In this respect, we note in Fig 10 that the curve at 53°53° is s

In this respect, we note in Fig. 10 that the curve at 53°53° is shallower than that at 71°71°, which is nicely reproduced in the simulations. Indeed, it is well known selleck that interactions with different strengths gives different T2T2 minima

as a function o temperature [49]. Based on that, a hypothesis that explain such unusual behavior is that the two components of the local field can lead to different T2T2 minima at different temperatures. Despite not seen in our constant-time experiments [33], there is a T2-relatedT2-related loss of the overall signal, which may changes the relative weighting of the two components at higher temperature producing the observed effect. Another feature that can be noted in Fig. 10 is that at lower motional rates (at the

lowest temperatures) the curves obtained by spin dynamics simulations have a flatter bottom around t1=tr/2t1=tr/2 than the ones calculated with the AW approach. This highlights the generic limit of the AW approximation already discussed before, when the coupling is too strong and/or Doramapimod the MAS rates is too slow. Even in this situation, by proper scaling of the second moments we find good agreement between the rates calculated using the full treatment and the AW approximation. Note that data at t1,max=trt1,max=tr corresponds again to short times, as one observes the “back“ of the rotor echo, i.e., the AW approximation remains valid

at the edges of the modulation Selleck Rucaparib interval. Unfortunately, information about the specific motion geometry is rather limited. This is a general feature of DIPSHIFT experiments because even in an ideal geometry, the amount of the “averaged part” of M2M2 varies with the angle, which is a free parameter. So it is difficult to distinguish between a different angle and deviations from the chosen model, which is also to some degree arbitrary. Indeed, one of the advantages of using the AW approach to estimate the motion rates is that it does not depend severely on the motion geometry, but only on the averaged M2M2s, making possible to reliably. The detailed evaluation of the motion geometry will required the use of methods such as Exchange NMR. In this respect, Centerband-Only Detection of Exchange (CODEX) and variants provide an efficient way of separating the effects of the motion geometry and rates [12], but is usually much more time consuming than DIPSHIFT experiments. Also, the motion rates probed by Exchange NMR and DIPSHIFT (or other SLF methods) are in different frequency scales, so they are indeed complementary [13]. Based upon recent work of Hirschinger [32], a combination of the Anderson–Weiss and memory-function approximations was used to derive a fitting formula that describes NMR signals obtained in tCtC-recDIPSHIFT SLF experiments.

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