Wednesday, May 18, 2016

Dynamic Nuclear Polarization enhanced NMR at 187GHz/284MHz using an Extended Interaction Klystron amplifier #DNPNMR


Kemp, T.F., et al., Dynamic Nuclear Polarization enhanced NMR at 187GHz/284MHz using an Extended Interaction Klystron amplifier. J Magn Reson, 2016. 265: p. 77-82.


A Dynamic Nuclear Polarisation (DNP) enhanced solid-state Magic Angle Spinning (MAS) NMR spectrometer which uses a 187GHz (corresponding to (1)H NMR frequency of 284MHz) Extended Interaction Klystron (EIK) amplifier as the microwave source is briefly described. Its performance is demonstrated for a biomolecule (bacteriorhodopsin), a pharmaceutical, and surface functionalised silica. The EIK is very compact and easily incorporated into an existing spectrometer. The bandwidth of the amplifier is sufficient that it obviates the need for a sweepable magnetic field, once set, for all commonly used radicals. The variable power (CW or pulsed) output from the EIK is transmitted to the DNP-NMR probe using a quasi-optic system with a high power isolator and a corrugated waveguide which feeds the microwaves into the DNP-NMR probe. Curved mirrors inside the probe project the microwaves down the axis of the MAS rotor, giving a very efficient system such that maximum DNP enhancement is achieved with less than 3W output from the microwave source. The DNP-NMR probe operates with a sample temperature down to 90K whilst spinning at 8kHz. Significant enhancements, in excess of 100 for bacteriorhodopsin in purple membrane (bR in PM), are shown along with spectra which are enhanced by approximately 25 with respect to room temperature, for both the pharmaceutical furosemide and surface functionalised silica. These enhancements allow hitherto prohibitively time consuming experiments to be undertaken. The power at which the DNP enhancement in bR in PM saturates does not change significantly between 90K and 170K even though the enhancement drops by a factor of approximately 11. As the DNP build up time decreases by a factor 3 over this temperature range, the reduction in T1n is presumably a significant contribution to the drop in enhancement.