Multiple-Quantum J-Resolved NMR Spectroscopy (MQ-JRES): Measurement of Multiple-Quantum Relaxation Rates and Relative Signs of Spin Coupling Constants

The technique of multiple-quantum J-resolved NMR spectroscopy (MQ-JRES) is introduced and applied to the spin system SI₃–M (such as in the example given here, the ¹³CH₃–¹²CH in alanine). The SI₃ spin system was excited to its highest quantum state (8S_yI_xI_yI_y), which consists of four coherences: quadruple quantum of (3I + S), double quantum of (3I − S), double quantum of (I + S), and zero quantum of (I − S). In the MQ spectrum generated from the projection onto the F₁ dimension, the resonances of the different multiple-quantum coherences are resolved by their coupling constants to the remote spin (M). The absorptive lineshapes in both F₁ and F₂ dimensions enable accurate measurements of transverse relaxation rates, and both amplitude and relative signs of the long-range coupling constants are to be derived from either frequency or time domain data. The selective detection of MQ-JRES spectra of the individual MQ coherences using either phase cycling or pulsed field gradients is presented.