Department of Pharmacy, Faculty of Health and Medical Sciences, University of Copenhagen, Copenhagen, Denmark.
Langmuir. 2012 Jul 3;28(26):10105-19. doi: 10.1021/la3019716. Epub 2012 Jun 22.
In recent years, there has been a surge of interest in exploring the effect of trans-fatty acids (TFAs) on biological membrane properties. The research studies are motivated by an increasing body of evidence suggesting that the consumption of TFAs increases the risk of developing negative health effects such as coronary heart disease and cancer. The ultimate goal of studying the lipid-fatty acid interactions at the molecular level is to predict the biological role of fatty acids in cells. In this regard, it is interesting to elucidate the effect of loading TFAs and their counterpart cis-fatty acids (CFAs) on the physical properties of lipid model membranes. Here, the present study focuses on discussing the following: (1) the effect of mixing monoelaidin (ME, TFA-containing lipid) with its counterpart monoolein (MO, CFA-containing lipid) on modulating the fully hydrated self-assembled structure, and (2) the influence of solubilizing oleic acid (OA) and its trans counterpart elaidic acid (EA) on the fully hydrated ME system. The ME model membrane was selected due to its sensitivity to variations in lipid composition and temperature. Synchrotron small-angle X-ray scattering (SAXS) was applied for studying the temperature-dependent structural behavior of the fully hydrated ME/MO-based system prepared with an equal ME/MO weight ratio and also for characterizing the fully hydrated OA- and EA-loaded ME systems. Wide-angle X-ray (WAXS) experiments were also performed for characterizing the formed crystalline lamellar phases at ambient temperatures. The results demonstrate the significant influence of the partial replacement of ME by MO on the phase behavior. The addition of MO induces the lamellar-nonlamellar phase transitions at ambient temperatures and promotes the formation of the inverted type hexagonal (H(2)) phase above 72 °C. The fully hydrated ME/EA and ME/OA systems with their rich polymorphism exhibit an interesting temperature-dependent complex behavior. The experimental findings show that the temperature-induced phase transitions are dictated by the solubilized fatty acid concentration and its configuration. Both EA and OA have a significant impact on the fully hydrated ME system. Similar to previous published studies, OA induces a significantly stronger mean negative membrane curvature as compared to EA. The two phase diagrams are discussed in terms of water-lipid and lipid-fatty acid interactions, membrane bending, and lipid packing concepts. A newly observed interesting epitaxial relationship for the lamellar-hexagonal phase transition in the EA-loaded ME system is illustrated and discussed in detail.
近年来,人们对研究反式脂肪酸(TFAs)对生物膜性质的影响产生了浓厚的兴趣。研究的动机是越来越多的证据表明,TFAs 的摄入会增加患心脏病和癌症等负面健康影响的风险。在分子水平上研究脂质-脂肪酸相互作用的最终目标是预测脂肪酸在细胞中的生物学作用。在这方面,阐明加载 TFAs 和它们的顺式脂肪酸(CFAs)对脂质模型膜物理性质的影响是很有趣的。在这里,本研究集中讨论以下两个方面:(1)混合单油酰基-2-甘油(ME,含 TFA 的脂质)与其对应物单油酸基-2-甘油(MO,含 CFA 的脂质)对调节完全水合自组装结构的影响,以及(2)溶解油酸(OA)及其反式对应物亚油酸(EA)对完全水合 ME 系统的影响。选择 ME 模型膜是因为它对脂质组成和温度的变化敏感。同步加速器小角 X 射线散射(SAXS)用于研究具有相等 ME/MO 重量比的完全水合 ME/MO 基系统的温度依赖性结构行为,也用于表征完全水合的 OA 和 EA 加载 ME 系统。广角 X 射线(WAXS)实验也用于在环境温度下表征形成的结晶层状相。结果表明,部分用 MO 替代 ME 对相行为有显著影响。MO 的添加会在环境温度下诱导层状-非层状相变,并在 72°C 以上促进反式六方(H(2))相的形成。具有丰富多态性的完全水合 ME/EA 和 ME/OA 系统表现出有趣的温度相关复杂行为。实验结果表明,温度诱导的相转变受溶解脂肪酸浓度及其构型的控制。EA 和 OA 对完全水合 ME 系统都有重大影响。与之前发表的研究类似,OA 比 EA 诱导出显著更强的平均负膜曲率。这两个相图是根据水-脂质和脂质-脂肪酸相互作用、膜弯曲和脂质堆积概念来讨论的。详细说明了和讨论了在 EA 加载 ME 系统中观察到的有趣的层状-六方相转变的新的外延关系。