Morii Nahoko, Kido Giyuu, Suzuki Hiroyuki, Nimori Shigeki, Morii Hisayuki
Nanomaterials Laboratory, National Institute for Materials Science, Tsukuba, Ibaraki 305-0003, Japan.
Biomacromolecules. 2004 Nov-Dec;5(6):2297-307. doi: 10.1021/bm0496460.
DNA films showing highly homogeneous orientation of molecular chains were successfully prepared by drying a semidiluted solution in a horizontal magnetic field. Most of the molecular chain elements in the obtained film were found to be one-dimensionally oriented, as shown by X-ray diffraction, polarization microscopy, and linear dichroism spectroscopy. Because a DNA chain is theoretically expected to orientate only in divergent directions perpendicular to a magnetic field, this result suggests that the DNA chains were aligned not only by a magnetic field but also by the interfacial effect that induced the chains to fit along the air-liquid interface. The descent speed of an air-liquid interface by evaporation was faster than the estimated diffusion rate of DNA, suggesting an emergence of a concentrated layer near the surface. As proved by polarization microscopy, this emergence led to the transitional formation of a nematic-like liquid crystalline phase, which resulted in a DNA film with good chain alignment and unitary orientation. This mechanism underlying chain alignment was supported by molecular weight dependency, in which higher molecular weight DNA is more likely to evince chain alignment that exhibits a higher degree of birefringence. Low molecular weight components have such high thermal motility that it would be difficult to fit them along the air-liquid interface in the early stage of drying. For chain alignment, it was preferable to use an initial concentration of DNA lower than a critical concentration for liquid crystal formation so that the possible diffusion and assembly in a diluted solution would be essential for chain alignment. The DNA film exhibited obvious linear dichroism, indicating the potential for further applications.
通过在水平磁场中干燥半稀释溶液,成功制备出分子链具有高度均匀取向的DNA薄膜。如X射线衍射、偏光显微镜和线性二色光谱所示,所得薄膜中的大多数分子链元素呈一维取向。由于理论上预计DNA链仅在垂直于磁场的发散方向上取向,这一结果表明DNA链不仅通过磁场排列,还通过诱导链沿气液界面排列的界面效应排列。气液界面因蒸发而下降的速度比估计的DNA扩散速率快,这表明在表面附近出现了一个浓缩层。偏光显微镜证明,这种浓缩层的出现导致了向列型液晶相的过渡形成,从而得到具有良好链排列和单一取向的DNA薄膜。链排列的这一机制得到了分子量依赖性的支持,即较高分子量的DNA更有可能表现出具有更高双折射程度的链排列。低分子量组分具有如此高的热运动性,以至于在干燥初期很难使其沿气液界面排列。为了实现链排列,最好使用低于液晶形成临界浓度的DNA初始浓度,这样在稀释溶液中可能的扩散和组装对于链排列至关重要。该DNA薄膜表现出明显的线性二色性,表明其具有进一步应用的潜力。