Separating an overlapped 1H peak and identifying its 1H-1H correlations with the use of single-channel 1H solid-state NMR at fast MAS

Abstract

Fast magic-angle spinning (≥60 ​kHz) technique has enabled the acquisition of high-resolution ¹H NMR spectra of solid materials. However, the spectral interpretation is still difficult because the ¹H peaks are overlapped due to the narrow chemical shift range and broad linewidths. An additional ¹³C or ¹⁴N or ¹H dimension possibly addresses the issues of overlapped proton resonances, but it leads to the elongated experimental time. Herein, we introduce a single-channel ¹H experiment to separate the overlapped ¹H peak and identify its spatially proximal ¹H–¹H correlations. This sequence combines selective excitation, selective ¹H–¹H polarization transfer by selective recoupling of protons (SERP), and broadband ¹H recoupling by back-to-back (BABA) recoupling sequences. The concept for ¹H separation is based on (i) the selective excitation of a well-resolved ¹H peak and (ii) the selective dipolar polarization transfer from this isolated ¹H peak to one of the ¹H peaks in the overlapped/poor resolution region by SERP and (iii) the detection of ¹H–¹H correlations from these two ¹H peaks to other neighboring ¹Hs by BABA. We demonstrated the applicability of this approach to identify overlapped peaks on two molecules, β-L-aspartyl-l-alanine and Pioglitazone.HCl. The sequence allows the clear observation of ¹H–¹H correlations from an overlapped ¹H peak without an additional heteronuclear dimension and ensures efficient polarization transfers that leads to twelve fold reduction in experimental time compared to ¹⁴N edited experiments. The limitation and the conditions of applicability for this approach are discussed in detail.