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
and then further transformation with respect to t 1 gives 1 SP ( F1, F2)= 4 A1+ + iD1+ A2 iD2 [ ][ + ] The real part of this spectrum is 1 Re { SP( F1, F2) }= A + A − D + D [ ] 4 1 2 1 2 The quantity in the square brackets on the right represents a phase-twist lineshape at F 1 = +Ω, F 2 = Ω Perspective view and contour plot of the phase-twist lineshape. Negative contours are shown dashed. This lineshape is an inextricable mixture of absorption and dispersion, and it is very undesirable for high-resolution NMR. So, although a phase modulated signal gives us frequency discrimination, which is desirable, it also results in a phase-twist lineshape, which is not. The time domain signal for the amplitude modulated data set can be written as 1 S t , t cos Ωt exp iΩt exp t T exp t T C ( )= ( ) ( ) ( − ) ( − ) 1 2 2 1 2 1 2 2 2 Fourier transformation with respect to t 2 gives which can be rewritten as 1 S t , F cos Ωt exp t T A iD C ( 1 2)= 2 ( 1) ( − 1 2) [ 2 + 2] [ ] − ( )= ( )+ ( − ) ( )[ + ] 1 SC t1, F2 exp iΩt exp iΩt exp t T A iD 4 1 1 1 2 2 2 Fourier transformation with respect to t 1 gives, in the real part of the spectrum { ( )}= [ ]+ 4 [ 1 2 1 2] 1 1 Re SC F1, F2 4 A1+ A2 – D1+ D2 A −A – D – D This corresponds to two phase-twist lineshapes, one at F 1 = +Ω, F 2 = Ω and the other at F 1 = –Ω, F 2 = Ω; the lack of frequency discrimination is evident. Further, the undesirable phase-twist lineshape is again present. The lineshape can be restored to the absorption mode by discarding the imaginary part of the time domain signal after the transformation with respect to t 2 , i.e. by taking the real part { C( 1 2) }= 2 ( 1) ( − 1 2) 2 1 Re S t , F cos Ωt exp t T A Subsequent transformation with respect to t 1 gives, in the real part 9–16
A A + A A 1 1 4 1+ 2 4 1− 2 which is two double absorption mode lineshapes. Frequency discrimination is lacking, but the lineshape is now much more desirable. The spectra with the two phase-twist and two absorption mode lines are shown below on the left and right, respectively. F 2 F 1 F 1 F 2 0 0 9.4.4 Frequency discrimination with retention of absorption mode lineshapes For practical purposes it is essential to be able to achieve frequency discrimination and at the same time retain the absorption mode lineshape. There are a number of ways of doing this. 9.4.4.1 States-Haberkorn-Ruben (SHR) method The key to this method is the ability to record a cosine modulated data set and a sine modulated data set. The latter can be achieved simply by changing the phase of appropriate pulses. For example, in the case of the NOESY experiment, all that is required to generate the sine data set is to shift the phase of the first 90° pulse by 90° (in fact in the NOESY sequence the pulse needs to shift from x to –y). The two data sets have to kept separate. The cosine data set is transformed with respect to t 1 and the imaginary part discarded to give { C( 1 2) }= 2 ( 1) ( − 1 2) 2 1 Re S t , F cos Ω t exp t T A [9] The same operation is performed on the sine modulated data set 1 S t , t sin Ωt exp iΩt exp t T exp t T S ( 1 2)= 2 ( 1) ( 2) ( − 1 2) ( − 2 2) 1 Re { SS( t1, F2) }= 2 sin( t1) exp( −t1 T2) A2 Ω [10] A new complex data set is now formed by using the signal from Eq. [9] as the real part and that from Eq. [10] as the imaginary part ( )= { ( )}+ ( ) ( ) { } S t , F Re S t , F i Re S t , F SHR 1 2 C 1 2 S 1 2 1 = 2 exp( iΩt1) exp −t1 T2 A2 Fourier transformation with respect to t 1 gives, in the real part of the spectrum 1 Re { SSHR( F1 , F2 )}= 2 A1+ A2 This is the desired frequency discriminated spectrum with a pure absorption 9–17
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- Page 19 and 20: [ ] 1 S+ ( F1, F2)= 2 A1+ + iD1+ A2
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A A<br />
+<br />
A A<br />
1<br />
1<br />
4 1+ 2 4 1−<br />
2<br />
which is two double absorption mode lineshapes. Frequency discrimination is<br />
lacking, but the lineshape is now much more desirable. <strong>The</strong> spectra with the<br />
two phase-twist <strong>and</strong> two absorption mode lines are shown below on the left <strong>and</strong><br />
right, respectively.<br />
F 2<br />
F 1 F 1<br />
F 2<br />
0<br />
0<br />
9.4.4 Frequency discrimination with retention of absorption mode<br />
lineshapes<br />
For practical purposes it is essential to be able to achieve frequency<br />
discrimination <strong>and</strong> at the same time retain the absorption mode lineshape.<br />
<strong>The</strong>re are a number of ways of doing this.<br />
9.4.4.1 States-Haberkorn-Ruben (SHR) method<br />
<strong>The</strong> key to this method is the ability to record a cosine modulated data set <strong>and</strong> a<br />
sine modulated data set. <strong>The</strong> latter can be achieved simply by changing the<br />
phase of appropriate pulses. For example, in the case of the NOESY<br />
experiment, all that is required to generate the sine data set is to shift the phase<br />
of the first 90° pulse by 90° (in fact in the NOESY sequence the pulse needs to<br />
shift from x to –y). <strong>The</strong> two data sets have to kept separate.<br />
<strong>The</strong> cosine data set is transformed with respect to t 1<br />
<strong>and</strong> the imaginary part<br />
discarded to give<br />
{ C( 1 2)<br />
}=<br />
2 ( 1) ( −<br />
1 2)<br />
2<br />
1<br />
Re S t , F cos Ω t exp t T A<br />
[9]<br />
<strong>The</strong> same operation is performed on the sine modulated data set<br />
1<br />
S t , t sin Ωt exp iΩt exp t T exp t T<br />
S<br />
( 1 2)= 2 ( 1) ( 2) ( −<br />
1 2) ( −<br />
2 2)<br />
1<br />
Re { SS( t1, F2)<br />
}=<br />
2<br />
sin( t1) exp( −t1 T2)<br />
A2<br />
Ω [10]<br />
A new complex data set is now formed by using the signal from Eq. [9] as the<br />
real part <strong>and</strong> that from Eq. [10] as the imaginary part<br />
( )= { ( )}+ ( )<br />
( )<br />
{ }<br />
S t , F Re S t , F i Re S t , F<br />
SHR 1 2 C 1 2 S 1 2<br />
1<br />
=<br />
2<br />
exp( iΩt1) exp −t1 T2 A2<br />
Fourier transformation with respect to t 1<br />
gives, in the real part of the spectrum<br />
1<br />
Re { SSHR( F1 , F2<br />
)}= 2<br />
A1+<br />
A2<br />
This is the desired frequency discriminated spectrum with a pure absorption<br />
9–17