Cardon Thomas B, Dave Paresh C, Lorigan Gary A
Department of Chemistry and Biochemistry, Miami University, Oxford, Ohio 45056, USA.
Langmuir. 2005 May 10;21(10):4291-8. doi: 10.1021/la0473005.
The magnetic alignment behavior ofbicelles (magnetically alignable phospholipid bilayered membranes) as a function of the q ratio (1,2-dihexanoyl-sn-glycerol phosphatidylcholine/1,2-dimyristoyl-sn-glycerol phosphatidylcholine mole ratio) and temperature was studied by spin-labeled X-band electron paramagnetic resonance (EPR) spectroscopy and solid-state 2H and 31P NMR spectroscopy. Well-aligned bicelle samples were obtained at 45 degrees C for q ratios between 2.5 and 9.5 in both the EPR and NMR spectroscopic studies. The molecular order of the system, S(mol), increased as the q ratio increased and as the temperature decreased. For higher q ratios (> or = 5.5), bicelles maintained magnetic alignment when cooled below the main phase transition temperature (approximately 30 degrees C when in the presence of lanthanide cations), which is the first time, to our knowledge, that bicelles were magnetically aligned in the gel phase. For the 9.5 q ratio sample at 25 degrees C, S(mol) was calculated to be 0.83 (from 2H NMR spectra, utilizing the isotopic label perdeuterated 1,2-dimyristoyl-sn-glycerol phosphatidylcholine) and 0.911 (from EPR spectra utilizing the spin probe 3beta-doxyl-5alpha-cholestane). The molecular ordering of the high q ratio bicelles is comparable to literature values of S(mol) for both multilamellar vesicles and macroscopically aligned phospholipid bilayers on glass plates. The order parameter S(bicelle) revealed that the greatest degree of bicelle alignment was found at higher temperatures and larger q ratios (S(bicelle) = -0.92 for q ratio 8.5 at 50 degrees C).
通过自旋标记X波段电子顺磁共振(EPR)光谱以及固态2H和31P核磁共振(NMR)光谱,研究了双分子层(可磁排列的磷脂双层膜)的磁排列行为与q比值(1,2 - 二己酰 - sn - 甘油磷脂酰胆碱/1,2 - 二肉豆蔻酰 - sn - 甘油磷脂酰胆碱摩尔比)和温度之间的关系。在EPR和NMR光谱研究中,于45℃下获得了q比值在2.5至9.5之间排列良好的双分子层样品。系统的分子有序度S(mol) 随着q比值的增加和温度的降低而增大。对于较高的q比值(≥5.5),当冷却至低于主相变温度时(在镧系阳离子存在下约为30℃),双分子层保持磁排列,据我们所知,这是双分子层在凝胶相中实现磁排列的首次报道。对于25℃下q比值为9.5的样品,利用氘代标记的全氘代1,2 - 二肉豆蔻酰 - sn - 甘油磷脂酰胆碱从2H NMR光谱计算出S(mol) 为0.83,利用自旋探针3β - 氧基 - 5α - 胆甾烷从EPR光谱计算出S(mol) 为0.911。高q比值双分子层的分子有序度与多层层状囊泡以及玻璃板上宏观排列的磷脂双层膜的S(mol) 文献值相当。序参数S(bicelle) 表明,在较高温度和较大q比值下双分子层的排列程度最高(50℃下q比值为8.5时S(bicelle) = -0.92)。