Piculell L, Rochas C
Physical Chemistry 1, University of Lund, Chemical Center, Sweden.
Carbohydr Res. 1990 Dec 15;208:127-38. doi: 10.1016/0008-6215(90)80092-h.
The temperature dependences of the transverse (R2) and longitudinal (R1) n.m.r. relaxation rates of 87Rb+ in aqueous 5% iota-carrageenan have been compared with similar data for a sample purified by treatment with kappa-carrageenase. In each sample, the relaxation rates were sensitive to the conformation (helix or random coil). In the intact sample, the small (less than or equal to 5%) fraction of kappa-carrageenan (which, in its helical state, specifically binds rubidium ions) was solely responsible for the pronounced line-broadening that has been observed hitherto for 87Rb in iota-carrageenan gels. In the purified sample, the effects on the relaxation of 87Rb induced by iota-carrageenan are similar to those found in comparable systems in the absence of site-binding of the ions. Thus, there was a modest enhancement of the relaxation with R1 approximately R2 for the flexible coil conformation and a comparably larger effect, with significant contributions from dynamic processes on the time-scale of the inverse resonance frequency or longer, for the thicker, more highly charged and rigid helix conformation of iota-carrageenan.
已将87Rb+在5%ι-角叉菜胶水溶液中的横向(R2)和纵向(R1)核磁共振弛豫率的温度依赖性与经κ-角叉菜胶酶处理纯化后的样品的类似数据进行了比较。在每个样品中,弛豫率对构象(螺旋或无规卷曲)敏感。在完整样品中,κ-角叉菜胶(处于螺旋状态时能特异性结合铷离子)的小部分(小于或等于5%)是迄今在ι-角叉菜胶凝胶中观察到的87Rb明显谱线展宽的唯一原因。在纯化样品中,ι-角叉菜胶对87Rb弛豫的影响与在不存在离子位点结合的可比体系中发现的影响相似。因此,对于柔性卷曲构象,弛豫有适度增强,R1约等于R2;而对于ι-角叉菜胶更厚、电荷更高且更刚性的螺旋构象,弛豫有相对更大的影响,且在逆共振频率或更长时间尺度上的动态过程有显著贡献。