QMGreensite_merged

(bbancia) #1

Section 3.4.4), then the rf pulses in the spin echo sequence can be applied
toonly oneof the scalar coupled spins (theIspins in the following
example). For example, the spin echo sequence can be applied selectively
to the proton spins in an^1 H–^15 N scalar coupled spin system. Again,I
spin chemical shift is refocused and can be ignored. As before, following
the 90xpulse on theIspin, evolution occurs as follows:


Iy^2 JISIzSzt)IycosðJIStÞþ 2 IxSzsinðJIStÞ
!
Ix
IycosðJIStÞþ 2 IxSzsinðJIStÞ: ½ 2 : 280 Š

Only theIyterm is inverted by the 180xpulse; theSspin is unaffected.
The second delay generates


IycosðJIStÞþ 2 IxSzsinðJIStÞ
)
2 JISIzSzt
Iycos^2 ðJIStÞ 2 IxSzsinðJIStÞcosðJIStÞ
þ 2 IxSzcosðJIStÞsinðJIStÞþIysin^2 ðJIStÞ, ½ 2 : 281 Š

which reduces to


IycosðJIStÞþ 2 IxSzsinðJIStÞ )
2 JISIzSzt
Iy: ½ 2 : 282 Š

So, for the heteronuclear spin echo,


Iy )
tIxt
Iy ½ 2 : 283 Š

andboththe chemical shift and the heteronuclear coupling are refocused.
In essence, theSspins have been decoupled from theIspins by use of the
echo sequence.
The scalar coupling interaction evolves over the entire duration of
the spin echo sequence in ahomonuclear spin echobecause the 180 8
echo pulse affects both theIand theSspins equally. By analogy, the
heteronuclear scalar coupling interaction evolves over the duration of a
spin echo sequence if 1808 pulses are applied to both the I and the S spins
simultaneously(usually using two rf transmitter channels). The overall
effect of the –t– 180xðÞI,S –t– pulse sequence on initialIymagnetiza-
tion is given by


Iy )
tIx,Sxt
Iycosð 2 JIStÞ 2 IxSzsinð 2 JIStÞ: ½ 2 : 284 Š

2.7.7.2 Insensitive Nuclei Enhanced by Polarization Transfer Pulse
sequence elements can be combined to produce more complex sequences


96 CHAPTER 2 THEORETICALDESCRIPTION OFNMR SPECTROSCOPY

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