Polymer(Korea), Vol.21, No.4, 539-548, July, 1997
정렬된 iota-와 kappa-Corrageenan 사슬의 X-ray 회절과 분자구조의 상변화와의 연관성
X-lay Diffraction Patterns from Oriented Samples of iota-and kappa-Carrageenans and Implications for Conformational Transition
초록
정확히 180°위상차를 갖는 이중나선 구조로부터의 변화 또는 이중나선 구조의 각사슬의 부동한 구조변환을 보여주는 새로운 X-ray 회절모양을 관찰하였다. Iota- carrageenan 용액속에 Nal 함유량을 증가시킴에 따라 새로 출현된 첫번째와 다섯번째 layer line의 모양은 더욱 선명해졌으나 여섯번채 layer llne의 모양은 점점 약화되어졌다. 또 X-ray 회절 모양에 의하면 Cl-와 Br-이온의 역활도 용액속에서 I-이온이 iota-carrageenan에 주는 역할과 같음을 보여 주었다. 이러한 관계는 분자구조의 변환이 용액속에서 counteranion과 countercation의 수용해 에너지의 차이에 의존함을 보여주는 듯하다. 더우기 섬유상태를 유지한 상태에서 투입확산과 추출확산 방법을 적용하여 분자구조의 가역적 변화를 X-ray 회절실험을 통해 관찰할 수 있었다. 가역적 구조변화의 출현은 iota-carrageenan의 분자구조가 이중나선 구조임을 보여주는 좋은 증거가 된다. 이러한 결과들을 통해 iota-carrageenan 분자구조의 상변화는 나선 수준에서 유연성 사슬로부터 견고성 사슬구조로의 변화임을 유추할 수 있으며, gelation은 side-by-side stacking임을 시사해 주고 있다.
New additional X-ray diffraction layers were observed from KI induced iota-carrageenan, being interpreted:1) as a screw displacement from exact half-staggered double-helix. 2) as a difference between the two chains resulting conformational perturbation. As Nal wt. ratio in iota-carrageenan solution increases, the 1st and the 5st layer line get stronger, but the 6th layer line becomes weaker According to X-ray diffraction observation, Cl- or Br- ions with a counterpart metallic cation in aqueous solution give almost the same result as I- ions. It seems that the structural changes depend on the relative difference of hydration energy between counteranions and countercations in solution. Upon the addition of NaI and Ki In fiber state reversible change was detected by X-ray diffraction with performing diffusion-in and-out techniques. Reversible conformation change supports a double-helix model for iota-carrageenans. Therefore, the structural changes of 2iota-carrageenan implicate to a conformational transition from a flexible molecule to a stiff molecule showing no topological constraint and gelation can be conside red in helical level by side-by-side stacking.
Keywords:X-ray diffraction;double-helix;conformational transition;diffusion techniques;relative hydration;gelation
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