Optimisation of excitation schemes for 14N overtone MAS NMR using numerically exact simulations.

Numerically exact simulations of the 14N overtone (14NOT) MAS NMR experiment are used to investigate the effects of the applied magnetic field strength as well as three types of excitation pulse. The results show that both the resolution and sensitivity of 14NOT MAS NMR increase linearly with the applied static magnetic field strength. Standard RF excitation pulses are compared with frequency-swept WURST pulses as well as several composite pulses. WURST pulses are demonstrated to provide the largest bandwidths, while the direction of the frequency sweep is shown to be important when these pulses are used for the direct observation of 14NOT signals. A composite pulse is shown to provide the most efficient excitation overall, but only when applied on resonance. WURST excitation pulses are therefore the best option when studying a sample with unknown 14N NMR parameters.

Revisiting NMR composite pulses for broadband (2)H excitation.

Quadrupolar echo NMR spectroscopy of static solids often requires RF excitation that covers spectral widths exceeding 100 kHz, which is difficult to obtain due to instrumental limitations. In this work we revisit four well-known composite pulses (COM-I, II, III and IV) for broadband excitation in deuterium quadrupolar echo spectroscopy. These composite pulses are combined with several phase cycling schemes that were previously shown to decrease finite pulse width distortions in deuterium solid-echo experiments performed with two single pulses. The simulations and experiments show that COM-II and IV composite pulses combined with an 8-step phase cycling aid in achieving broadband excitation with limited pulse width distortions.

Towards shorter composite 180° refocusing pulses for NMR.

Novel composite 180° pulses are designed for use in nuclear magnetic resonance (NMR) and verified experimentally using solution-state 1H NMR spectroscopy. Rather than being constructed from 180° pulses (as in much recent work), the new composite pulses are constructed from 90° pulses, with the aim of finding sequences that are shorter overall than existing equivalents. The primary (but not exclusive) focus is on composite pulses that are dual compensated - simultaneously broadband with respect to both inhomogeneity of the radiofrequency field and resonance offset - and have antisymmetric phase schemes, such that they can be used to form spin echoes without the introduction of a phase error. In particular, a new antisymmetric dual-compensated refocusing pulse is presented that is constructed from ten 90° pulses, equivalent to just five 180° pulses.

Composite pulse combinations for chirp excitation.

Composite pulses are the efficient method for broadband excitation to get control of the limitations of high field NMR, such as resonance offset effects with constraints on rf power that leads to signal intensity distortion. Phase-modulated chirp pulses are used as ordered composite pulse sequences in this paper as CHORUS sequence in a high-field NMR spectrometer (BRUKER 750 MHz) for broadband excitation. The composite pulse sequence applies chirp pulses with the forward and the reverse sweep mechanisms. A single excitation pulse combines adiabatic and non-adiabatic rotation, explained as a three-phase rotation, which leaves the magnetizing vectors to a non-uniform phase dispersion as a function of the offset frequency. One adiabatic refocusing pulse of the double sweep rate after the excitation pulse cannot satisfactorily compensate for the phase dispersion. Hence, composite self-refocussing CHORUS excitation pulse, with forward, reverse, and their combinations are used to remove the non-uniform phase dispersion generated due to offset resonance frequency. Four such combinations of composite pulses are produced with analytical explanation in this paper. MATLAB simulation results and experimental verification on the BRUKER 750 MHz NMR spectrometer of the composite pulses are also presented in this paper.

Rf-inhomogeneity compensation using method of Fourier synthesis.

In this paper, we propose a new method for design of composite pulses that are robust to rf-amplitude (rf-inhomogeneity). We call this, the method of Fourier synthesis. The method is general enough to design excitation, inversion, refocusing or arbitary flip angle pulses that are robust to rf-amplitude. The method can be tailored to have amplitude selective excitation. We experimentally show rf-compensation over a order of magnitude (20db) variation in rf-amplitude. The method is expected to find use in invivo NMR studies using surface coils, where there is large dispersion in rf-amplitude over the sample.

Composite pulses for RF phase encoded MRI: A simulation study.

BACKGROUND: In B1 encoded MRI, a realistic non-linear phase RF encoding coil will generate an inhomogeneous B1 field that leads to spatially dependent flip angles. The non-linearity of the B1 phase gradient can be compensated for in the reconstruction, but B1 inhomogeneity remains a problem. The effect of B1 inhomogeneity on tip angles for conventional, B0 encoded MRI, may be minimized using composite pulses. The objective of this study was to explore the feasibility of using composite pulses with non-linear RF phase encoding coils and to identify the most appropriate composite pulse scheme. METHODS: RF encoded signals were simulated via the Bloch equation for various symmetric, asymmetric and antisymmetric composite pulses. The simulated signals were reconstructed using a constrained least squares method. RESULTS: Root mean square reconstruction errors varied from 6% (for an asymmetric composite pulse) to 9.7% (for an antisymmetric composite pulse). CONCLUSION: An asymmetric composite pulse scheme created images with fewer artifacts than other composite pulse schemes in inhomogeneous B0 and B1 fields making it the best choice for decreasing the effects of spatially varying flip angles. This is contrary to the conclusion that antisymmetric composite pulses are the best ones to use for spin echo sequences in conventional, B0 encoded, MRI.

Composite-pulse and partially dipolar dephased multiCP for improved quantitative solid-state 13C NMR.

Improved multiple cross polarization (multiCP) pulse sequences for quickly acquiring quantitative 13C NMR spectra of organic solids are presented. Loss of 13C magnetization due to imperfect read-out and storage pulses in multiCP has been identified as a significant mechanism limiting polarization enhancement for 13C sites with weak couplings to 1H. This problem can be greatly reduced by composite 90° pulses with non-orthogonal phases that flip the magnetization onto the spin-lock field and back to the longitudinal direction for the 1H repolarization period; the observed loss is <3% for over ±10 kHz resonance offset and up to 20% flip-angle error. This composite-pulse multiCP (ComPmultiCP) sequence consistently provides performance superior to that of conventional multiCP, without any trade-off. The longer total CP time enabled by the composite pulses allows for a wider amplitude ramp during CP, which decreases the sensitivity to Hartmann-Hahn mismatch by a factor of two, with a <7% root-mean-square deviation within a 1-dB range for Boc-alanine. In samples with very short T1ρ, under-polarization of non-protonated carbons can be compensated by slight dipolar dephasing of CHn signals resulting from relatively weak decoupling during the Hahn spin echo period before detection. Quantitative spectra have been obtained by ComPmultiCP for low-crystallinity branched polyethylene at 4.5 kHz MAS, and in combination with partial dipolar dephasing for soil organic matter at 14 kHz MAS.

Effect of convection and B1 inhomogeneity on singlet relaxation experiments.

Nuclear spin singlet lifetimes can often exceed the T1 length scales by a large factor. This property makes them suitable for polarization storage. The measurement of such long lifetimes itself can become challenging due to the influence of even very weak relaxation mechanisms. Here we show that a judicious choice of the singlet-to-triplet conversion method is highly important in order to achieve reliable singlet relaxation measurements. In particular, we identify thermal convection, in connection with B1 field gradients, asa significant apparent decay mechanism, which limits the ability to measure the true singlet state lifetimes. Highly B1-compensated broadband singlet excitation/detection sequences are shown to minimize the influence of macroscopic molecular motion and B1 inhomogeneity.

The use of composite pulses for improving DEER signal at 94GHz.

The sensitivity of pulsed electron paramagnetic resonance (EPR) measurements on broad-line paramagnetic centers is often limited by the available excitation bandwidth. One way to increase excitation bandwidth is through the use of chirp or composite pulses. However, performance can be limited by cavity or detection bandwidth, which in commercial systems is typically 100-200MHz. Here we demonstrate in a 94GHz spectrometer, with >800MHz system bandwidth, an increase in signal and modulation depth in a 4-pulse DEER experiment through use of composite rather than rectangular π pulses. We show that this leads to an increase in sensitivity by a factor of 3, in line with theoretical predictions, although gains are more limited in nitroxide-nitroxide DEER measurements.

Optimization of identity operation in NMR spectroscopy via genetic algorithm: Application to the TEDOR experiment.

Identity operation in the form of π pulses is widely used in NMR spectroscopy. For an isolated single spin system, a sequence of even number of π pulses performs an identity operation, leaving the spin state essentially unaltered. For multi-spin systems, trains of π pulses with appropriate phases and time delays modulate the spin Hamiltonian to perform operations such as decoupling and recoupling. However, experimental imperfections often jeopardize the outcome, leading to severe losses in sensitivity. Here, we demonstrate that a newly designed Genetic Algorithm (GA) is able to optimize a train of π pulses, resulting in a robust identity operation. As proof-of-concept, we optimized the recoupling sequence in the transferred-echo double-resonance (TEDOR) pulse sequence, a key experiment in biological magic angle spinning (MAS) solid-state NMR for measuring multiple carbon-nitrogen distances. The GA modified TEDOR (GMO-TEDOR) experiment with improved recoupling efficiency results in a net gain of sensitivity up to 28% as tested on a uniformly 13C, 15N labeled microcrystalline ubiquitin sample. The robust identity operation achieved via GA paves the way for the optimization of several other pulse sequences used for both solid- and liquid-state NMR used for decoupling, recoupling, and relaxation experiments.

Theoretical calculation of a composite pulse for 2H broadband excitation by average Hamiltonian theory.

Quadrupolar echo NMR spectroscopy of solids often requires RF pulse excitation that covers spectral widths exceeding 100 kHz. In a recent work we found out that a four pulse, composite pulse COM-II ( [Formula: see text] ), provided robust broadband excitation for deuterium quadrupolar echo spectroscopy. Moreover, when combined with an eight step phase cycle, spectral distortions arising from finite pulse widths were greatly supressed. In this paper we report on a theoretical analysis COM-II with 8-step phase cycle by average Hamiltonian theory. This treatment is combined with the fictitious spin-1 operator formalism, and the mechanism of the 8-step phase cycling that minimizes the spectral distortions is discussed.

Genetic algorithm optimized triply compensated pulses in NMR spectroscopy.

Sensitivity and resolution in NMR experiments are affected by magnetic field inhomogeneities (of both external and RF), errors in pulse calibration, and offset effects due to finite length of RF pulses. To remedy these problems, built-in compensation mechanisms for these experimental imperfections are often necessary. Here, we propose a new family of phase-modulated constant-amplitude broadband pulses with high compensation for RF inhomogeneity and heteronuclear coupling evolution. These pulses were optimized using a genetic algorithm (GA), which consists in a global optimization method inspired by Nature's evolutionary processes. The newly designed π and π/2 pulses belong to the 'type A' (or general rotors) symmetric composite pulses. These GA-optimized pulses are relatively short compared to other general rotors and can be used for excitation and inversion, as well as refocusing pulses in spin-echo experiments. The performance of the GA-optimized pulses was assessed in Magic Angle Spinning (MAS) solid-state NMR experiments using a crystalline U-(13)C, (15)N NAVL peptide as well as U-(13)C, (15)N microcrystalline ubiquitin. GA optimization of NMR pulse sequences opens a window for improving current experiments and designing new robust pulse sequences.

A comparison and evaluation of reduced-FOV methods for multi-slice 7T human imaging.

Eight different reduced field-of-view (FOV) MRI techniques suitable for high field human imaging were implemented, optimized, and evaluated at 7T. These included selective Inner-Volume Imaging (IVI) based methods, and Outer-Volume Suppression (OVS) techniques, some of which were previously unexplored at ultra-high fields. Design considerations included use of selective composite excitation and adiabatic refocusing radio-frequency (RF) pulses to address B1 inhomogeneities, twice-refocused spin echo techniques, frequency-modulated pulses to sharply define suppressed regions, and pulse sequence designs to improve SNR in multi-slice scans. The different methods were quantitatively compared in phantoms and in vivo human brain images to provide measurements of relative signal to noise ratio (SNR), power deposition (specific absorption rate, SAR), suppression of signal, artifact strength and prevalence, and general image quality. Multi-slice signal losses in out-of-slice locations were simulated for IVI methods, and then measured experimentally across a range of slice numbers. Corrections for B1 nonuniformities demonstrated an improved SNR and a reduction in artifact power in the reduced-FOV, but produced an elevated SAR. Multi-slice sequences with reordering of pulses in traditional and twice-refocused IVI techniques demonstrated an improved SNR compared to conventional methods. The combined results provide a basis for use of reduced-FOV techniques for human imaging localized to a small FOV at 7T.