Heteronuclear single quantum correlation pulse sequence

Figure 15 (A) The basic HSQC (heteronuclear single quantum coherence) pulse sequence. (B) The HSQC spectrum of the aliphatic region of [1] with the C along and the H spectrum along f2- The C- H connectivities are marked for the same molecular fragment as in Figure 14. Other sequences of proto-nated carbons can be determined from the same spectrum while an />bond (n=2,3) C- H shift correlation spectrum such as HMBC, COLOC or FLOCK (see Table 2) can identify non-proto-nated carbons and tie together the molecular fragments into a complete structure.

A sequence suitable for measurement of J(H, P) and J(C, P) couplings is shown in Fig. 7.9a. The pulse sequence is a constant-time [13C, H]-HSQC (heteronuclear single-quantum correlation), in which 31P decoupling is applied in ot, in the first experiment and in co2 in the second. 

The final step in the assignment of all resonances is correlating the C peaks with the proton peaks. This can often be done from chemical shift alone for the anomeric resonances, but not for other ring atoms. The most important pulse sequence here is HSQC (Heteronuclear Single Quantum Correlation), which involves six pulses to protons and four to C. The spectrum is now a non-symmetrical map with a peak at each carbon attached to a proton the projection on the C axis is the C DEPT spectrum and on the proton axis the ordinary proton spectrum (Figure 4.18). 

Figure 2 Heteronuclear single quantum correlation (HSQC) pulse sequences with optional decoupling of the 5-spin (a) standard sequence (b) modified for the /-spin-multiplicity determination.

HC HMQC (heteronuclear multiple quantum coherence) and HC HSQC (heteronuclear single quantum coherence) are the acronyms of the pulse sequences used for inverse carbon-proton shift correlations. These sensitive inverse experiments detect one-bond carbon-proton connectivities within some minutes instead of some hours as required for CH COSY as demonstrated by an HC HSQC experiment with a-pinene in Fig. 2.15. 

HSQC Heteronuclear single quantum coherence, e.g. inverse CH correlation via one-bond coupling providing the same result as HMQC but using an alternative pulse sequence... 

Fig. 10.15. Pulse sequence for the multiplicity-edited gradient HSQC experiment. Heteronuclear single quantum coherence is created by the first INEPT step within the pulse sequence, followed by the evolution period, t . Following evolution, the heteronuclear single quantum coherence is reconverted to observable proton magnetization by the reverse INEPT step. The simultaneous 180° XH and 13C pulses flanked by the delays, A = l/2( 1 edits magnetization inverting signals for methylene resonances, while leaving methine and methyl signals with positive phase (Fig. 16A). Eliminating this pulse sequence element affords a heteronuclear shift correlation experiment in which all resonances have the same phase (Fig. 16B).

Other strategies that show great promise in reducing NMR acquisition time utilise methods to obtain multiple sets of data from one experiment through a concept known as time-shared evolution. An example of this process that should find utility in natural products elucidation was demonstrated by a pulse sequence called CN-HMBC.93 Traditionally, a separate 13C-HMBC and 15N-HMBC were acquired independently. However, the CN-HMBC allows both 13C- and 15N-HMBC spectra to be obtained simultaneously. By acquiring both data sets simultaneously, an effective 50% time reduction can be achieved.93 This approach has also been demonstrated for a sensitivity-enhanced 2D HSQC-TOCSY (heteronuclear multiple bond correlation total correlation spectroscopy) and HSQMBC (heteronuclear single quantum... 

In heteronuclear correlation experiments, magnetization transfer between protons and heteronuclei can be via either heteronuclear single quantum coherence (HSQC) or heteronuclear multiple quantum coherence (HMQC) pathways. The HSQC sequence gives rise to narrower lines, but uses more pulses and requires a longer phase cycle than the HMQC. Thus, HSQC is used for 2D experiments where the highest resolution is required and HMQC is preferred for 3D sequences in which the experimental time is limited. 

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