Phase-alternated pulse sequence

The proton noise-decoupled 13c-nmr spectra were obtained on a Bruker WH-90 Fourier transform spectrometer operating at 22.63 MHz. The other spectrometer systems used were a Bruker Model HFX-90 and a Varian XL-100. Tetramethylsilane (TMS) was used as internal reference, and all chemical shifts are reported downfield from TMS. Field-frequency stabilization was maintained by deuterium lock on external or internal perdeuterated nitromethane. Quantitative spectral intensities were obtained by gated decoupling and a pulse delay of 10 seconds. Accumulation of 1000 pulses with phase alternating pulse sequence was generally used. For "relative" spectral intensities no pulse delay was used, and accumulation of 200 pulses was found to give adequate signal-to-noise ratios for quantitative data collection. 

Fig. 8. Pulse sequences for nuclear quadrupole resonance (NQR) excitation (a) spin-lock-spin-echo (SLSE) (b) phase-alternated spin-lock-spin-echo (PASLSE) (c) spin-lock-inversion-midecho (SLIME) (d) non-phase-alternated pulse sequence (NPAPS) (e) phase-alternated pulse sequence (PAPS). Numbers above the pulses indicate the relative phase of the RF dashed lines represent expected NQR signals.

Multipulse techniques, widely used in magnetic resonance, are also very common in NQR spectroscopy. They are effectively used for increasing sensitivity, reducing the duration of the experiment, and for measuring relaxation times in the sample. In NQR such well-known sequences as spin-echo, Carr-Purcell (CP), Meiboom-Gill-modified CP, spinlocking sequence and phase-alternated pulse sequence are widely used. There is a large practical... 

Fig. 14. The pulse sequence for recording the double-quantum 2H experiment.37 The entire experiment is conducted under magic-angle spinning. This two-dimensional experiment separates 2H spinning sideband patterns (or alternatively, static-like 2H quadrupole powder patterns) according to the 2H double-quantum chemical shift, so improving the resolution over a single-quantum experiment. In addition, the doublequantum transition frequency has no contribution from quadrupole coupling (to first order) so, the double-quantum spectrum is not complicated by spinning sidebands. Details of molecular motion are then extracted from the separated 2H spinning sideband patterns by simulation.37 All pulses in the sequence are 90° pulses with the phases shown (the first two pulses are phase cycled to select double-quantum coherence in q). The r delay is of the order 10 gs. The q period is usually rotor-synchronized.

As before, we use the table to adjust the phase according to the reference axis for each scan. Now we see that the 2IaIb terms alternate sign and cancel as we move from first scan, first term to second scan, second term to third scan, first term and finally to fourth scan, second term. Likewise, the 2IbIa terms alternate sign and cancel as we move down. So the ZQC, which exists between the second and third pulses of the DQF-COSY pulse sequence (Fig. 10.28) does not contribute anything to the observed FID after four scans. Just for completeness, we can show that all of the other terms present at the end of the 90S-fi-90j sequence are also destroyed by the phase cycle... 

Fig. 6. Top 2D MAT sequence for correlating isotopic chemical shift and CSA with two separate experiments P+ and P . All pulses following CP are 90°. A four-step phase cycling is used with 6 = —y, x, —y, x. and 62 = —y, x, x, -y. The receiver phases are x, -x, — y, -y for the P+ pulse sequence and x, —x,y, y for the P pulse sequence. (The sign of receiver phases with an asterisk depends on the relation between the pulse phase and the receiver phase of the particular spectrometer in use. These receiver phases must be changed in sign when the quadrature phase cycle (x,y, —x, -y) of the excitation pulse and the receiver phase in a single-pulse test experiment result in a null signal.) Phase alternation of the first H 90° pulse and quadrature phase cycling of the last 13C 90° pulse can be added to the above phase cycle. The time period T can be any multiple of a rotor period except for multiples of 3. Bottom 2D isotropic chemical shift versus CSA spectrum of calcium formate powder with a three-fold MAT echo extension. (Taken from Gan and Ernst178 with permission.)...

Fig. 16. Pulse sequence used in slow-spinning version of DECODER experiment. Each of the solid rectangles represents a 90° pulse. Standard CYCLOPS and spin-temperature alternation were used for phase cycling, (b) Pulse sequence used in the 3D experiment the phase cycling for the t part was similar to Grans170. (Adapted from Lewis et al.260 with permission.)...

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). 

This approach for the development of multiple-pulse sequences is only practical if a large number of sequences can be assessed in a short period of time. The final assessment of the quality of a multiple-pulse sequence must always be based on experiments. However, for the optimization of multiple-pulse sequences, experimental approaches are, in general, too slow and too expensive (instrument time ). An attractive alternative to experiments at the spectrometer is formed by numerical simulations, that is, experiments in the computer. In simulations it is also possible to take relaxation and experimental imperfections such as phase errors or rf inhomogeneity into account. In addition to the direct translation of a laboratory experiment into a computer experiment, it is possible to numerically assess the properties of a multiple-pulse sequence on several abstract levels, for example, based on the created effective Hamiltonian. If simple necessary conditions can be defined for a multiple-pulse sequence with the... 

Fig. 22. Maps of global quality factors (2 for multiple-pulse sequences based on phase-alternated, symmetric composite pulses R = SS with 5 = and A...

The BE-1 sequence is not compensated for rf inhomogeneity and after repeated application of the basis sequence, magnetization components that are orthogonal to the phase of the rf pulse are dephased. In BE-2, phase alternation of the rf pulses compensates for rf inhomogeneity and within the bandwidth of operation, isotropic transfer of x, y, and z magnetization is possible. Braunschweiler and Ernst (1983) also proposed more complicated isotropic-mixing sequences composed of 90° pulses with phases x, y, —X, and —y and delays. 

Bax and co-workers demonstrated that a homonuclear Hartmann-Hahn transfer of net magnetization can be obtained by the application of a spin-lock field, using CW irradiation (Bax and Davis, 1985a Davis and Bax, 1985) or by the DB-1 sequence that consists of a series of phase-alternated spin-lock pulses (Davis and Bax, 1985). The homonuclear Hartmann-Hahn effect caused by CW irradiation was discovered when artifacts in ROESY experiments were analyzed (Bax and Davis, 1985a). CW irradiation can be regarded as a homonuclear analog of spin-lock experiments for heteronuclear cross-polarization (Hartmann and Hahn,... 

In addition to multiple-pulse sequences that were derived from heteronuclear decoupling experiments, a number of rf sequences have been specifically developed for homonuclear Hartmann-Hahn transfer. A systematic search for phase-alternated composite 180° pulses R expanded in an MLEV-16 supercycle was reported by Glaser and Drobny (1990). Several clusters of good sequences were found for the transfer of magnetization in the offset range of 0.Av. However, substantially improved Hartmann-Hahn sequences were found after the condition that restricted R to be an exact composite 180° pulse on-resonance was lifted. For example, the GD-2 sequence is based on R = 290° 390° 290°, which is a composite 190° pulse on-resonance and is one of the best sequences based on composite pulses of the form R = (Glaser and Drobny, 1990). 

NOESY) sequence (see Fig. 26D, Table 3), which was computer-optimized by Kadkhodaei et al. (1993), is based on the MLEV-16 expanded composite pulse R = 15° 75°, 279°45°. In the TOWNY sequence, a 2 1 ratio of and is achieved by the created trajectory of z magnetization during the course of the optimized phase-alternated composite pulse R, without the need for additional delays or modulation of the rf amplitude. Clean Hartmann-Hahn mixing sequences based on shaped pulses were developed by Mayr et al. (1993). The parameters of the shaped MW-1 sequence (Mayr and Warren, 1995) are given in Table 3. 

Both limitations can be avoided if tailor-made multiple-pulse sequences are used for band-selective Hartmann-Hahn transfer. The so-called tailored TOCSY sequences TT-1 and TT-2 (see Table 4) were the first crafted band-selective Hartmann-Hahn sequences to be reported in the literature (Glaser and Drobny, 1989). Both phase-alternated sequences do not use any supercycling scheme. The TT-1 sequence with vf = 10 kHz was developed for band-selective coherence transfer between the offset ranges R- (-2.5 kHz < < —1.5 kHz) and Rj (1.5 kHz < Vj < 2.5 kHz). 

Only recently, new multiple-pulse sequences that were developed specifically for broadband heteronuclear Hartmann-Hahn experiments in liquids were reported. The SHR-1 sequence developed by Sunitha Bai et al. (1994) consists of a windowless phase-alternated composite pulse R, which is expanded according to the MLEV-8 supercycle. R was optimized based on a phase-distortionless single-spin 180° composite pulse and is related to the composite pulses used in DIPSI-1 (Shaka et al., 1988) and the composite pulses in the homonuclear IICT-1 sequence (Sunitha Bai and Ramachandran, 1993). The bandwidth of the SHR-1 sequence is comparable to the bandwidth of DIPSI-3, albeit with a slightly reduced transfer efficiency (Sunitha Bai et al., 1994 Fig. 33F). 

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