HMQC heteronuclear multiple-quantum coherence

An alternative way of acquiring the data is to observe the signal. These experiments are referred to as reverse- or inverse-detected experiments, in particular the inverse HETCOR experiment is referred to as a heteronuclear multiple quantum coherence (HMQC) spectmm. The ampHtude of the H nuclei is modulated by the coupled frequencies of the C nuclei in the evolution time. The principal difficulty with this experiment is that the C nuclei must be decoupled from the H spectmm. Techniques used to do this are called GARP and WALTZ sequences. The information is the same as that of the standard HETCOR except that the F and F axes have been switched. The obvious advantage to this experiment is the significant increase in sensitivity that occurs by observing H rather than C. 

H-Detected Heteronuclear Multiple-Quantum Coherence (HMQC) Spectra... 

The heteronuclear multiple-quantum coherence (HMQC) spectrum, H-NMR chemical shift assignments, and C-NMR data of podophyllo-toxin are shown. Determine the chemical shifts of various carbons and connected protons. The HMQC spectra provide information about the one-bond correlations of protons and attached carbons. These spectra are fairly straightforward to interpret The correlations are made by noting the position of each crossf)eak and identifying the corresponding 8h and 8c values. Based on this technique, interpret the following spectrum. 

J splittings cannot be directly resolved. In addition to the obvious advantage of providing a map of chemical bonds between the spins, /-based transfers do not require spin-locking and are not disturbed by molecular motions. The major drawback of polarization transfer through J coupling is that the delays involved in the pulse sequences, such as insensitive nuclei enhanced by polarization transfer (INEPT) [233] or heteronuclear multiple-quantum coherence (HMQC)... 

All one-bond H- C connectivities were established by a heteronuclear multiple-quantum coherence (HMQC) experiment. Partial structures including a tetraene system, a phenyl group and a diol moiety as shown in Figure 27A were determined by a COSY experiment. 

Inverse-detected experiments have had the greatest effect in making 15N NMR experiments feasible for small samples. These experiments take advantage of the higher sensitivity of NMR to facilitate the observation of insensitive nuclei like 13C and 15N. The H-13C heteronuclear multiple quantum coherence (HMQC) and the related heteronuclear multiple-bond correlation (HMBC) experiments are important in contemporary natural products... 

Heterocorrelations can be detected both in direct and reverse modes. In the latter mode, dramatic enhancements of sensitivity can be achieved owing to the larger sensitivity of protons with respect to heteronuclei. In the most common heterocorrelation pulse sequences for reverse detection, called heteronuclear multiple quantum coherence (HMQC) (Fig. 8.2G) [25,26], H-I3C MQ (multiple quantum) coherence is generated by first applying a 90° pulse on protons and, after a time t chosen equal to 1/2 J[j, by applying a 90° pulse on carbon (Fig. 8.19). 

In order to carry out complete structural elucidation of unknown compounds (especially for complex molecules), the RF probe should enable a variety of heteronuclear NMR techniques to be performed. In particular, inverse detection H-15N and 1H-13C experiments such as heteronuclear multiple quantum coherence (HMQC) [29,30] and heteronuclear single quantum coherence (HSQC) [31] find almost ubiquitous application in myriad research environments. Although the microliter-scale probes described above feature both heteronuclear and homonuclear capabilities, no commerical product is... 

By way of example, useful 2-D techniques are homonuclear correlation spectroscopy (COSY), total correlation spectroscopy (TOCSY), heteronuclear multiple quantum coherence (HMQC) spectroscopy, and heteronuclear multiple quantum coherence/total... 

HETERONUCLEAR MULTIPLE-QUANTUM COHERENCE (HMQC) SPECTROSCOPY... 

Heteronuclear multiple-quantum coherence (HMQC) allows one to edit all of the different isotopomers of a Pt cluster using the sequence described in ref. [20] with the preparation pulse only being cycled between +x and —x. More sophisticated phase cycling procedures lead to the selective editing of the different isotopomers. An example of Pt3(CO)3(PPh2 Pr)3 is presented in Figure 2. 

Figure 13(b) shows a JH—15N HSQC spectrum acquired from 0.5 mmol l-1 sample of a 41-residue peptide toxin from the spider Agelena orientalis. The toxin was produced recombinantly and uniformly labeled with 15N. This HSQC spectrum was collected in 30 min, compared with the 12 h required to acquire a natural abundance spectrum from an unlabeled sample of equivalent concentration (see Figure 11). The HSQC, together with the related heteronuclear multiple quantum coherence (HMQC)54 experiment, forms the cornerstone of a wide range of 2D, 3D, and 4D experiments that are designed to facilitate sequence-specific resonance assignment and determination of protein structure. Note that the HSQC technique is the technique of choice for correlation of H and 15N shifts due to generally narrower linewidths in the 15N dimension.55,56 Furthermore, because these and most of the other heteronuclear experiments described below are designed to observe amide protons, the sample must be in H20 (rather than D20). Consequently, a means of suppressing the H20 resonance is required (for details see Section 9.09.2.6).

The inverse detection heteronuclear multiple quantum coherence (HMQC) experiment is another approach to two-dimensional NMR techniques, which consists of a transfer of chemical shift and coupling information from relatively insensitive nuclei such as and some metals, to more sensitive nuclei such as H. The advantage of this method is a substantial increase in the sensitivity obtained, due to the greater natural abundance of H (Kingery et al., 2001). 

Heteronuclear multiple quantum coherence (HMQC) is MQ coherence involving spins of different types, eg. lK/l3C, 2H/13C, lK/l5N. Mi-... 

The DEPT pulse sequence is illustrated in Fig. 4.31. To follow events during this, consider once more a H- C pair and note the action of the two 180 pulses is again to refocus chemical shifts where necessary. The sequence begins in a similar manner to INEPT with a 90 (H) pulse after which proton magnetisation evolves under the influence of proton-carbon coupling such that after a period 1 /2J the two vectors of the proton satellites are antiphase. The application of a 90 (C) pulse at this point produces a new state of affairs that has not been previously encountered, in which both transverse proton and carbon magnetisation evolve coherently. This new state is termed heteronuclear multiple quantum coherence (hmqc) which, in general, cannot be visualised with the vector model, and without recourse to mathematical formalisms it is... 

NMR is the tool most widely used to identify the structure of triterpenes. Different one-dimension and two-dimension techniques are usually used to study the structures of new compounds. Correlation via H-H coupling with square symmetry ( H- H COSY), homonuclear Hartmann-Hahn spectroscopy (HOHAHA), heteronuclear multiple quantum coherence (HMQC), heteronuclear multiple bond correlation (HMBC), distortionless enhancement by polarisation transfer (DEPT), incredible natural abundance double quantum transfer experiment (INADEQUATE) and nuclear Overhauser effect spectroscopy (NOESY) allow us to examine the proton and carbon chemical shift, carbon types, coupling constants, carbon-carbon and proton-carbon connectivities, and establish the relative stereochemistry of the chiral centres. 

Is the probe direct, or inverse The former is good for direct observation with or without INEPT enhancement. The latter will give poor signaTto-noise in direct experiments since the sample does not fill the coil space, but is much preferred for indirect detection via, for example, a heteronuclear multiple quantum coherence (HMQC) or heteronuclear single quantum coherence (HSQC) experiment. 

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