Amplitude modulation, heteronuclear

Aluminum complexes, 2D NMR, 116 Amplitude modulation, heteronuclear spin coupling, 99... 

The pulse sequence for an amplitude modulated heteronuclear 2DJ experiment is shown in Fig. 8.6 [75]. The experiment consists of a 90° pulse to rotate magnetization into the xy-plane where it begins to evolve with the decoupler turned on. After the first half of the evolution time has elapsed, t/2, a 180° pulse is applied and the decoupler is gated off for the second half of the evolution period. 

Fig. 10.12. Pulse sequence for amplitude modulated 2D J-resolved spectroscopy. The experiment is effectively a spin echo, with the 13C signal amplitude modulated by the heteronuclear coupling constant(s) during the second half of the evolution period when the decoupler is gated off. Fourier transformation of the 2D-data matrix displays 13C chemical shift information along the F2 axis of the processed data and heteronuclear coupling constant information, scaled by J/2, in the F1 dimension.

Fig. 10.13. 2D J-resolved NMR spectrum of santonin (4). The data were acquired using the pulse sequence shown in Fig. 10.12. Chemical shifts are sorted along the F2 axis with heteronuclear coupling constant information displayed orthogonally in F . Coupling constants are scaled as J/2, since they evolve only during the second half of the evolution period, t /2. 13C signals are amplitude modulated during the evolution period as opposed to being phase modulated as in other 13C-detected heteronuclear shift correlation experiments.

An alternative method for excitation of nuclei over a range of chemical shifts is by irradiation with a weak, noise-modulated radio-frequency, instead of with strong r.f. pulses. In one realization of this method, protons were irradiated with repetitive sequences of noise that was truly random,162 and, in another,163 fluorine nuclei were excited by pseudo-random noise generated by amplitude modulation of the r.f. with maximum-length sequences of pulses from a computer or shift register (a series of flip-flop devices connected by feedback loops). With the carrier wave suppressed, the latter process is equivalent to phase modulation of the r.f. by+7r/2 radians when the pulse is turned on, and by —ir/2 radians when it is turned off. This method is identical with that used in most broadband, heteronuclear, noise decouplers, except that greater power is required for decoupling. 

In this review, we shall introduce some basic concepts about sohd-state NMR of half-integer quadrupolar nuclei and discuss the most useful and promising methods presently available to study them. These include older methods, such as Double Rotation (DOR) and Dynamic Angle Spinning (DAS), and novel techniques including MQMAS, Quadrupolar Phase Adjusted Spinning Sidebands QPASS, SateUite Transition (ST) MAS and Inverse-STMAS NMR, and Fast Amplitude Modulation (FAM). We also discuss several techniques based on dipolar interactions between quadrupolar and spin-1/2 nuclei, such as Cross-Polarization (CP) MQMAS, MQ Heteronuclear Correlation Spectroscopy... 

M. Bjerring and N. C. Nielsen, Solid-state NMR heteronuclear coherence transfer using phase and amplitude modulated rf irradiation at the Hartmann-Hahn sideband conditions. Chem. Phys. Lett., 2003, 382, 671-678. 

Figure 7.2. Amplitude modulation of the X-spin signal by heteronuclear coupling evolution during ti, illustrated for a coupled X-H pair. The doublet vectors evolve throughout ti but are frozen during t2 by the application of proton decoupling so the resultant X-spin signal displays pure amplitude modulation according to the heteronuclear coupling constant.

Fig. 8.8 Interferograms from the region surrounding the amplitude modulated resonance shown in Fig. 8.7. These data would correspond to transposition of the S[ti, F2] data set to the form S[F2, t ]. Fourier transformation of the interferograms extracts the heteronuclear cou-...

An improved variant of the popular double cross-polarisation (DCP) experiment for heteronuclear dipolar re-coupling in solid state NMR spectroscopy under MAS was introduced by Bjerring and Nielsen. By simple phase and amplitude modulation of the RF irradiation at the Hartman-Hahn sideband conditions, the new pulse sequence, dubbed iDCP, was shown to enable broadband excitation with the high efficiency of y-encoded coherence transfer. The efficiency and robustness of iDCP towards isotropic chemical shift variations and chemical shift anisotropies in the case of uniformly C, N-labelled proteins has been demonstrated numerically and experimentally by N to C coherence transfer for N-labelled N-Ac-L-valyl-L-leucine and C, N-labelled-L-threonine. 

A new pulse sequence has been described for the recoupling of heteronuclear dipolar interactions under MAS. " The method is similar to the PISEMA experiment, but employs a well-defined amplitude modulation of one of the two RF fields. The technique was used for measurements of dipolar couplings in... 

Figure 4-10. (a) 2D FSLG-CP MAS experiment. [64] Amplitude modulated FSLG-CP sequence is applied in the evolution period to recouple the heteronuclear dipolar interactions with simultaneous decoupUng of homonuclear H dipolar interactions, (b) Frequency offset refocused FSLG-CP sequence [54]... 

MAS does have an effect on the cross-polarization efficiency for mobile systems like elastomers [72]. For a static sample, the transfer rate is a function of u>c and has a maximum polarization-transfer rate at the Hartman-Hahn match and a slower polarization transfer with increasing mismatch. However, when the sample is spun with MAS, there is a very slow transfer of polarization at the Hartman-Hahn match, where the transfer is expected to be most rapid. A series of maxima in the transfer rate occurs when co c and co w are mismatched by a multiple of the spinning firequency. Thus, mismatching the cuic and )ih produces high signals at multiples of the MAS firequency. A series of maxima in Tch are observed as a result of an amplitude-modulated pattern due to C-H heteronuclear coupling [73]. 

Although in general, only one multiple-pulse sequence is applied to homonuclear spin systems, it can be useful to apply different multiple-pulse sequences to several nuclear species at the same time by using separate rf channels. In heteronuclear Hartmann-Hahn experiments, the same multiple-pulse sequence is usually applied simultaneously to two or more nuclear species. However, some selective homonuclear Hartmann-Hahn experiments are also based on the simultaneous irradiation of a multiple-pulse sequence at two or more different frequencies (see Section X). If only a single homonuclear rf channel is used, this can be achieved experimentally by adding an amplitude or phase modulation to the sequence, in order to create appropriate irradiation sidebands (Konrat... 

Phase-modulated multiple-pulse sequences with constant rf amplitude form a large class of homonuclear and heteronuclear Hartmann-Hahn sequences. WALTZ-16 (Shaka et al., 1983b) and DIPSI-2 (Shaka et al., 1988) are examples of windowless, phase-alternating Hartmann-Hahn sequences (see Table II). 

The decoupling efficiency depends on two factors [Engl, Mehl] (1) The amplitude (Oil = - y fii/ of the decoupling field in comparison with the strength of the heteronuclear dipole-dipole interaction. (2) The modulation of the heteronuclear dipole-dipole coupling by flip-flop transitions in the system of the abundant / spins, which communicate by the homonuclear dipole-dipole interaction. In addition to this, the influence of thermal motion has to be considered [Mehl]. 

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