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反胶束中间体以及层状、立方相和反六角相亲水相之间的转变。III. 通过Lα相和HII相之间转变过程中的中间体形成各向同性和反立方相状态

Inverted micellar intermediates and the transitions between lamellar, cubic, and inverted hexagonal amphiphile phases. III. Isotropic and inverted cubic state formation via intermediates in transitions between L alpha and HII phases.

作者信息

Siegel D P

出版信息

Chem Phys Lipids. 1986 Dec 31;42(4):279-301. doi: 10.1016/0009-3084(86)90087-3.

Abstract

Inverted cubic and isotropic phases have been observed in phospholipid and glycolipid systems. These phases exhibit characteristic morphologies in freeze-fracture electron micrographs, isotropic 31P-NMR resonances and (in some cases) cubic X-ray diffraction patterns. It is proposed here that these phases may form from the same intermediates that are involved in lamellar/inverted hexagonal (L alpha/HII) phase transitions, and that it is possible that these cubic and isotropic phases are metastable. According to a kinetic theory of L alpha/HII phase transitions, intermediates in such transitions can form structures known as interlamellar attachments (ILAs). It is shown that ILAs should form in large numbers during L alpha/HII transitions in systems like those reported to form inverted cubic or isotropic structures. ILAs cannot readily assemble into either the HII phase or well-ordered arrays of L alpha phase bilayers, and represent a kinetic trap for intermediates in L alpha/HII transitions (although it is possible that they are marginally more stable in a thermodynamic sense than the L alpha phase in a small temperature range below TH). It is also shown that arrays of ILAs should form metastable arrays with the same morphology and isotropic 31P-NMR resonances that are observed in isotropic and inverted cubic states. In particular, under some circumstances ILAs will assemble into a structure identical to the bicontinuous inverted cubic phase previously described in monoglycerides and very similar in morphology to structures observed in phospholipid systems. Finally, since isotropic and cubic states form from ILAs, which also can mediate fusion of unilamellar vesicles, unilamellar vesicles should fuse to at least some extent under the same conditions in which multilamellar samples of the same lipid form isotropic or inverted cubic states. This correlation has been observed.

摘要

在磷脂和糖脂体系中已观察到反立方相和各向同性相。这些相在冷冻断裂电子显微镜图像、各向同性的³¹P - NMR共振以及(某些情况下)立方X射线衍射图谱中呈现出特征形态。本文提出,这些相可能由参与层状/反六角(Lα/HII)相转变的相同中间体形成,并且这些立方相和各向同性相有可能是亚稳态的。根据Lα/HII相转变的动力学理论,此类转变中的中间体可形成称为层间附着(ILA)的结构。结果表明,在据报道能形成反立方或各向同性结构的体系中,Lα/HII转变过程中应大量形成ILA。ILA不易组装成HII相或Lα相双层的有序阵列,并且代表了Lα/HII转变中间体的动力学陷阱(尽管在低于TH的小温度范围内,从热力学意义上讲它们可能比Lα相略微更稳定)。还表明,ILA阵列应形成具有与在各向同性和反立方状态中观察到的相同形态和各向同性³¹P - NMR共振的亚稳态阵列。特别是,在某些情况下,ILA将组装成与单甘油酯中先前描述的双连续反立方相相同的结构,并且形态与磷脂体系中观察到的结构非常相似。最后,由于各向同性和立方状态由ILA形成,而ILA也可介导单层囊泡的融合,在相同脂质的多层样品形成各向同性或反立方状态的相同条件下,单层囊泡应至少在一定程度上融合。这种相关性已被观察到。

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