Horwitz A F, Horsley W J, Klein M P
Proc Natl Acad Sci U S A. 1972 Mar;69(3):590-3. doi: 10.1073/pnas.69.3.590.
We have used Fourier transform nuclear magnetic resonance methods to measure the spin-lattice and transverse relaxation times at 220 MHz of the choline N-methyl and the fatty-acid alpha-carbonyl, allyl, vinyl, methylene, and methyl protons of sonicated egg-yolk lecithin. Over the temperature range investigated the T(1) values were, in general, similar to, but different from, one another, suggesting that the relaxation rates of all of the fatty-acid protons are not determined solely by spin-diffusion to a heat sink. Arrhenius plots of the T(1) data gave activation energies similar to those for the barriers to internal rotation in alkanes. The values of the transverse relaxation rate, T(2), showed a relatively large variation among the proton resonances; about 20% of the methylene protons had a T(2) of 56 msec, while the remaining protons relaxed according to a distribution of values all shorter than 20 msec. Such a distribution of relaxation times is envisioned to arise from a distribution of correlation times stemming from complex motions in which extended angular excursions of the fatty acid chain are coupled to trans-->gauche conformational transitions.
我们利用傅里叶变换核磁共振方法,在220兆赫下测量了超声处理过的蛋黄卵磷脂中胆碱N-甲基以及脂肪酸α-羰基、烯丙基、乙烯基、亚甲基和甲基质子的自旋晶格弛豫时间和横向弛豫时间。在所研究的温度范围内,T(1)值总体上彼此相似但又有所不同,这表明并非所有脂肪酸质子的弛豫速率都仅由向热沉的自旋扩散决定。T(1)数据的阿累尼乌斯图给出的活化能与烷烃内旋转势垒的活化能相似。横向弛豫速率T(2)的值在质子共振之间显示出相对较大的变化;约20%的亚甲基质子的T(2)为56毫秒,而其余质子则根据均短于20毫秒的值的分布进行弛豫。这种弛豫时间分布被设想为由脂肪酸链的扩展角偏移与反式→顺式构象转变相耦合的复杂运动所产生的相关时间分布引起。