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Monolayer behavior of pure F-DPPC and mixed films with DPPC studied by epifluorescence microscopy and infrared reflection absorption spectroscopy.
Chemistry and Physics of Lipids ( IF 3.4 ) Pub Date : 2020-05-15 , DOI: 10.1016/j.chemphyslip.2020.104918
Syed W H Shah 1 , Christian Schwieger 2 , Jörg Kressler 3 , Alfred Blume 3
Affiliation  

The monolayer behavior of a l-DPPC derivative with a single fluorination in one of its terminal methyl groups (F-DPPC) at air-water interface was investigated by epifluorescence microscopy and infrared reflection absorption spectroscopy (IRRAS). Epifluorescence microscopy was utilized to study the shape and morphology of liquid-condensed (LC) domains observed upon compression of the film. IRRAS was employed for the determination of chain order and orientation. The shapes of LC-domains in a monolayer of F-DPPC are more dependent on the rate of compression than those of DPPC. The LC domains of F-DPPC display pronounced fractal growth patterns depending on the compression speed. The evolution of LC domain occurs under dominating electrostatic dipolar forces in F-DPPC. IRRAS measurements with the analysis of the frequency of the methylene stretching vibrations as a function of film compression show that the acyl chains in an F-DPPC monolayer in the LE-phase are more disordered than those in a DPPC film. The reason for the higher chain disorder in LE phase F-DPPC monolayers is a back folding of the fluorinated sn-2 chain terminus towards the air-water interface leading to larger molecular area requirement. Angular dependent IRRA spectra of monolayers at a surface pressure of 30 mN m−1 show that in the LC phase DPPC and F-DPPC exhibit a similar tilt of the acyl chains of ca. 28−30 ° relative to the surface normal. F-DPPC is ideally miscible with l-DPPC-d62 having the same chirality, as indicated by epifluorescence images and by IRRAS. However, the LC domains in an equimolar mixture of d-DPPC and F-DPPC having opposite chirality show multi-lobed complex domain patterns indicating chiral phase separation within LC domains.



中文翻译:

通过表面荧光显微镜和红外反射吸收光谱研究了纯F-DPPC及其与DPPC混合膜的单层行为。

l-的单层行为通过表面荧光显微镜和红外反射吸收光谱法(IRRAS)研究了在空气-水界面的一个末端甲基之一(F-DPPC)中具有单一氟化的DPPC衍生物。利用落射荧光显微镜研究在压缩薄膜时观察到的液体冷凝(LC)域的形状和形态。IRRAS用于确定链的顺序和方向。与DPPC相比,F-DPPC单层中LC域的形状更依赖于压缩率。F-DPPC的LC域显示出明显的分形增长模式,具体取决于压缩速度。在F-DPPC中,主要的静电偶极力作用下会发生LC域的演变。IRRAS测量分析了亚甲基拉伸振动的频率与薄膜压缩的关系,结果表明,LE相中F-DPPC单层中的酰基链比DPPC薄膜中的酰基链更加无序。LE相F-DPPC单层中较高链紊乱的原因是氟化物向后折叠朝向空气-水界面的sn -2链末端导致更大的分子面积需求。在30 mN m -1的表面压力下,单分子膜的角度依赖性IRRA光谱表明,在LC相中,DPPC和F-DPPC的ca酰基链具有相似的倾斜度。相对于表面法线28–30°。F-DPPC在理想情况下可与具有相同手性的1 -DPPC -d 62混溶,如落射荧光图像和IRRAS所示。然而,具有相反手性的d -DPPC和F-DPPC的等摩尔混合物中的LC结构域显示出多叶的复杂结构域模式,表明LC结构域内的手性相分离。

更新日期:2020-05-15
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