Field-cycling method with central transition readout for pure quadrupole resonance detection in dilute systems.
We present a modification of a field-cycling method which uses the NMR signal of the central transition at high field to indirectly detect zero-field quadrupole transitions. The quadrupole transitions at zero-field are detected as changes in the overall intensity of the central transition signal after the field cycle, and the method is relatively immune to lineshape distortions of the central transition caused by receiver dead time, frequency response of the probe, longer pulse lengths, etc. Cross-polarization with protons is used to enhance the central-transition signal and to increase the recycling rate of the experiment. The technique is especially useful when mixtures of several species are present. In a frozen solution of phenylboronic acid, 11B quadrupole signals of the tetrahedral species at 600 kHz and planar-trigonal species at 1450 kHz are clearly resolved. The field-cycling approach allows high-sensitivity detection of low-frequency quadrupole transitions; the experiment is sensitive enough to study boronic-acid protease inhibitors bound to proteins and may possibly be extended to lower sensitivity nuclei. The experiments are performed using a low-temperature field-cycling apparatus, operated at 10-30 K, capable of pneumatically moving the sample from the high field of a commercial 500 MHz magnet to the area above the top of the magnet where the low field is controlled by a pair of Helmholz coils.
Ivanov
Dmitri
D
Biophysics and Structural Biology Graduate Program, Brandeis University, Waltham, MA 02454, USA. dmitri.ivanov@rdls.nestle.com
Redfield
Alfred G
AG
D001897:Boronic Acids / Q000737:chemistry*; D019544:Equipment Failure Analysis; D005240:Feasibility Studies; D005615:Freezing; D009682:Magnetic Resonance Spectroscopy / Q000295:instrumentation* / Q000379:methods*; D008280:Magnetics / Q000295:instrumentation*; D012680:Sensitivity and Specificity; D012996:Solutions / Q000737:chemistry; D014159:Transducers
D001897:Boronic Acids; D012996:Solutions; C010686:benzeneboronic acid