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The selective 1D HMQC-TOCSY experiment is the selective version of the 2D HMQC-TOCSY experiment. As in the conventional TOCSY experiments, it allows to obtain 1H subspectra but from a selected 13C nucleus. This experiment has also been used to measure long-range proton-carbon coupling constants.REQUIREMENTS
Easy implementation on AVANCE spectrometers equipped with an inverse probehead and selective excitation using shaped pulses.VERSIONS
The selective 1D HMQC-TOCSY pulse sequence is easily derived from the conventional 2D HMQC-TOCSY experiment in which one of the two 90º 13C pulses is made selective for a given 13C resonance and the variable evolution delay is fixed to a minimum value ( 90MRC696 and 90TL5273 ). In other words, it consists of a selective 1D HMQC pulse train followed by a TOCSY block. A BIRD-recovery delay cluster can be incorporated as a preparation period to suppress the large and undesired 1H-12C magnetization.EXPERIMENTAL DETAILS
Related modified sequences have been proposed:
- Analog selective 1D HSQC-TOCSY ( 94JMRA94-107 and 94JMRA95-110 ) and selective 1D reverse-INEPT-TOCSY ( 94JMRA94-107 , 94JMRA90-110 , and 94JMRA95-110 ) experiments have also been proposed for the same purpose.
- Better results are obtained from the gradient-enhanced version (see selective ge-1D HMQC-TOCSY experiment).
- Measurement of long-range proton-carbon coupling constants ( 94JMRA119-106 ).
- Analog experiments are used to measure long-range 1H-13C coupling constants by recording two separate 1D spectra from the alpha and beta 13C spin states ( 94MRC97 , 94JMRB284-103 , 94JMRA103-108 , 94JMRA262-110 , 95JMRA267-117 , 96JMRA105-123 , 96JMRA260-119 , and 96JMRA117-118 ).
- Use of a 13C chemical shift-selective filter ( 94JMRA119-106 ).
- Application on 31P has been reported ( 93JMRA304-105 ).
The selective 1D HMQC-TOCSY experiment can be recorded in a fully automated way. Minor changes from a predefined parameter set are required. The most important parameters to define is the TOCSY mixing time and the selective 13C pulse: the offset, the shape, the duration and the power level needed for a specific excitation profile.SPECTRAFor further details on practical implementation of the selective 1D HMQC-TOCSY experiment on AVANCE spectrometers see Tutorial: selective 1D HMQC-TOCSY experiment
The selective 1D HMQC-TOCSY experiment affords a 13C-edited 1D TOCSY spectrum from the selected 13C resonance. It can be an useful alternative to achieve 1D 1H subspectra in high overlapped regions. The direct response appears as a large doublet due to 1J(CH) if no 13C decoupling is applied during acquisition while all other 1H nuclei belonging to the same spin system will also show the residual long-range 1H-13C coupling constant (nJ(CH)) with respect to the selected 13C nucleus. However, accurate measurement of even tiny nJ(CH) values can be obtained by recording two separate selective 1D HMQC-TOCSY spectra on each line (alpha and beta state) of the 13C doublet resonance of the corresponding 1H-coupled 13C spectrum.RELATED TOPICS