Journal of Magnetic Resonance - Vol 193 Issue 1

Probing the validity of average Hamiltonian theory for spin I = 1, 3/2 and 5/2 nuclei by analyzing a simple two-pulse sequence
E.S. Manangaa, b, C.D. Hsuc, S. Ishmaela, T. Islama and G.S. Boutis
In this work, we investigate the accuracy of controlling spin I = 1, 3/2 and 5/2 spin systems by average Hamiltonian theory. By way of example, we consider a simple two-pulse echo sequence and compare this perturbation scheme to a numerical solution of the Von Neumann equation. For the different values of I, we examine this precision as a function of the quadrupolar coupling as well as various experimental parameters such as the pulse spacing and pulse width. Experiments and simulations on I = 3/2 and I = 5/2 spin systems are presented that highlight a spectral artifact introduced due to finite pulse widths as predicted by average Hamiltonian theory. The control of these spin systems by this perturbation scheme is considered by investigating a phase cycling scheme that suppresses these artifacts to zeroth-order of the Magnus expansion.

Direct measurement of dipole–dipole/CSA cross-correlated relaxation by a constant-time experiment
Yizhou Liua and James H. Prestegard
Relaxation rates in NMR are usually measured by intensity modulation as a function of a relaxation delay during which the relaxation mechanism of interest is effective. Other mechanisms are often suppressed during the relaxation delay by pulse sequences which eliminate their effects, or cancel their effects when two data sets with appropriate combinations of relaxation rate effects are added. Cross-correlated relaxation (CCR) involving dipole–dipole and CSA interactions differ from auto-correlated relaxation (ACR) in that the signs of contributions can be changed by inverting the state of one spin involved in the dipole–dipole interaction. This property has been exploited previously using CPMG sequences to refocus CCR while ACR evolves. Here we report a new pulse scheme that instead eliminates intensity modulation by ACR and thus allows direct measurement of CCR. The sequence uses a constant time relaxation period for which the contribution of ACR does not change. An inversion pulse is applied at various points in the sequence to effect a decay that depends on CCR only. A 2-D experiment is also described in which chemical shift evolution in the indirect dimension can share the same constant period. This improves sensitivity by avoiding the addition of a separate indirect dimension acquisition time. We illustrate the measurement of residue specific CCR rates on the non-myristoylated yeast ARF1 protein and compare the results to those obtained following the conventional method of measuring the decay rates of the slow and fast-relaxing 15N doublets. The performances of the two methods are also quantitatively evaluated by simulation. The analysis shows that the shared constant-time CCR (SCT–CCR) method significantly improves sensitivity.

An analysis of phase-modulated heteronuclear dipolar decoupling sequences in solid-state nuclear magnetic resonance
Rajendra Singh Thakura, Narayanan D. Kururb and P.K. Madhu
The design of variants of the swept-frequency two-pulse phase modulation sequence for heteronuclear dipolar decoupling in solid-state NMR is reported, their performance evaluated, and compared with other established sequences like TPPM and SPINAL. Simulations performed to probe the role of the homonuclear 1H–1H bath show that the robustness of the decoupling schemes improves with the size of the bath. In addition, these simulations reveal that the homonuclear 1H–1H bath also leads to broad baselines at high MAS rates. Results from a study of the SPINAL decoupling scheme indicate that optimisation of the starting phase and phase increment improves its performance and efficiency at high MAS rates. Additionally, experiments performed on a liquid crystal display the role of the initial phase in SPINAL-64 and sequences in the SWf-TPPM family.

Fast amplitude-modulated pulse trains with frequency sweep (SW-FAM) in solid-state NMR of spin-7/2 nuclei
Thomas Bräunigera and P.K. Madhu
We here investigate the sensitivity enhancement of central-transition NMR spectra of quadrupolar nuclei with spin-7/2 in the solid state, generated by fast amplitude-modulated RF pulse trains with constant (FAM-I) and incremented pulse durations (SW-FAM). Considerable intensity is gained for the central-transition resonance of single-quantum spectra by means of spin population transfer from the satellite transitions, both under static and magic-angle-spinning (MAS) conditions. It is also shown that incorporation of a SW-FAM train into the excitation part of a 7QMAS sequence improves the efficiency of 7Q coherence generation, resulting in improved signal-to-noise ratio. The application of FAM-type pulse trains may thus facilitate faster spectra acquisition of spin-7/2 systems.

The generation of intense radiofrequency fields in μcoils
Edward W. Hagamana, Jian Jiaoa and Tony Moore
Large amplitude radiofrequency (rf) fields hold great promise in wide line NMR where it becomes possible to excite the full breadth of the line in a quantitative fashion. Applications in quadrupole NMR and in NMR of paramagnetic systems benefit greatly from intense fields. Spin manipulations in multiple quantum NMR experiments, specifically, the generation of multiple quantum coherence in MQ NMR, are more efficiently produced using intense rf fields. In this work we describe a μcoil probe that produces an rf field of 25 MHz, more than five times larger than the greatest rf field reported in the literature. We accomplish this in a robust, 127 μm diameter solenoid coil using 1 kW of rf power.

An alternative tuning approach to enhance NMR signals
Denis J.-Y. Mariona and Hervé Desvaux
By using spin-noise type measurement we show that the resonance frequency of the reception circuit of classical NMR spectrometers does not match the Larmor frequency even if, in emission, the electronic circuit is perfectly tuned at the Larmor frequency and matches the amplifier impedance. We also show that this spin-noise method can be used to ensure a match between the Larmor frequency and the reception circuit resonance frequency. In these conditions, (i) the radiation damping field is in perfect quadrature to the magnetization and (ii) the NMR signal level and potentially the signal-to-noise ratio, are enhanced. This choice induces a change of the probe resonance frequency by several hundreds of kHz for 500 or 700 MHz spectrometer. We show that the resulting mismatch condition for emission can be removed by adding other tuning and matching degrees of freedom located on the excitation line (or by symmetry on the reception line) decoupled to the probe resonance circuit by the crossed diodes.