Phase Cycling and Gradient Pulses - The James Keeler Group
Phase Cycling and Gradient Pulses - The James Keeler Group
Phase Cycling and Gradient Pulses - The James Keeler Group
Create successful ePaper yourself
Turn your PDF publications into a flip-book with our unique Google optimized e-Paper software.
y the gradient at the edges of the sample, γB g<br />
(r max<br />
), is of the order of ω 1<br />
. (b)<br />
<strong>The</strong> rate of dephasing is proportional to the zero-quantum frequency in the<br />
absence of a gradient, (Ω k<br />
– Ω l<br />
). (c) <strong>The</strong> gradient must be switched on <strong>and</strong> off<br />
adiabatically. (d) <strong>The</strong> zero-quantum coherences may also be dephased using<br />
the inherent inhomogeneity of the radio-frequency field produced by typical<br />
NMR probes, but in such a case the optimum dephasing rate is obtained by spin<br />
locking off-resonance so that<br />
tan – 1( ω1 Ω kl , )≈ 54°.<br />
(e) Dephasing in an inhomogeneous B 1<br />
field can be accelerated by the use of<br />
special composite pulse sequences.<br />
<strong>The</strong> combination of spin-locking with a gradient pulse allows the<br />
implementation of essentially perfect purging pulses. Such a pulse could be<br />
used in a two-dimensional TOCSY experiment whose pulse sequence is shown<br />
below as (a).<br />
(a)<br />
(b)<br />
y<br />
DIPSI<br />
t t 1 2<br />
t 1<br />
τ m<br />
t 2<br />
g<br />
G A G A G A G 2<br />
Pulse sequences using purging pulses which comprise a period of spin locking with a magnetic field<br />
gradient. <strong>The</strong> field gradient must be switched on <strong>and</strong> off in an adiabatic manner.<br />
In this experiment, the period of isotropic mixing transfers in-phase<br />
magnetization (say along x) between coupled spins, giving rise to cross-peaks<br />
which are absorptive <strong>and</strong> in-phase in both dimensions. However, the mixing<br />
sequence also both transfers <strong>and</strong> generates anti-phase magnetization along y,<br />
which gives rise to undesirable dispersive anti-phase contributions in the<br />
spectrum. In sequence (a) these anti-phase contributions are eliminated by the<br />
use of a purging pulse as described here. Of course, at the same time all<br />
magnetization other than x is also eliminated, giving a near perfect TOCSY<br />
spectrum without the need for phase cycling or other difference measures.<br />
<strong>The</strong>se purging pulses can be used to generate pure z-magnetization without<br />
contamination from zero-quantum coherence by following them with a 90°(y)<br />
pulse, as is shown in the NOESY sequence (b). Zero-quantum coherences<br />
present during the mixing time of a NOESY experiment give rise to<br />
troublesome dispersive contributions in the spectra, which can be eliminated by<br />
the use of this sequence.<br />
9–49