Caffrey M, Hogan J, Mencke A
Department of Chemistry, Ohio State University, Columbus 43210-1173.
Biophys J. 1991 Aug;60(2):456-66. doi: 10.1016/S0006-3495(91)82072-0.
We present here the first study of the use of a pressure-jump to induce the ripple (P beta')/lamellar liquid crystal (L alpha) phase transition in fully hydrated 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC). The transition was monitored by using time-resolved x-ray diffraction (TRXRD). Applying a pressure-jump from atmospheric to 11.3 MPa (1640 psig, 111.6 atm) in 2.5 s induces the L alpha to P beta' phase transition which takes place in two stages. The lamellar repeat spacing initially increases from a value of 66.0 +/- 0.1 A (n = 4) to a maximum value of 70.3 +/- 0.8 A (n = 4) after 10 s and after a further 100-150 s decreases slightly to 68.5 +/- 0.3 A (n = 4). The reverse transition takes place following a pressure jump in 5.5 s from 11.3 MPa to atmospheric pressure. Again, the transition occurs in two stages with the repeat spacing steadily decreasing from an initial value of 68.5 +/- 0.3 A (n = 3) to a minimum value of 66.6 +/- 0.3 A (n = 3) after 50 s and then increasing by approximately 0.5 A over a period of 100 s. The transition temperature increases linearly with pressure up to 14.1 MPa in accordance with the Clapeyron relation, giving a dT/dP value of 0.285 degrees C/MPa (28.5 degrees C/kbar) and an associated volume change of 40 microliters/g. A dynamic compressibility of 0.13 +/- 0.01 A/MPa has been determined for the L alpha phase. This value is compared with the equilibrium compressibilities of bilayer and nonbilayer phases reported in the literature. The results suggest testable mechanisms for the pressure-induced transition involving changes in periodicity, phase hydration, chain order, and orientation. A more complete understanding of the transition mechanism will require improvement in detector spatial resolution and sensitivity, and data on the pressure sensitivity of phase hydration.
我们在此展示了对使用压力阶跃诱导完全水合的1,2 - 二肉豆蔻酰 - sn - 甘油 - 3 - 磷酸胆碱(DMPC)中波纹(Pβ')/层状液晶(Lα)相变的首次研究。通过时间分辨X射线衍射(TRXRD)监测该相变。在2.5秒内从大气压施加到11.3兆帕(1640磅力/平方英寸,111.6大气压)的压力阶跃会诱导Lα到Pβ'的相变,该相变分两个阶段发生。层状重复间距最初从66.0±0.1埃(n = 4)的值增加到10秒后70.3±0.8埃(n = 4)的最大值,再经过100 - 150秒后略微降至68.5±0.3埃(n = 4)。反向相变在5.5秒内从11.3兆帕压力阶跃到大气压时发生。同样,该相变分两个阶段,重复间距从初始值68.5±0.3埃(n = 3)稳步下降到50秒后66.6±0.3埃(n = 3)的最小值,然后在100秒内增加约0.5埃。根据克拉佩龙关系,相变温度随压力线性增加直至14.1兆帕,dT/dP值为0.285℃/兆帕(28.5℃/千巴),相关体积变化为40微升/克。已确定Lα相的动态压缩率为0.13±0.01埃/兆帕。将该值与文献中报道的双层和非双层相的平衡压缩率进行了比较。结果表明了压力诱导相变的可测试机制,涉及周期性、相水合、链序和取向的变化。对相变机制更全面的理解将需要提高探测器的空间分辨率和灵敏度,以及关于相水合压力敏感性的数据。