Max-Planck Institute of Colloids and Interfaces, D-14424 Potsdam/Golm, Germany.
Langmuir. 2016 Jul 26;32(29):7316-25. doi: 10.1021/acs.langmuir.6b01379. Epub 2016 Jul 14.
1-Monopalmitoyl-rac-glycerol is omnipresent in numerous biological and applied systems. Systematic GIXD measurements of 1-monopalmitoyl-rac-glycerol monolayers are carried out over a large pressure interval at 5, 10, and 15 °C to construct the phase diagram on the basis of reliable 2D lattice structures. These studies are complemented by other monolayer characteristics, such as π-A isotherms and mesoscopic domain topographies. A phase transition is found between the two orthorhombic structures with NN and NNN tilted alkyl chains at low temperatures (5 and 10 °C). It increases linearly with increasing temperature. With a further increase in temperature to 15 °C, only NN-tilted orthorhombic lattices are observed in the whole pressure region. The cross-sectional area, A0, is less affected by surface pressure and temperature and amounts to values of between 19.7 and 19.8 Å(2), as expected for a rotator phase at the lower limit. The tilt angle t with respect to the surface normal decreases with increasing pressure and is only slightly influenced by the temperature. The transition pressure to untilted alkyl chains, as determined by the extrapolation of 1/cos(t) to zero tilt angle, is >50 mN/m for all temperatures. The results of lattice distortion d versus sin 2(t) suggest for 10 and 15 °C the tilt of the aliphatic chains as the reason for the monolayer lattice distortion whereas at 5 °C the nonzero-tilt-angle intercept d0 could be an indication of the prevention of hexagonal packing. The generic π-T phase diagram of racemic monoacylglycerol monolayers is constructed on the basis of the phase diagrams of 1-monopalmitoyl-rac-glycerol and 1-monostearoyl-rac-glycerol, which shows that for 1-monopalmitoyl-rac-glycerol monolayers the oblique phase can occur only close to and below 0 °C. The possible phase behavior of other racemic monoacylglycerol monolayers with alkyl chain lengths of C14 and C20 is discussed on the basis of the generic phase diagram.
1-单棕榈酸甘油酯在众多生物和应用系统中无处不在。在 5、10 和 15°C 的较大压力间隔内对 1-单棕榈酸甘油酯单层进行系统的 GIXD 测量,以基于可靠的二维晶格结构构建相图。这些研究还补充了其他单层特性,例如π-A 等温线和介观畴形貌。在低温(5 和 10°C)下,发现两种正交结构之间存在相转变,其中 NN 和 NNN 倾斜的烷基链。它随温度线性增加。随着温度进一步升高到 15°C,在整个压力区域仅观察到 NN 倾斜的正交晶格。横截面面积 A0 受表面压力和温度的影响较小,在 19.7 和 19.8 Å(2)之间,这是下限旋转相的预期值。相对于表面法线的倾斜角 t 随压力的增加而减小,并且仅受温度的轻微影响。通过将 1/cos(t) 外推到零倾斜角来确定无倾斜烷基链的转变压力,对于所有温度,该压力均>50 mN/m。晶格畸变 d 与 sin 2(t) 的关系的结果表明,对于 10 和 15°C,脂肪链的倾斜是单层晶格畸变的原因,而对于 5°C,非零倾斜角截距 d0 可能表明阻止了六边形堆积。基于 1-单棕榈酸甘油酯和 1-单硬脂酸甘油酯的相图构建了外消旋单酰基甘油单分子层的通用π-T 相图,表明对于 1-单棕榈酸甘油酯单分子层,斜相只能在接近和低于 0°C 时发生。基于通用相图,讨论了具有 C14 和 C20 烷基链长的其他外消旋单酰基甘油单分子层的可能相行为。