Spin selective pulse

The first QST procedure dedicated to quadrupolar systems was developed by Kampermann and Veeman for spin 3/2 nuclei [8]. It is a direct adaptation from the method used for spin 1/2, but uses transition selective pulses instead of spin selective pulses. Similar to the spin 1 /2 method, the transition selective pulses are used to bring an specific set of populations and coherences to the reading position of the deviation density matrix (single quantum coherences) and after that the NMR spectrum is acquired. The transformations (transition selective pulses) that are applied to the deviation density matrix Ap in order to bring the unknown elements to the reading positions are. 

Closer examination of equation B 1,14,3 reveals that, after the slice selection pulse, the spin isocln-omats at different positions in the gradient direction are not in phase. Rather they are rotated by i exp jyC. )tind... 

A simple, non-selective pulse starts the experiment. This rotates the equilibrium z magnetization onto the v axis. Note that neither the equilibrium state nor the effect of the pulse depend on the dynamics or the details of the spin Hamiltonian (chemical shifts and coupling constants). The equilibrium density matrix is proportional to F. After the pulse the density matrix is therefore given by and it will evolve as in equation (B2.4.27). If (B2.4.28) is substituted into (B2.4.30), the NMR signal as a fimction of time t, is given by (B2.4.32). In this equation there is a distinction between the sum of the operators weighted by the equilibrium populations, F, from the unweighted sum, 7. The detector sees each spin (but not each coherence ) equally well. 

Selective experiments can also be performed by the tailored excitation method of Tomlinson and Hill. The selective pulse is frequency-modulated with a function designed to yield zero effective field at the resonance offset of the neighboring nuclei. Although this technique is especially promising for studies of more-complex spin systems, its use is as yet very limited, in part because the instrumentation needed is not yet commercially available. 

Figure 5.10 (A) Selective spin-flip pulse sequence for recording heteronuclear 2D / resolved spectra. (B) Its effect on magnetization vectors. The selective 180° pulse in the middle of the evolution period eliminates the large one-bond coupling constants, /< ...

Figure 7.17 Pulse sequence for soft H,H-COSY with two selective pulses exciting the / multiplet and the second mixing pulse exciting the li multiplet of a three-spin system (/, /,)). (Reprinted from Mag. Reson. Chem. 29, H. Kessler et al., 527,...

A wide variety of ID and wD NMR techniques are available. In many applications of ID NMR spectroscopy, the modification of the spin Hamiltonian plays an essential role. Standard techniques are double resonance for spin decoupling, multipulse techniques, pulsed-field gradients, selective pulsing, sample spinning, etc. Manipulation of the Hamiltonian requires an external perturbation of the system, which may either be time-independent or time-dependent. Time-independent... 

Figure 6 X-half filters used for filtering or selecting 13C and 15N-attached protons. Thick and thin closed rectangles are 180° and 90° pulses, respectively, open rectangles are spin lock pulses. (A) A simple X-half filter (2). The delay t is equal to 0/(2[1JXH]) where 1JXH is the one-bond coupling between proton and either 13C (120 to 140 Hz) or 15N (95 Hz). The second 90° pulse is the editing...

A typical example is to apply the selective pulse to the carbonyl (or methyl) spins implying that the magnetization measured at the surrounding spins exclusively reflects dephasing due to interaction with exactly this spin (or spin type) while couplings to other nearby spins are refocused - forming the basis for, e.g.,... 

Fig. 1 (a) Schematic representation of a slice-selective two-dimensional spin-echo pulse... 

This contribution will describe the manipulation of spin multiplets as a whole, and the word selective - or soft - will be used for multiplet-selective pulses, in contrast to band-selective, which refers to a broader bandwidth which may affect several spins, and to transition selective when only one line is affected. The discussion will be based on proton spectra, but all aspects are similar for other nuclei. Soft pulses use lower amplitudes and much longer irradiation times than non-selective hard pulses. Typical durations for soft pulses are of the order of 1 to 500 ms with a peak amplitude... 

Similarly to non-selective experiments, the first operation needed to perform experiments involving selective pulses is the transformation of longitudinal order (Zeeman polarization 1 ) into transverse magnetization or ly). This can be achieved by a selective excitation pulse. The first successful shaped pulse described in the literature is the Gaussian 90° pulse [1]. This analytical function has been chosen because its Fourier transform is also a Gaussian. In a first order approximation, the Fourier transform of a time-domain envelope can be considered to describe the frequency response of the shaped pulse. This amounts to say that the response of the spin system to a radio-frequency (rf) pulse is linear. An exact description of the... 

There exists meanwhile a variety of frequency selective experiments still using the conventional CW irradiation as the ID NOE experiment, or upgraded with one or more selective pulses, as the ID TOCSY or the ID COSY experiment. These experiments and their many variants are probably the best choice in such cases as long as the response of a spin system to the perturbation of only one single spin or one single group of equivalent spins is of interest. If, however, and this is the most common situation, informations on several rather than only one spin-spin interaction is needed. 

Properties of the selective pulses are used therefore twofold in such experiments. Firstly, a selective pulse selectively perturbs the selected spin and the perturbation is distributed in the course of the experiment among the coupled spins, depending on the type of coupling (scalar, dipolar) and depending on the type of exchange mechanism (polarization transfer, cross polarization or cross relaxation). Secondly, the phase (selective 90° pulse) or the frequency (selective 180° pulse) of the selective pulse serve to label the response of both the selected and the residual coupled spins as positive or negative. 

In this experiment a series of selective 180° pulses serves to individually label selected carbon spins prior to the series of C- and H-pulses used for refocusing and polarization transfer. Therefore the frequency of any of these initial 180° pulses is set either on-resonance to the resonance of carbon i (fi), or set off-resonance (/off-res.) which simply inverts (label —) or not inverts (label -f) the corresponding spin polarization respectively. In the example below three target spins with resonance frequencies f, fi and /3 are chosen. A series of three selective pulses has to be applied and at least four experiments have to be performed with the frequencies of the selected pulses set as shown in the acquisition scheme below and four separately... 

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