Tailoring NMR Experiments for Oriented Samples

Separated local field experiments

A. Free-induction decay

           
B. Spin Exchange
 

 

Lee Goldburg condition


Anatomy of the PISEMA sequence

- Cross Polarization transfer
- Flip H magnetization to magic angle
- Allow 1H/15N to spin-exchange
- Acquire 15N under 1H decoupling

Setup PISEMA step-by-step

- Find the Hartmann-Hahn match at on-resonance condition
- Find the 1H resonance frequency
- Measure the 1H nutation frequency
- Find the Hartmann-Hahn match at off-resonance condition
- Find the phase of the 35.7o pulse

Find the Hartmann-Hahn condition at on-resonance condition

- Use a N-acetyl-Leucine single-crystal sample
- Adjust X channel power level to match the 1H channel power



Find the 1H resonance frequency

•- - Turn the decoupler power way down
Sweep the 1H irradiation frequency

         


Measure the 1H nutation frequency

•-Initial pulse rise time prevent accurate nutation frequency measurement
Use pre Spin-lock pulse to accurate measure 1H nutation frequency


Find the Hartmann-Hahn condition at off-resonance condition

Require phase-continuous frequency switching
Match the X channel to 1H channel during the offset irradiation (+Df)
Match the X channel to 1H channel during the offset irradiation (-Df)
Precede with spin-lock pulse
No compensation pulse

 

Find the phase of the 35.7o pulse


Typical PISEMA spectra

The line width (FWHH) is <200 Hz typical for single-crystal
 

Hardware requirement

A. Proton transmitter
    1. DDS (direct digital synthesizer)
    2. Or use small angle phase shifter (PMLG: phase-modulated Lee-Goldburg)
B. Proton / X channel amplifier
    1. Frequent phase inversion may overwhelm protection circuit
C. Probe tuning
    1. use directional coupler to monitor the reflective power
    2. Triple frequency tuning
    3. Steady-state tuning

A.

B.