• Thermotropic Liquid Crystalline Properties of (8-Cholesteryloxycarbonyl)heptanoated Polysaccharides
  • Jeong SY, Ma YD
  • (8-콜레스테릴옥시카보닐)헵타노화 다당류들의 열방성 액정 특성
  • 정승용, 마영대
Abstract
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(λm,s) decrease with increasing temperature. Amylopectin derivative also formed a monotropic cholesteric phase with left-handed 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 λm at the same temperature, and the temperature dependence of the λm 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.

셀룰로오스, 아밀로오스, 키토산, 키틴, 알긴산, 풀루란 또는 아밀로펙틴을 (8-콜레스테릴옥시카보닐)헵타노일 클로라이드(CH8C)와 반응시켜 전치환 또는 거의 전치환 (8-콜레스테릴옥시카보닐)헵타노화 다당류 유도체들을 합성함과 동시에 이들의 열방성 액정의 거동들을 검토하였다. CH8C의 경우와 같이, 아밀로펙틴 유도체를 제외한 모든 다당류 유도체들은 좌측방향의 나선구조를 지니며 온도상승에 의해 광학피치들(λm,s)이 감소하는 단방성 콜레스테릭 상들을 형성하였다. 아밀로펙틴 유도체도 좌측방향의 나선구조를 지닌 단방성 콜레스테릭 상을 형성하나 다른 다당류 유도체들과 달리 콜레스테릭 상의 전 범위에서 반사색깔들을 나타내지 않았다. 이러한 사실은 콜레스테릴 그룹에 의한 나선의 비틀림력은 아밀로펙틴 중의 분기구조에 민감하게 의존함을 시사한다. 다당류 유도체들에서 관찰되는 액정 상의 열적 안정성과 질서도, 동일한 온도에서의 λm의 크기 그리고 λm의 온도 의존성은 콜레스테릴 그룹들을 유연한 스페이서들을 통하여 유연한 혹은 반강직한 골격들에 도입시켜 얻은 고분자들에 대해 보고된 결과와 전혀 다르다. 이들의 결과를 주사슬과 곁사슬의 화학구조 그리고 주사슬의 유연성의 차이와 관련하에서 검토하였다.

Keywords: polysaccharides; cholesterol; combined-type liquid crystalline; optical pitch; helicoidal sense

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This Article

  • 2006; 30(4): 338-349

    Published online Jul 25, 2006

  • Received on May 2, 2006
  • Accepted on Jun 20, 2006