RESUMEN
In this work, optimal control theory was used to design efficient excitation schemes in highly conductive materials, where both the radio frequency field strength and phase vary as a function of penetration depth. A pulse was designed to achieve phase alignment between signals at different depths within the conductor and thus to obtain higher signals from that region. In addition, an efficient suppression pulse was designed by insuring mutual suppression between the signals from various depths in the sample. The performance of the new approach was demonstrated experimentally for a bulk lithium sample for the excitation problem and for a biphasic metal/liquid sample for the selective suppression pulse.
RESUMEN
Total correlation spectroscopy (TOCSY) is a key experiment to assign nuclear magnetic resonance (NMR) spectra of complex molecules. Carbon-13 TOCSY experiments are essential to assign signals of protein side chains. However, the performance of carbon-13 TOCSY deteriorates at high magnetic fields since the necessarily limited radiofrequency irradiation fails to cover the broad range of carbon-13 frequencies. Here, we introduce a new concept to overcome the limitations of TOCSY by using two-field NMR spectroscopy. In two-field TOCSY experiments, chemical shifts are labelled at high field but isotropic mixing is performed at a much lower magnetic field, where the frequency range of the spectrum is drastically reduced. We obtain complete correlations between all carbon-13 nuclei belonging to amino acids across the entire spectrum: aromatic, aliphatic and carboxylic. Two-field TOCSY should be a robust and general approach for the assignment of uniformly carbon-13 labelled molecules in high-field and ultra-high field NMR spectrometers beyond 1000â MHz.
