the ideal phase diagram. It resulted from the repulsion between the head groups of acidic phospholipids. Heat capacity suggested by Harden McConell was calculated. The larger $C_p$ was, the sharper the endothermic peak became.

• Bulletin of the Korean Chemical Society
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• v.12 no.2
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• pp.199-206
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• 1991

A statistical thermodynamic theory of thermotropic main-chain polymeric liquid crystalline melts is developed within the framework of the lattice model by a generalization of the well-known procedure of Flory and DiMarzio. According to the results of Vasilenko et al., the theory of orientational ordering in melts of polymers containing rigid and flexible segments in the main chain is taken into account. When the ordering of flexible segments in the nematic melt is correlated with that of rigid mesogenic groups, the former is assumed to be given as a function of the ordering of rigid mesogenic cores. A free energy density that includes short-range packing contributions is formulated. The properties of the liquid-crystalline transiton are investigated for various cases of the system. The results calculated in this paper show not only the order-parameter values but also the first-order phase transition phenomena that are similar to those observed experimentally for the thermotropic liquid-crystalline polymers and show the transitional entropy terms which actually increase upon orientational ordering. In the orientational ordering values, it is shown that mesogenic groups, flexible segments, and gauche energy (temperature) may be quite substantial. Finally, by using the flexibility term, we predict the highly anisotropic mesophase which was shown by Vasilenko et al.

• Polymer(Korea)
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• v.33 no.4
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• pp.297-306
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• 2009

A homologous series of side chain liquid crystalline polymers, poly [1-{4-(4'-cyanophenylazo)phenoxyalkyloxy}ethylene]s(CAPETn, where n, the number of methylene units in the spacer, is $2{\sim}10$) were synthesized from poly(vinyl alcohol) and 1-{4-(4'-cyanophenylazo)phenoxy}alkylbromides(CAPBn, n=$2{\sim}10$), and their thermotropic liquid crystalline phase behaviors were investigated. The CAPBn with n of $2{\sim}5$ did not show any liquid crystalline behavior, while those with n of 6 and $7{\sim}10$ showed enantiotropic and monotropic nematic phases, respectively. In contrast, among the CAPETn polymers, only CAPET5 exhibited an enantiotropic nematic phase, while other polymers showed monotropic nematic phases. The isotropic-nematic transition temperatures of CAPETns and their entropy variation at the phase transition that were higher values than those of CAPBns, demonstrated a typical odd-even effect as a function of n. These phase transition behaviors were disscussed in terms of the 'virtual trimer model' by Imrie. The mesophase properties of CAPETns were largely different from those reported for the polymers in which the (cyanophenylazo) phenoxy groups are attached to polyacrylate, polymethacrylate, and polystyrene backbones through polymethylene spacers. The results indicate that the mode of chemical linkage of the side group with the main chain plays an important role in the formation, stabilization, and type of mesophase.

• Applied Chemistry for Engineering
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• v.22 no.4
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• pp.358-366
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• 2011

A homologous series of linear liquid crystal dimers, the ${\alpha},{\omega}$-bis(4-cyano-azobenzene-4'-oxy)alkanes (CATWETn, where n, the number of methylene units in the spacer, is 2~10) were synthesized, and their thermotropic liquid crystalline phase behavior were investigated. The CATWETn with n of 3 and 6 exhibited monotropic nematic phases, whereas other derivatives showed enantiotropic nematic phases. The nematic-isotropic transition temperatures of the dimers and their entropy variation at the phase transition showed a large odd-even effect as a function of n. This phase transition behavior was rationalized in terms of the change in the average shape of the spacer on varying the parity of the spacer. The thermal stability and degree of order in the nematic phase and the magnitude of the odd-even effect of CATWETn were similar to those for the methoxy-, nitro-, and pentyl-substituted dimers, while they were significantly different from those for the monomesogenic compounds, 1-{4-(4'-cyanophenylazo)phenoxy}alkylbromides and the side-chain liquid-crystalline polymers, the poly[1-{4-(4'-cyanophenylazo)phenoxyalkyloxy}ethylene]s. The results were discussed in terms of 'virtual trimer model' by Imrie.

• Elastomers and Composites
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• v.41 no.2
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• pp.108-115
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• 2006

A series of thermotropic polyurethanes containing biphenyl units was synthesized by polyaddition reaction of diisocyanates such as 2,6-tolylene diisocyanate, 2,5-tolylene diisocyanate, 2,4-tolylene diisocyanate, 1,4-phenylene diisocyanate, and hexamethylene diisocyanate with 4,4'-Bis(9-hydroxynonoxy)biphenyl (BP9). 4,4'-bis(9-hydroxynonoxy)biphenyl exhibited a smectic type mesophase. Mesophase was found for all synthesized liquid crystalline polyurethanes except 1,4-PDI/BP9 based polyurethane. Structures of the monomer and the corresponding polymers were identified using FT-IR and $^1H-NMR$ spectroscopies. Their phase transition temperatures and thermal stability were also investigated by differential scanning calorimetry and optical polarizing microscopy.

• Applied Chemistry for Engineering
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• v.20 no.6
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• pp.603-611
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• 2009

Thermotropic liquid crystalline behavior of a homologous series of penta-O-4-{4'-(cyanophenylazo)phenoxy}alkyl-D-glucopyranoses(CAGETn, n = 2~10, the number of methylene units in the spacer) has been investigated. The CAGETn with n of 2 and 7 exhibited enantiotropic nematic phases whereas other derivatives showed monotropic nematic phases. This is the first report of glucose derivatives that form thermotropic nematic phases. The isotropic-nematic transition temperatures ($T_{iNS}$) of CAGETns and their entropy variation at $T_{iN}$ showed the odd-even effect as a function of n. This behavior was rationalized in terms of the change in the average shape of the side chains as the parity of the spacer is varied. This rationalization also accounts for the observed variation of nematic-crystalline phase transition temperatures ($T_{NkS}$) and associoated entropy change at $T_{Nk}$. The entropy change at $T_{iN}$ or $T_{Nk}$ reaches a mininum at n = 3, before it increases again for n = 4. This may be attributed to the difference in the arrangement of the side groups. The mesophase properties of CAGETns were entirely different from those reported for partially or fully alkylated glucopyranoses. This result suggests that the degree of substitution and chemical structure of the substituents play an important role in the formation of the mesophase structures in the liquid crystals.