液体核磁共振中由分子间偶极耦合和分子内标量耦合共同作用后的谱图裂分模式

在高极化多自旋液体样品中,同时存在着分子间偶极（D）耦合和分子内标量（J）耦合,它们的共同作用产生了一些原来观测不到的分子间多量子相干信号。而且,信号的裂分模式与只存在J耦合的多自旋体系中观测到的多量子相干信号的裂分模式不同。本文从理论和实验上研究了这些禁阻的共振峰及其独特的裂分模式。为了比较验证,我们以I2S3+X自旋体系为例,结合使用选择和非选择性的射频脉冲序列来获得分子间双量子相干信号的五种裂分模式。进而归纳出对IpSq+Xk (p, q, k = 1, 2, 3,…)自旋体系普适的裂分模式规则。并指出,它们中如(1:0:-1)的裂分模式会放大J耦合裂分,使得J耦合常数的测量更精确,特别在J耦合常数很小或不均匀场中的J耦合常数的测量中具有诱人的应用前景。结果表明理论预测,计算机模拟和实验观测结果三者吻合的很好。     

DIRECT MEASUREMENT OF TRANSVERSE RELAXATION TIME OF INTERMOLECULAR MULTIPLE QUANTUM COHERENCES IN NMR

A one-dimensional NMR method is presented for measuring the transverse relaxation time, T_2,n, of intermolecular multiple quantum coherences (IMQCs) of coherence order n in highly polarized spin systems. The pulse sequence proposed in this paper effectively suppresses the effects of radiation damping, molecular diffusion, inhomogeneity of magnetic field, and variations of dipolar correlation distance, all of which may affect quantitation of T_2,n. This pulse sequence can be used to measure not only IMQC transverse relaxation time T_2,n(n>1) quickly and directly, but also the conventional transverse relaxation time. Experimental results demonstrate that the quantitative relationship between T_2,n(n≥1) and T₂ is T_2,n≈T₂/n. These results will be helpful for understanding the fundamental properties and mechanisms of IMQCs.