Generation of Biomembrane Functions in Organic Solvents and Its Application

合成了L-谷氨酸衍生的脂质，研究了其在有机溶剂中的聚集结构，并讨论了聚集的驱动力。a）由L-谷氨酸衍生的含三酰胺的脂质通过酰胺部分之间的氢键相互作用形成脂质聚集体，从而形成有机凝胶。这种凝胶化在各种有机溶液如甲醇、乙醇、苯、四氢呋喃、甲苯和环己烷中形成。B）TEM观察表明，从透明凝胶冷冻干燥后的干凝胶由微纤维聚集体网络构成。但在低浓度（溶胶状态）下没有观察到类似的网络，而可检测到碎片微纤维。实验证实了临界凝胶化（cgc）与有机溶剂的种类有关。例如，在室温下，在苯中cgc在1和0.1 mM之间。然而，SEM和TEM观察表明，在较低浓度下， ...更多信息 离子例如0.01mM。这表明cgc与临界聚集浓度（cac）并不一致。因此，凝胶形成归因于纤维聚集体的发展和随后的聚集体网络的形成。c）为了估计cac和聚集体结构，我们合成了具有芘基头部基团的新脂质。通过荧光发射光谱分析表明，脂质体在cac以上的浓度下产生准分子。d）合成了含三酰胺基的L-谷氨酸脂质体，该脂质体具有四烷基基团和原卟啉IX-头基。在苯、环己烷等有机溶剂中，脂质形成高度取向的纤维状聚集体，紫外-可见光谱显示形成了Soret带，该带由红移现象估计，但加入三氟乙酸（TFA）后，这些吸收带消失，从而提供了与单体分散态相对应的光谱。CD谱表明，聚集体诱导了正的Cotton效应，但TFA的加入降低了椭圆度。这些结果表明，氢键的工作作为一个驱动力的聚集和共面堆积的卟啉平面结构将包括。少

L-glutamic acid-derived lipids were synthesized in order to study the aggregation structures in organic solvents and discussed the driving force for aggregation.a) Triamide-containing lipids derived from L-glutamic acid produced organic gels through formation of lipid aggregation by hydrogen bonding interaction among the amide moieties. This gelation was formed in various organic solution such as methanol, ethanol, benzene, tetrahydrofuran, toluene and cyclohexane.b) TEM observation showed that the xerogel after freeze-dried from the clear gel was constructed from a network of microfibrous aggregates. But no similar network was observed at the low concentration (in the sol state) while fragmental microfibers were detectable. It was confirmed that critical gelation (cgc) depended on the kind of organic solvents. For example, the cgc lies between 1 and 0.1 mM at room temperature in benzene. However, SEM and TEM observations showed that fibrous aggregates were produced at lower concentrat … More ion such as 0.01 mM than cgc. This shows that the cgc doesn't agree with the critical aggregation concentration (cac). Therefore, the gel formation is attributed to the development of fibrous aggregates and subsequent formation of an aggregate network.c) To estimate cac and the aggregation structure, we synthesized new lipids having pyrenyl head group. By fluorescence emission spectra showed that the lipids produced excimers at the concentration above cac.d) We synthesized triamide-containing L-glutamic acid lipid with tetraalkyl groups and a protoporphyrin IX-head group. The lipid produced highly-oriented fibrous aggregates in organic solution such as benzene, cyclohexane and so on. UV-vis spectra indicated formation of a Soret band which was estimated by red shift phenomena, but these were lost by addition of trifuluoroacetic acid (TFA ) to provide spectra corresponding to those in monomeric dispersion states. CD spectra showed that the aggregates induced positive Cotton effect but addition of TFA reduced the elipticity. These results indicate that hydrogen bonding work as a driving force for aggregation and the cofacial packed-porphyrin planar structure will be included. Less