• Polymer(Korea)
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• v.28 no.1
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• pp.41-50
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• 2004

A new hydroxypropyl chitosan capable of forming a thermotropic liquid crystalline phase and two kinds of derivatives based on the hydroxypropyl chitosan (6-cholesteryloxycarbonylpentoxypropyl) chitosans (CHPCTs) and acrylic acid esters of CHPCT (CHPCTEs) were synthesized. The crosslinked films with liquid crystalline order were also prepared by photocrosslinking CHPCTE in mesophase. The liquid crystalline properties for all the samples and the swelling behavior of the crosslinked samples in acetone were investigated. In contrast with the hydroxypropyl chitosan, all the uncrosslinked cholesteryl-bearing samples farmed monotropic cholesteric phases with left-handed helicoidal structures and exhibited reflection colors over the full cholesteric range. This is the first report of a thermotropic cholesteric liquid crystalline chitosan derivative with reflection bands in the visible region. Both the optical pitches (λ$\_$m/'S) of CHPCT and CHPCTE decrease with temperature or with cholesteryl content at a given temperature. However, the λ$\_$m/ of CHPCT was larger than that of CHPCTE at the same temperature and at the same cholesteryl content. All the crosslinked samples did not display reflection colors, indicating that the cholesteric structure of CHPCTE significantly changes upon crosslinking. The two-dimentional anisotropic swelling characteristic of liquid crystalline networks was observed for all the crosslinked samples.

• Polymer(Korea)
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• v.31 no.1
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• pp.58-67
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• 2007

Fully cholesteryloxycarbonated and (8-cholesteryloxycarbonyl) heptanoated disaccharide derivatives were synthesized by reacting cellobiose, maltose, and lactose with cholesteryl chloroformate or 8- cholesteryloxycarbonylheptanoyl chloride, and their thermotropic liquid crystalline properties were investigated. All the cholesteryloxycarbonated derivatives (CH1DSs) formed enantiotropic cholesteric phases, whereas all the (8-cholesteryloxycarbonyl) heptanoated derivatives (CH8DSs) exhibited monotropic cholesteric phases with left-handed helicoidal structures whose optical pitches (${\lambda}m's$) decrease with increasing temperature. All the CH1DSs, contrast with the CH8DSs, did not display reflection colors over the full cholesteric range, suggesting that the helicoidal twisting power of the cholesteryl group highly depends on the length of the spacer joining the cholesteryl group to the disaccharide chain. The thermal stability and degree of order in the mesophase and the temperature dependence of the ${\lambda}m$ observed for EH8DSs were entirely different from those reported for the cholesterol-bearing dimers and triplet and the (8-cholesteryloxycarbonyl) heptanoated polysaccharide derivatives. The results were discussed in terms of the difference in the number of the mesogenic units per mole of repeating unit and the flexibility of the main chain.

• Korean Journal of Crystallography
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• v.13 no.1
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• pp.21-24
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• 2002

The crystal structure of cholesteryl crotonate was investigated by X-ray diffraction. Crystallo-graphic data for the title compound: P2₁, a = 13.446(4) , b = 11.802(3) , c = 18.782(5) , β = 103.99(2)°, Z = 4. Reflections were collected with an Enraf-Nonius CAD-4 diffractometer equipped with a graphite monochromator. The structure was solved by direct methods and refined by least-squares analyses. The final R value was 0.092 for 1604 reflections. The cholesterol fragment of the title compound were in good agreement with those for related cholesterol derivatives. The molecules were stacked in clearly separated layers. At the center of the layers, there were cholesterol-cholesteryl interactions between the symmetry-related A molecules and the cholesteryl-C(17) side chain of B molecules. There were also interactions between the C(17) side chain of A molecules and the crotonate chains off and B molecules in the interface region between layers. The crystal structure of the title compound turned out to be isostructural with those of cholesteryl ethylcarbonate, cholesteryl propylcarbonate, and cholesterol crotylcarbonate. The crystals show the liquid crystalline state having the cholesteric phase.

• Applied Chemistry for Engineering
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• v.30 no.2
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• pp.219-225
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• 2019

Side-chain liquid crystalline polymers with various compositions of azobenzene and cholesteryl functional groups as the mesogenic moiety were synthesized by direct polycondensation, and their properties were investigated. The inherent viscosity values of synthesized polymers were between 0.32 and 0.38 dL/g in 1,1,2,2-tetrachloroethane. All polymers except the SP-A10C0 polymer containing only the azobenzene group were amorphous or exhibited very low crystallinity due to the presence of bulky mesogenic side chains. All synthesized polymers exhibited enantiotropic liquid crystallinity; the SP-A10C0 polymer having only the azobenzene group exhibited a nematic phase, and all other polymers showed a cholesteric phase. In particular, it was found that when the content of cholesteryl groups in the side chain of the polymer increases, the liquid crystallinity decreases due to the bulkiness of cholesteryl groups.

• The Korean Journal of Rheology
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• v.9 no.4
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• pp.200-205
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• 1997

등방상에서는 폴리파라페닐렌테레프탈아미드(PPD-T)와 히드록시 프로필 셀룰로오 스(HPC)가 비슷한 유변학적 거동을 보였다. 그러나 이방성에서는 네마틱상을 형성하는 PPD-T와 콜레스테릭상(또는 꼬인 네마틱상)을 형성하는 HPC는 상이한 유변학적 특성을 나타냈다. 이방상을 나타내는 임계농도(C*)이상의 농도에서 Herchel-Bulkey 모델에 의해 얻 어진 항복응력을 보면 HPC의 경우 농도에 관계없이 거의 일정한 값을 나타낸 반면PPD-T 의경우에는 농도증가와 더불어 항북응력값이 크게 증가하였다. 또한 PPD-T가 일\ulcorner거으로 HPC보다 큰값의 항복응력을 나타냈다. 진동수 1 rad/s 에서는 PPD-T와 HPCahen 탄성계 수 G＇/2G＂가 농도의 증가와 더불어 증가하엿다. 그러나 100rad/s 에서는 HPCdmlruddn 임계농도이상의 농도에서 농도증가와 더불어 탄성계수값이 단순감소한 반면 PPD-T의 경우 에는 포화농도(B-point)이상의 농도에서 농도증가와 더불어 탄성계수값이 계속적으로 증가 하였다. HPC의 경우 저장탄성률이 변형정도의 영향을 받지 않았으나 PPD-T의 경우에는 저장탄성률이 변형정도에 매우 민감하였다.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.18 no.10
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• pp.69-74
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• 2017

In this study, cholesteryl 4-n-alkoxybenzoates (Chol-n), with alkyl groups used for controlling the temperature of transition to the liquid crystal phase, were synthesized, and the effects of the length of the alkyl groups on the physical properties of the liquid crystal compounds were investigated. The chemical structures and thermal and liquid crystalline properties of the synthesized compounds were investigated by Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy ($^1H$-NMR), differential scanning calorimetry (DSC), and polarizing optical microscopy (POM). The synthesized compounds showed melting transition temperatures ($T_m$) in the range of $103^{\circ}C$ to $143^{\circ}C$ and all of the compounds except Chol-6 exhibited a wide liquid crystal phase temperature range of about $60^{\circ}C$ to $100^{\circ}C$. No correlation between the number of carbon atoms in the molecule and the thermal properties of the compounds was found. All of the synthesized compounds showed an enantiotropic cholesteric phase, which was accompanied by a chiral smectic phase in the compounds Chol-6, Chol-8, Chol-9, and Chol-10. All of the compounds exhibited thermochromism in the liquid crystal state, and their color changed from red to blue as the temperature was increased.

• Elastomers and Composites
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• v.54 no.1
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• pp.14-21
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• 2019

Main-chain/side-chain liquid crystalline polymers (MCSCLCPs) combined with an azobenzene group and a cholesteryl group were synthesized to impart light and temperature sensitivity to the polymer. The polymers were designed with the azobenzene unit as the mesogenic group of the main-chain and various compositions of the azobenzene and cholesteryl units as the mesogenic group of the side-chain. The chemical structures and physical properties of the synthesized polymers were investigated by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, differential scanning calorimetry, thermogravimetric analysis, polarized optical microscopy, and ultraviolet-visible (UV-Vis) spectroscopy. All the MCSCLCPs were amorphous and exhibited enantiotropic liquid crystal phases; these polymers achieved the nematic phase with increasing content of the azobenzene group and exhibited the cholesteric phase with weak liquid crystallinity as the content of the cholesteryl group was increased. Furthermore, the polymers containing the azobenzene group showed photoisomerization when exposed to UV-Vis light, and the CP-A3C7 and CP-A5C5 polymers exhibited thermochromism in the temperature range of the liquid crystal phase.

• Polymer(Korea)
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• v.28 no.1
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• pp.92-102
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• 2004

(6-Cholesteryloxycarbonylpentoxypropyl)celluloses (CHPCs) with degree of esterification (DE) ranging from 2.25 to 2.91 were synthesized by reacting hydroxypropyl cellulose with 6-cholesteryloxycarbonylpentanoyl chloride. The acrylic esters of CHPCs (CHPCEs) and their photocrosslinked films with liquidcrystalline order were also synthesized. The thermotropic properties of mesophase for both uncrosslinked and crosslinked samples and the swelling behavior of the crosslinked samples in acetone were investigated. The hydroxypropyl cellulose exhibited an enantiotropic cholesteric phas, while all the uncrosslinked cholesterylbearing samples exhibited a monotropic cholesteric phases; the 6-cholesteryloxycarbonylpentanoyl chloride also showed a monotropic smectic phase. The hydroxypropyl cellulose formed a right-handed helix whose optical pitch (λ$\sub$m/) increases with temperature, whereas all the uncrosslinked derivatives farmed left-handed helices whose λ$\sub$m/'s decreased with temperature. The thermal stability of the mesophase and the magnitude of λ$\sub$m/ at the same temperature for both CHPCs and CHPCEs decreased with increasing DE. All the crosslinked samples, in constrast with CHPCEs, did not display reflection colors but exhibited an anisotropic swelling characteristic of crosslinked gel retaining liquid-crystalline order.

• Journal of the Korean Graphic Arts Communication Society
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• v.18 no.2
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• pp.41-54
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• 2000

Photochemical modulation of Bragg-reflection wavelengths based on isomerization of an azobenzene (Azo) and subsequent change in reflectance was investigated in cholesteric liquid crystals (ChLCs) which reflect light in visible wavelength region. Irradiation at 366 nm, which causes an efficient transcis isomerization of Azo, led to change in reflected color of ChLCs toward shorter wavelengths with a concomitant lowering of phase transition. Reversible change in color was induced all-optically by alternate irradiation at effective wavelengths for reversible isomerization of Azo. A considerable variation in reflectance was also observed when the photoinduced change in color was measured by a probe light with the same handedness as the ChLCs. The spectral Position of selective light reflection in the initial states played an important role to produce a normal-mode and a reverse-mode switching in photoinduced modulation of reflectance of the ChLCs with respect to the probe light.

• Polymer(Korea)
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• v.30 no.4
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• pp.338-349
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• 2006

Fully or nearly fully(8-cholesteryloxycarbonyl)heptanoated polysaccharide derivatives were synthesized by reacting cellulose, amylose, chitosan, chitin, alginic acid, pullulan or amylopectin with (8-cholesteryloxycarbonyl)heptanoyl chloride (CH8C), and their thermotropic liquid crystalline behaviors were investigated. Like in the case of CH8C, all the polysaccharide derivatives formed monotropic cholesteric phases with left-handed helicoidal structures whose optical pitches $({\lambda_m}'s)$ decrease with increasing temperature. Amylopectin derivative also formed a monotropic cholesteric phase with lefthanded helicoidal structures but, in contrast with the other derivatives, did not display reflection colors over the full cholesteric range, suggesting that the helicoidal twisting power of the cholesteryl group highly depends on the branched structure in amylopectin. The thermal stability and degree of order in the mesophase, the magnitude of ${\lambda}_m$ at the same temperature, and the temperature dependence of the ${\lambda}_m$ observed for polysaccharide derivatives were entirely different from those reported for the polymers in which the cholesteryl groups are attached to flexible or semiflexible backbones through flexible spacers. The results were discussed in terms of the difference in the chemical structures of the main and side chains and flexibility of the main chain.