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Phase Cycling and Gradient Pulses - The James Keeler Group

Phase Cycling and Gradient Pulses - The James Keeler Group

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pulse goes x, –x <strong>and</strong> the receiver goes x, –x.<br />

For non-axial peaks, the two phase shifts cancel one another out, <strong>and</strong> so have<br />

no effect. However, magnetization which gives rise to axial peaks does not<br />

experience the first phase shift, but does experience the receiver phase shift.<br />

<strong>The</strong> sign alternation in concert with t 1<br />

incrementation adds a frequency of SW 1<br />

/2<br />

to each peak, thus shifting it to the edge of the spectrum. Note that in States-<br />

TPPI the spectral range in the F 1<br />

dimension is –(SW 1<br />

/2) to +(SW 1<br />

/2) <strong>and</strong> the<br />

sampling interval is 1/2SW 1<br />

, just as in the SHR method.<br />

<strong>The</strong> nice feature of States-TPPI is that is moves the axial peaks out of the<br />

way without lengthening the phase cycle. It is therefore convenient to use in<br />

complex three- <strong>and</strong> four-dimensional spectra were phase cycling is at a<br />

premium.<br />

9.5 <strong>Phase</strong> cycling<br />

In this section we will start out by considering in detail how to write a phase<br />

cycle to select a particular value of ∆p <strong>and</strong> then use this discussion to lead on to<br />

the formulation of general principles for constructing phase cycles. <strong>The</strong>se will<br />

then be used to construct appropriate cycles for a number of common<br />

experiments.<br />

9.5.1 Selection of a single pathway<br />

To focus on the issue at h<strong>and</strong> let us consider the case of transferring from<br />

coherence order +2 to order –1. Such a transfer has ∆p = (–1 – (2) ) = –3. Let<br />

us imagine that the pulse causing this transformation is cycled around the four<br />

cardinal phases (x, y, –x, –y, i.e. 0°, 90°, 180°, 270°) <strong>and</strong> draw up a table of the<br />

phase shift that will be experienced by the transferred coherence. This is<br />

simply computed as – ∆p φ, in this case = – (–3)φ = 3φ.<br />

step<br />

pulse phase<br />

phase shift experienced by<br />

transfer with ∆p = –3<br />

equivalent phase<br />

1 0 0 0<br />

2 90 270 270<br />

3 180 540 180<br />

4 270 810 90<br />

<strong>The</strong> fourth column, labelled "equivalent phase", is just the phase shift<br />

experienced by the coherence, column three, reduced to be in the range 0 to<br />

360° by subtracting multiples of 360° (e.g. for step 3 we subtracted 360° <strong>and</strong><br />

for step 4 we subtracted 720°).<br />

If we wished to select ∆p = –3 we would simply shift the phase of the<br />

receiver in order to match the phase that the coherence has acquired; these are<br />

the phases shown in the last column. If we did this, then each step of the cycle<br />

would give an observed signal of the same phase <strong>and</strong> so they four contributions<br />

would all add up. This is precisely the same thing as we did when considering<br />

9–21

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