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The DIPSI (Decoupling In the Presence of Scalar Interactions) schemes are composite pulse sequences specifically designed for isotropic mixing purpose in TOCSY experiments (see The TOCSY block). The excellent efficiency over large bandwidths allows to be applied for homonuclear cross polarization in 13C NMR of labeled biomolecules.REQUIREMENTS
Easy implementation on AVANCE spectrometers.VERSIONS
Several versions of the DIPSI scheme have been proposed ( 88JMR274-77 and 92JMR670-96 ):EXPERIMENTAL DETAILSDIPSI-2: R(0)R(0)R(180)R(180) where
R=320(0)-410(180)-290(0)-285(180)-30(0)-245(180)-375(0)-265(180)-370(0)DIPSI-3: R(0)R(180)R(180)R(0) where
R=245(180)-395(0)-250(180)-275(0)-30(180)-230(0)-360(180)-245(0)-
370(180)-340(0)-350(180)-260(0)-270(180)-30(0)-225(180)-365(0)-255(180)-395(0)All flip angles and phases are specified in degrees (e.g., 46(0) denotes a 46 degree pulse with a relative phase of zero), and R(180) indicates a phase shift of all constituent pulses by 180 degrees.
The relative length of several mixing sequences are:
WALTZ-16 1.00The DIPSI-2 offers an excellent global offset quality factor (Q) ensuring that coherence transfer is efficiently achieved over the chemical-shift range of interest:
DIPSI-2 1.20
DIPSI-3 2.25
FLOPSY-8 0.98
Sequence Qx Qy Qz IICT-1 0.73 0.52 0.57 IICT-2 0.71 0.51 0.5 IICT-3 0.72 0.52 0.52 IICT-4 0.59 0.58 0.63 MLEV-16 -0.31 -0.31 0.16 DIPSI-2 0.68 0.44 0.46 FLOPSY-2 0.62 0.55 0.61 A modified DIPSI sequence has been proposed to suppress cross-relaxation effects in TOCSY spectra ( 92JMR670-96 ) in which a t delay is adjusted to minimize the net cross-relaxation rate.
DIPSI-2rc: R(0)R(180)R(180)R(0) where
R=180(0)-t-140(0)-320(180)-t-90(180)-270(0)-t-20(0)-200(180)-t-85(180)-30(0)- 125(180)-t-120(180)-300(0)-t-75((0)-225(180)-t-10(180)-190(0)-t-180(0)-tThe DIPSI schemes are also widely used for effective heteronuclear cross-polarization purposes ( 91JMR413-91 )
Calibration of 90º and 180º pulses must be made at the required power. In general, for TOCSY applications, the power is adjusted to give a 90º pulse about 30-35 microseconds. A 10% variation in such calibrations could be tolerated.RELATED TOPICSFor further experimental details, see the following tutorials: