Investigation on the artificial exchange signals induced by the RIDER effect in CODEX experiments

The CODEX (center-band only detection of exchange) NMR experiment is widely used for the detection of slow motions in organic solids, especially polymers. However, the RIDER (relaxation-induced dipolar exchange with recoupling) effect may result in artificial exchange signals in the CODEX pure exchange spectrum, which greatly limits the application of CODEX method. Herein, we investigate the distance range that the RIDER effect can reach by performing CODEX experiments on two typical organic solids, hexadecyltrimethylammonium bromide (CTAB) and semi-crystalline polyamide-6 (PA6) where there are no slow molecular motions at room temperature. Our experimental results demonstrate that generally two-bond distance is far enough to ignore the RIDER effect resulted from the dipolar interactions between (13)C and the fast relaxing heteronucleus (14)N. From the built-up curve of RIDER signals as a function of recoupling time and mixing time, it is clearly revealed that the RIDER effect can greatly affect the signal from (13)C directly bonded with (14)N. However, this RIDER effect accounts less than 3% of the reference intensity for signals from (13)C not directly bonded with (14)N if typical recoupling (~0.5 ms) and mixing times (~0.5 s) are used for the investigation of slow motions. When longer recoupling and mixing time are used, there are small RIDER signals even for the (13)C far away from the (14)N. These signals, to a large degree, result from the spin diffusion effect and/or the special microscopic molecule arrangement. However, they are so small compared to the reference signal (~5%) that they can be ignored. Finally, according to the simulation results, it is worth noting that the RIDER signal is still generally negligible compared to the signals due to slow motions if the chemical shift anisotropy reorientation during the mixing time is not too small(larger than 20°) under the condition of 4t(r) recoupling time at the magic-angle-spinning speed of 6.5 kHz.