Friday, June 25, 2010
Tuesday, June 22, 2010
Magic angle spinning is a technique used by solid state NMR spectroscopists to obtain high resolution NMR spectra of solids. Magic angle spinning at infinite speed completely averages the first order quadrupolar interaction but only partially averages out the second order interaction. The energy level diagram for a spin I = 5/2 nucleus spinning infinately fast at the magic angle is shown in the figure below along with a simulated spectrum. The spectrum consists of a central transition, CT, and two satellite transitions, ST1 and ST2. Note that along with a lineshape due to the orientational dependence of the nucleus in the magnetic field, there is also an isotropic quadrupolar shift. The central and satallite transitions are not at the same frequency. This effect is completely separate from the chemical shift.
In practice, we cannot spin at infinite speed, however, we can often spin at a rate fast with respect to the width of the central transition. If the quadrupolar coupling constant is small enough, the central transition will be observed and affected only by the second order interaction. The satellite transitions, affected by both the first and second order interaction, are observed as a manifold of spinning sidebands. The intensity of the centerbands for the satellite transitions is greatly attenuated as the overall intensity is spread among all of the sidebands. Often the centerbands for the satellite transitions are so small in comparison to that of the central transition that they are not observed. This is illustrated with simulations in the lower portion of the figure below. For comparison, the upper portion shows similar simulated spectra without magic angle spinning. The spectra highlighted in yellow are expansions of the central portion of the spectrum. These simulations are also supported by observations.
Thursday, June 17, 2010
After years of service, two of our Bruker AVANCE spectrometers were running very warm. Using "UniTool" to check the temperature of the SGUs revealed that the board temperatures averaged 58° C! The DDS temperatures were all >55° C and not regulated. The air filters in the console doors were removed and cleaned and all eight fans of the AQS unit, housing the SGU's, were replaced on each spectrometer. After a day for the instruments to come to a thermal steady state, the SGU and DDS temperatures were again measured. The SGU board temperatures averaged 49°C. The DDS units in three of the five SGU's were now regulated properly at 55°C. The other two were still > 55°C and unregulated. In an attempt to lower the temperature further, the backs of the spectrometers were removed and again the instruments were allowed to reach a thermal steady state over a 24 hour period. The SGU and DDS temperatures were measured again. This time the SGU board temperatures averaged 38°C and all five DDS units were regulated properly at 55°C. The SGU temperatures in our AVANCE II and III spectrometers (with backs on) did not exceed 40°C and the DDS temperatures were regulated properly.
Although this may not be recommended by Bruker, I now run our AVANCE spectrometers with the back panels removed.
Friday, June 11, 2010
Friday, June 4, 2010
1. C. Griesinger, O.W. Sorensen & R.R. Ernst, J. Magn. Reson. 75, ; 474 - 492 (1987).
2. The ecosygpph pulse program produces spectra similar to those described in reference 1 as "complimentary" E.COSY spectra. The slope of the lines through the cross peaks in "complementary" E.COSY spectra are of opposite sign to those obtained from the E.COSY spectra described in reference 1.