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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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lineshapes can be obtained. Also, both in generating the double quantum<br />

coherence, <strong>and</strong> in reconverting it to observable magnetization, all possible<br />

pathways have been retained. If we do not do this, signal intensity is lost.<br />

One way of viewing this sequence is to group the first two pulses together<br />

<strong>and</strong> view them as achieving the transformation 0 → ±2 i.e.<br />

∆p = ±2. This is exactly the problem considered in section 9.5.5.2, where we<br />

saw that a suitable four step cycle is for the first two pulses to go 0°, 90°, 180°,<br />

270° <strong>and</strong> the receiver to go 0°, 180°, 0°, 180°. This unambiguously selects p =<br />

±2 just before the last pulse, so phase cycling of the last pulse is not required<br />

(see section 9.5.5.3).<br />

An alternative view is to say that as only p = –1 is observable, selecting the<br />

transformation ∆p = +1 <strong>and</strong> –3 on the last pulse will be equivalent to selecting p<br />

= ±2 during the period just before the last pulse. Since the first pulse can only<br />

generate p = ±1 (present during t 1<br />

), the selection of ∆p = +1 <strong>and</strong> –3 on the last<br />

pulse is sufficient to define the CTP completely.<br />

A four step cycle to select ∆p = +1 involves the pulse going 0°, 90°, 180°,<br />

270° <strong>and</strong> the receiver going 0°, 270°, 180°, 90°. As this cycle has four steps is<br />

automatically also selects ∆p = –3, just as required.<br />

<strong>The</strong> first of these cycles also selects ∆p = ±6 for the first two pulses i.e.<br />

filtration through six-quantum coherence; normally, we can safely ignore the<br />

possibility of such high-order coherences. <strong>The</strong> second of the cycles also selects<br />

∆p = +5 <strong>and</strong> ∆p = –7 on the last pulse; again, these transfers involve such high<br />

orders of multiple quantum that they can be ignored.<br />

9.5.6 Axial peak suppression<br />

Peaks are sometimes seen in two-dimensional spectra at co-ordinates F 1<br />

= 0 <strong>and</strong><br />

F 2<br />

= frequencies corresponding to the usual peaks in the spectrum. <strong>The</strong><br />

interpretation of the appearance of these peaks is that they arise from<br />

magnetization which has not evolved during t 1<br />

<strong>and</strong> so has not acquired a<br />

frequency label.<br />

A common source of axial peaks is magnetization which recovers due to<br />

longitudinal relaxation during t 1<br />

. Subsequent pulses make this magnetization<br />

observable, but it has no frequency label <strong>and</strong> so appears at<br />

F 1<br />

= 0. Another source of axial peaks is when, due to pulse imperfections, not<br />

all of the original equilibrium magnetization is moved into the transverse plane<br />

by the first pulse. <strong>The</strong> residual longitudinal magnetization can be made<br />

observable by subsequent pulses <strong>and</strong> hence give rise to axial peaks.<br />

A simple way of suppressing axial peaks is to select the pathway ∆p = ±1 on<br />

the first pulse; this ensures that all signals arise from the first pulse. A two-step<br />

cycle in which the first pulse goes 0°, 180° <strong>and</strong> the receiver goes 0°, 180°<br />

selects ∆p = ±1. It may be that the other phase cycling used in the sequence<br />

will also reject axial peaks so that it is not necessary to add an explicit axial<br />

peak suppression steps. Adding a two-step cycle for axial peak suppression<br />

9–28

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