離子刺激應答低分子量醣脂質凝膠因子的開發研究

Studies on the Development of the Ionic Stimulus Responsive Low-Molecular-Mass Glycolipid-Based Gelators

蔡政哲(Cheng-Che Tsai)

指導教授 ： 蔡祐輔

中原大學/理學院/化學研究所/碩士(2010年)

https://doi.org/10.6840/cycu201000689

摘要

低分子量凝膠因子可以藉由分子間的吸引力自組裝形成三維網狀結構，使溶液轉變成膠體。在凝膠分子上引進具應答性質官能基並且使用外界刺激可以控制凝膠溶液-相轉換，使應用性大幅提升。
本論文合成醣體組成不同、碳鏈長度及組成不同的低分子量醣脂質凝膠因子CCT-1～CCT-6及CCT-1a～CCT-6a，探討陰離子、陽離子對此些化合物凝膠化的影響，發展新類型的離子應答低分子量醣酯質凝膠因子。
合成化合物CCT-5a、CCT-6a所需要的β羥基羧酸建構單元體，本實驗室以掌性池塘策略開拓出一條新的合成路徑，只需六步即可合成不同碳鏈長度的β羥基羧酸化合物M-7a、M-8a。
凝膠測試中，化合物CCT-5a可在純水中形成凝膠；化合物CCT-2、CCT-2a、CCT-3、CCT-3a、CCT-5、CCT-5a、CCT-6可在水與醇類的混合溶液中形成凝膠，其中CCT-2、CCT-2a為超級凝膠(最小凝膠濃度 = 1.6 mM)；化合物CCT-2、CCT-2a、CCT-3、CCT-3a除了在水與醇類混合溶液中之外，也可在有機溶液中形成凝膠。
凝膠的型態學可藉由掃描式電子顯微鏡觀察，在水、水與醇類混合溶液形成的結構為纖維狀；在有機溶液中形成的結構為不規則顆粒狀；微觀下的分子間作用力，可藉由氫核磁共振光譜不同濃度下化學位移的變化，證明形成凝膠時分子間作用力，如：氫鍵、π-π堆積的存在。
陰離子刺激測試中，化合物CCT-2a在有機溶劑中可回應氟離子刺激，狀態會由凝膠轉變成沉澱。由氫核磁共振光譜化學位移的變化，可以證實氟離子與β羥基醯胺官能基的羥基氫原子產生氫鍵。
陽離子刺激測試中，化合物CCT-2a在水/醇類溶液中可以回應銅離子刺激，狀態由凝膠轉變成溶液；化合物上碳鏈數目較長及醣體上的羥基官能基則會降低其回應效果。

關鍵字

離子刺激應答 ； 水凝膠 ； 凝膠因子

並列摘要

Low-molecular-mass gelators can self-assemble to form three dimensional network resulting to the change the state from solution to gel. After introducing the responsible functional group on the gelators’ structure and addition of external stimuli, the gel-solution phase transition was controlled to improve the gelators’ application.
In this thesis, we synthesized CCT-1~ CCT-6 and CCT-1a ~ CCT6a with various sugar substitutions; different alkyl chain length with its functional group to determine the influence of the anions and cations on the gelation process. The latter would be of use for the development of new types of ionic responsive gelators.
β hydroxyl carboxylic acid was used as building block for the synthesis of compounds CCT-5a、CCT-6a. Our laboratory explored a new synthetic route that used chiral pool stratagem resulting to the formation of respective β hydroxyl carboxylic compound with different alkyl chains that required only six steps.
In gelation test, compound CCT-5a formed gel in pure water; compounds CCT-2、CCT-2a、CCT-3、CCT-3a、CCT-5、CCT-5a、CCT-6 formed gel in water and alcohol mixture, CCT-2、CCT-2a are supergelators (minimum gelation concentration = 1.6 mM); aside from water and alcohol mixture compounds CCT-2、CCT-2a、CCT-3、CCT-3a also formed gel in organic solvent.
Morphology of the gel was observed by electron microscopy. Photomicrographs revealed that the compounds forming gels in both water and water-alcohol mixture appeared as fibers while compounds forming gels in organics were seen as irregularly shaped granules. Based from Nuclear Magnetic Resonance Spectroscopic spectra, the intermolecular interactions such as H-bonding and π-π stacking were seen from the shifting of the peaks.
In anion response test, the CCT-2a in organic solvent formed precipitation suggesting its ability for change of state from gel to a precipitate. The NMR spectra proved that there is intermolecular H-bonding established between fluoride atom and the hydrogen attached to the hydroxyl group in the β hydroxy amide compound.
In cation response test, the CCT-2a in water/alcohol solvent formed precipitation suggesting its ability for change of state from gel to a precipitate. Longer alkyl and hydroxyl group attached to the compounds resulting to reduce responsive ability.

並列關鍵字

hydrogel ； gelators ； ionic stimulus responsive

參考文獻

6. (a) Joerg C. Tiller. Angew. Chem. Int. Ed. 2003, 42, 3072. (b) Jun Li; George John. J. Am. Chem. Soc. 2006, 128, 8932

7. Haering, G.; Luisi, P. L. J. Phys. Chem. 1986, 90, 5892.

8. (a) Estroff, L. A.; Hamilton, A. D. Chem. Rev. 2004, 104, 1201. (b) Tiller, J. C. Angew. Chem., Int. Ed. 2003, 42, 3072.

12. Kiyonaka, S.; Sugiyasu, K.; Shinkai, S.; Hamachi, I. J. Am. Chem. Soc. 2002, 124, 10954.

29. Kawano, S. I.; Fujita, N.; Shinkai, S. J. Am. Chem. Soc. 2004, 126, 8592