DEPT spectroscopy

The imaging of conversion within the fixed bed was achieved by using a distortionless enhancement by polarization transfer (DEPT) spectroscopy pulse sequence integrated into an imaging sequence, as shown in Fig. 44. In theory, a signal enhancement of up to a factor of 4 (/hZ/c 7i is the gyromagnetic ratio of nucleus i) can be achieved with DEPT. In this dual resonance experiment, initial excitation is on the H channel. Consequently, the repetition time for the DEPT experiment is constrained by Tih (< T lc) where Tn is the Ty relaxation time of... 

In this edition, Jan co-authored the section on DEPT spectroscopy, most of the new problems, and all of the Answers to Selected Problems. Particular thanks are also due to Carol Pritchard-Martinez and Ray Mullaney, who both made thousands of useful suggestions throughout the writing and revision process, and who helped to shape this new edition. 

Fig. 6.19. Pulse sequence for DEPT spectroscopy. The third H pulse is variable with 9 = 45°, 90° and 135°, The delay time t is set to (2ycH) - (Reproduced from Ref. [52]. 1986 American Chemical Society.)...

The C line assignments were made from the combination of DEPT and 2D C- H correlated spectroscopy despite the complexity of the conventional C spectrum. DEPT spectroscopy allowed the multiplicity of each resonance to be determined unambiguously. Hence, C assignments were made easily from the 2D C- H correlated spectrum even in situations where overlap of methine and methylene signals occurs in the proton spectrum. Furthermore, equivalent and nonequivalent methylenes were distinguished in the 2D C- H correlated spectrum, and this allowed assignments to be made despite spectral overlap of proton resonances. Proton chemical shifts were determined more accurately from the correlated... 

Generally, the most powerful method for stmctural elucidation of steroids is nuclear magnetic resonance (nmr) spectroscopy. There are several classical reviews on the one-dimensional (1-D) proton H-nmr spectroscopy of steroids (267). C-nmr, a technique used to observe individual carbons, is used for stmcture elucidation of steroids. In addition, C-nmr is used for biosynthesis experiments with C-enriched precursors (268). The availability of higher magnetic field instmments coupled with the arrival of 1-D and two-dimensional (2-D) techniques such as DEPT, COSY, NOESY, 2-D J-resolved, HOHAHA, etc, have provided powerful new tools for the stmctural elucidation of complex natural products including steroids (269). 

Other two-dimensional techniques, such as COSY (122), DEPT (123), HOHAHA, soHd state (124) etc. give varying degrees of success when apphed to the stmcture-property relationship of cellulose triesters. The recent appHcation of multiple-bond correlation (HMBC) spectroscopy for... 

Population transfer experiments may be selective or nonselective. Selective population transfer experiments have found only limited use for signal multiplicity assignments (SSrensen et al, 1974) or for determining signs of coupling constants (Chalmers et al., 1974 Pachler and Wessels, 1973), since this is better done by employing distortionless enhancement by polarization transfer (DEPT) or Correlated Spectroscopy (COSY) experiments. However, nonselective population transfer experiments, such as INEPT or DEPT (presented later) have found wide application. 

F. Aguirre, Electronic spectroscopy of Au CH2 and intermediates involved in the conversion of methane to methanol by FeO Ph.D. Dissertation, Dept, of Chemistry. University of Massachusetts, 2002. 

Multidimensional spectraas well as techniques including DEPT (distortionless enhancement by polarization transfer), COSY (correlated spectroscopy), and ROESY (rotating-frame overhauser enhancement spectroscopy) have been increasingly used. 

There are a large number of structural parameters for NMR of different nuclei and many examples of how they can be applied to the analysis of hydroxylamines, oximes and hydroxamic acids. Fortunately though, there are many very clear, meticulously written descriptions of INEPT, DEPT, INADEQUATE, COSY, NOESY and the like, in one- and two-dimensional NMR spectroscopy, that are cited in the references. Since their content is beyond the scope of the present chapter, a brief mention of some of the fundamental concepts that are essential for its understanding by the nonspecialist is in order. 

The isotope N, with a natural abundance of 99.9%, has nuclear spin 7 = 1 and gives broad signals which are of little use for structural determinations. The N nucleus, with I = 1/2, is therefore preferred. However, the low natural abundance of about 0.4% and the extremely low relative sensitivity (Table 1) make measurements so difficult that N NMR spectroscopy was slow to become an accepted analytical tool. A further peculiarity is the negative magnetogyric ratio since, in proton decoupled spectra, the nuclear Overhauser effect can strongly reduce the signal intensity. DEPT and INEPT pulse techniques are therefore particularly important for N NMR spectroscopy. 

The INEPT (Insensitive Nuclei Enhanced by Polarization Transfer) experiment [6, 7] was the first broadband pulsed experiment for polarization transfer between heteronuclei, and has been extensively used for sensitivity enhancement and for spectral editing. For spectral editing purposes in carbon-13 NMR, more recent experiments such as DEPT, SEMUT [8] and their various enhancements [9] are usually preferable, but because of its brevity and simplicity INEPT remains the method of choice for many applications in sensitivity enhancement, and as a building block in complex pulse sequences with multiple polarization transfer steps. The potential utility of INEPT in inverse mode experiments, in which polarization is transferred from a low magnetogyric ratio nucleus to protons, was recognized quite early [10]. The principal advantage of polarization transfer over methods such as heteronuclear spin echo difference spectroscopy is the scope it offers for presaturation of the unwanted proton signals, which allows clean spec-... 

We see from Table 1 that the only observable nuclide for oxygen, 0, has a very low natural abundance, even in comparison with those of popular nuclides like (1.108%) and N (031%). Moreover, its quadrupole moment prevents any practical utilization of polarization transfer techniques like INEPT or DEPT, now widely used in and N NMR spectroscopies. A range of chemical shifts much wider than those of and N is an important point in favour of utilization of 0. All these properties did not prevent important applications of O NMR spectroscopy in organic chemistry, even from the times of continuous wave NMR spectroscopy. Interesting examples of such pioneering works can be found both at natural abundance as well as with enriched samples . However, also in the case of O NMR spectroscopy, FT NMR proved to be decisive for its development. 

The structure of the stable ozonide of a diterpene (300) was elucidated based on knowledge of the original structure assisted by H and NMR spectroscopies. Thus, a NMR DEPT experiment points to the presence of six quaternary C, six CH, three... 

The structures of the compounds were elucidated by a combination of NMR techniques (lH-, 13C-, and 13C-DEPT NMR) and chemical transformation, enzymatic degradation, and as well as mass spectrometry, which gives information on the saccharide sequence. A more recent approach consists of an extensive use of high-resolution 2D NMR techniques, such as homonuclear and heteronuclear correlated spectroscopy (DQF-COSY, HOHAHA, HSQC, HMBC) and NOE spectroscopy (NOESY, ROESY), which now play the most important role in the structural elucidation of intact glycosides. These techniques are very sensitive and non destructive and allow easy recovery of the intact compounds for subsequent biological testing. 

Key experiments useful for substructure determination by NMR include the DEPT sequence (c.. Figs. 2.44-2.46) for analysis of CH multiplicities, as well as the two-dimensional CH correlation for identification of all CH bonds (e.g. Fig. 2.55 and Table 2.2) and localization of individual proton shifts. If, in addition, vicinal and longer-range proton-proton coupling relationships are known, all CH substructures of the sample molecule can be derived. Classical identification of homonuclear proton coupling relationships involves homonuclear proton decoupling. A two-dimensional proton-proton shift correlation would be an alternative and the complementary experiment to carbon-proton shift correlation. Several methods exist [68], Of those, the COSTsequence abbreviated from Correlation spectroscopy [69] is illustrated in Fig. 2.56. 

Shin, H. S., Rhee, S. W., Lee, B. H., and Moon, C. H. (1996). Metal binding sites and partial structures of soil fulvic and humic acids compared Aided by Eu(III) luminescence spectroscopy and DEPT/QUAT 13C NMR pulse techniques. Org. Geochem. 24, 523-529. 

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