High-resolution proton-detected MAS experiments on self-assembled diphenylalanine nanotubes enabled by fast MAS and high magnetic field

Abstract

The advent of ultrahigh magnetic field and fast magic-angle-spinning (MAS) probe technology has led to dramatically enhanced spectral resolution and sensitivity in solid-state NMR spectroscopy. In particular, proton-based multidimensional solid-state NMR techniques have become feasible to investigate the structure and dynamics at atomic resolution, due to the increased chemical shift span and spectral resolution. Herein, the benefits of faster MAS and higher magnetic field are demonstrated on a self-assembled diphenylalanine (Phe-Phe) nanomaterial. Proton-detected 2D ¹H/¹H single-quantum/single-quantum (SQ/SQ) correlation, double-quantum/single-quantum (DQ/SQ) correlation, and ¹H chemical shift anisotropy/chemical shift (CSA/CS) correlation spectra obtained at two different spinning speeds (60 and 100 kHz) and two different magnetic fields (600 and 900 MHz) are reported. The dramatic enhancement of proton spectral resolution achieved with the use of a 900 MHz magnetic field and 100 kHz MAS is remarkable and enabled the measurement of proton CSA tensors, which will be useful to better understand the self-assembled structures of Phe-Phe nanotubes. We also show through numerical simulations that the unaveraged proton-proton dipolar couplings can result in broadening of CSA lines, leading to inaccurate determination of CSA tensors of protons. Thus, our results clearly show the insufficiency of a 600 MHz magnetic field to resolve ¹H spectra lines and the inability of a moderate spinning speed of 60 kHz to completely suppress ¹H-¹H dipolar couplings, which further justify the pursuit of ultrahigh magnetic field beyond 1 GHz and ultrafast MAS beyond 100 kHz.

Keywords: Proton NMR; Proton chemical shift anisotropy; Self-assembled material; Ultrafast MAS; Ultrahigh magnetic field.