• 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.

• Polymer(Korea)
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• v.32 no.5
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• pp.446-457
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• 2008

Three kinds of hydroxypropyl cellulose (HPC) derivatives: 6- (cholesteryloxycarbonyl) pentoxypropyl celluloses(CHPCs) with degree of esterification(DE) ranging from 0.6 to 3, 6-[4-{4'-(nitrophenylazo)phenoxycarbonyl}] pentoxypropyl celluloses (NHPCs) with DE ranging from 0.4 to 3, and fully 6-(cholesteryloxycarbonyl) pentanoated NHPCs (CNHPCs) were synthesized, and their thermotropic liquid crystalline properties were investigated. All the CHPCs and NHPCs with $DE{\leq}1.7$ formed enantiotropic cholesteric phases, whereas CNHPCs with 6-(cholesteryloxycarbonyl) pentanoyl DE(DEC) more than 1.6 exhibited monotropic cholesteric phases. On the other hand, NHPCs with $DE{\geq}2.4$ and CNHPCs with $DEC{\leq}1.3$ showed monotropic nematic phases. NHPCs with $DE{\leq}l$, as well as HPC, formed right-handed helices whose optical pitches (${{\lambda}_m}'s$) increase with temperature, while all the CHPCs formed left-handed helices whose ${{\lambda}_m}'s$ decrease with temperature. In contrast with these derivatives, NHPCs with $1.4{\leq}DE{\leq}1.7$ and CNHPCs with $DEC{\geq}1.6$ did not display reflection colors over the full cholesteric range, suggesting that the helical twisting power of the cellulose chain and the cholesteryl group highly depends on the chemical structure and DE of mesogenic group.

• Polymer(Korea)
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• v.33 no.2
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• pp.144-152
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• 2009

The thermal and optical properties of poly {1-(cholesteryloxycarbonylalkanoyloxy) ethylene}s (PCALEn, n=2$\sim$8,10, the number of methylene units in the spacer) were investigated. All of the homologues formed monotropic cholesteric phases with left-handed helical structures. PCALEn with n=2 or 10, in constrast with PCALEn with $3{\leq}n{\leq}8$, did not display reflection colors over the full cholesteric range, suggesting that the helical twisting power of the cholesteryl group highly depends on the length of the spacer connecting the cholesteryl group to the polyethylene chain. The glass transition temperatures decreased with increasing n. The isotropic-cholesteric phase transition temperatures decreased with increasing n up to 7 and showed an odd-even effect. However it became almost constant when n is more than 7. This behavior is rationalized in terms of the change in the average shape of the side chain on varing the parity of the spacer. This rationalization also accounts for the observed variation of the entropy gain for the clearing transition. The thermal stability and degree of order in the mesophase and the temperature dependence of the optical pitch observed for PCALEn were significantly different from those reported for cellulose tri(cholesteryloxycarbonyl)alkanoates. The results were discussed in terms of the differences in the chemical structure and flexibility of main chain and the number of the mesogenic units per repeating unit.

• Applied Chemistry for Engineering
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• v.18 no.5
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• pp.475-482
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• 2007

The thermal and optical properties of glucose penta(cholesteryloxycarbonyl)alkanoates (CAGLn, n = 2~8, 10, the number of methylene units in the spacer) were investigated. All the CAGLn formed monotropic cholesteric phases with left-handed helical structures. CAGLn with n = 2 or 10, in contrast with CAGLn with $3{\leq}n{\leq}8$, did not display reflection colors over the full cholesteric range, suggesting that the helical twisting power of the cholesteryl group highly depends on the length of the spacer joining the cholesteryl group to the glucose chain. The isotropic-cholesteric transition point ($T_{ic}$) decreased with increasing n and showed no odd-even effect. The plot of transition entropy at $T_{ic}$ against n had a sharp negative inflection at n = 7. The optical pitches (${{\lambda}_m}^{\prime}$ s) of CAGLn with $3{\leq}n{\leq}8$ decreased with increasing temperature. However, the temperature dependence of the ${\lambda}_m$ of the derivatives exhibited pronounced dependence on n. The transitional properties and the temperature dependence of the ${\lambda}_m$ observed for CAGLn were discussed in terms of the differences in arrangement of the cholesteryl groups and the conformation of the molecules.

• Polymer(Korea)
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• v.32 no.3
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• pp.230-238
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• 2008

The thermal and optical properties of cellobiose octa(cholestryloxycarbonyl)alkanoates CCCBn, $n=2{\sim}8$,10, the number of methylene units in the spacer) were investigated. All the samples formed monotropic cholesteric phases with left-handed helical structures. CCBn with n=2 or 10, in contrast with CCBn with $3{\leq}n{\leq}8$, did not display reflection colors over the full cholesteric range, suggesting that the helical twisting power of the cholesteryl group highly depends on the length of the spacer connecting the cholesteryl group to the cellobiose chain. The isotropic-cholestropic transition ($T_{ic}$) and glass transition temperatures decreased with increasing n and showed no odd-even effect. The transition entropy at $T_{ic}$ increased with increasing n from 2 up 6, but at n=7 it drops significantly and then increased again with increasing n from 8 to 10. The sharp change at n=7 may be attributed to a difference in arrangement of the side groups. The thermal stability and degree of order in the mesophase and the temperature dependence of the optical pitch observed for CCBn were significantly different from those reported for the cellulose tri(cholesteryloxycarbonyl)alkanoates and glucose penta(cholesteryloxycarbonyl)alkanoates. The results were discussed in terms of the differences in the degree of polymerization, the number of the mesogenic units per mole-glucose unit, and the conformation of the molecules.