Adiabatic TOCSY MAS in liquids

The effect of magic angle spinning (MAS) of liquids upon the performance of various isotropic mixing sequences is investigated. Although the mathematical formalism for isotropic mixing under MAS conditions is similar for both liquids and solids, the mechanism through which the coherence transfer is disturbed is different. In liquids, the use of sample spinning in the presence of both RF and magnetic-field inhomogeneities introduces a modulation of the effective field, which compromises the performance of the conventional mixing sequences. This effect is further amplified by supercycles, which normally improve the performance of the mixing and decoupling experiments. It is demonstrated that adiabatic mixing sequences are less susceptible to such modulations and perform considerably better in TOCSY MAS experiments. The best performance of TOCSY MAS is observed under the rotational resonance condition when the sample appears static in the nutation reference frame.     

Broadband 13C-13C adiabatic mixing in solution optimized for high fields

Experiments which require mixing among spins with large frequency differences are generally performed with sequences based on composite pulses or computer-optimized cycles. Adiabatic pulses generally offer several advantages over other approaches, including greater single spin inversion bandwidths and tolerance to RF inhomogeneity. Here, a novel theoretical framework is presented in order to understand how spin-spin interactions are influenced by adiabatic inversion pulses, and insights from this approach are used to design more efficient adiabatic coherence exchange experiments. For very large frequency differences, this new approach generally offers improved results over previously applied mixing sequences, as applied to 13C-13C experiments which are the basis of modern sidechain assignment techniques in proteins. It is also anticipated that the approach presented here will be applicable to the analysis of various alternative approaches to adiabatic mixing.     

Heteronuclear decoupling by optimal tracking

The problem to design efficient heteronuclear decoupling sequences is studied using optimal control methods. A generalized version of the gradient ascent engineering (GRAPE) algorithm is presented that makes it possible to design complex non-periodic decoupling sequences which are characterized by tens of thousands of pulse sequence parameters. In contrast to conventional approaches based on average Hamiltonian theory, the concept of optimal tracking is used: a pulse sequence is designed that steers the evolution of an ensemble of spin systems such that at a series of time points, a specified trajectory of the density operator is tracked as closely as possible. The approach is demonstrated for the case of low-power heteronuclear decoupling in the liquid state for in vivo applications. Compared to conventional sequences, significant gains in decoupling efficiency and robustness with respect to offset and inhomogeneity of the radio-frequency field were found in simulations and experiments.     

Design of Selective Adiabatic Inversion Pulses Using the Adiabatic Condition

Adiabatic RF pulses play an important role in spin inversion due to their robust behavior in the presence of inhomogeneous RF fields. These pulses are characterized by the trajectory swept by the tip of theB_effvector and the rate of motion along it. In this paper, we describe a method by which optimized modulation functions can be constructed to render insensitivity toB₁inhomogeneity over a predeterminedB₁range and over a wide band of frequencies. This is accomplished by requiring that the optimized pulse fulfill the adiabatic condition over this range ofB₁inhomogeneity and over the desired frequency band for the complete duration of the pulse. A trajectory similar to the well-known sech/tanh adiabatic pulse, i.e., a half-ellipse, is used. The optimization process improves the slice profile by optimizing the rate of motion along this trajectory. The optimized pulse can be tailored to the specific design requirements; in particular, the transition sharpness may be traded off against the inverted bandwidth. Two design examples, including experimental results, demonstrate the superiority of the optimized pulses over the conventional sech/tanh pulse: in the first example, a large frequency band is to be inverted using a weak RF amplitude in a short time. In the second example, a pulse with a very sharp transition is required.     

Tagging of the Magnetization with the Transition Zones of 360° Rotations Generated by a Tandem of Two Adiabatic DANTE Inversion Sequences

A new technique is presented for generating myocardial tagging using the signal intensity minima of the transition zones between the bands of 0° and 360° rotations, induced by a tandem of two adiabatic delays alternating with nutations for tailored excitation (DANTE) inversion sequences. With this approach, the underlying matrix corresponds to magnetization that has experienced 0° or 360° rotations. The DANTE sequences were implemented from adiabatic parent pulses for insensitivity of the underlying matrix to B₁ inhomogeneity. The performance of the proposed tagging technique is demonstrated theoretically with computer simulations and experimentally on phantom and on the canine heart, using a surface coil for both RF transmission and signal reception. The simulations and the experimental data demonstrated uniform grid contrast and sharp tagging profiles over a twofold variation of the B₁ field magnitude.     

Radio-frequency μSR experiments at the ISIS pulsed muon facility

This paper explores the use of pulsed radio-frequency (RF) techniques to remove the frequency limitations imposed on conventional transverse muon spin rotation (μSR) experiments at a pulsed muon source by the finite muon pulse width. The implementation of the 90° pulse technique is demonstrated by observing the free precession signal of diamagnetic muons implanted in polythene, the change in signal amplitude as a function of RF pulse length is plotted and the precise condition for a 90° pulse determined. The technique is evaluated by comparing measurements made using conventional spin rotation experiments to those employing pulsed RF methods. The potential for applying standard NMR multiple-pulse methods to the μSR experiment is considered and the use of two-pulse RF sequences (90° _x ?τ?90° _x and 90° _x ?τ?180° _x ) to form a muon spin echo demonstrated.     

Majorana flipping of quarkonium spin states in transient magnetic field

We demonstrate that spin flipping transitions occur between various quarkonium spin states due to transient magnetic field produced in non central heavy ion collisions (HICs). The inhomogeneous nature of the magnetic field results in non adiabatic evolution of (spin)states of quarkonia moving inside the transient magnetic environment. Our calculations explicitly show that the consideration of azimuthal inhomogeneity gives rise to dynamical mixing between different spin states owing to Majorana spin flipping. Notably, this effect of non-adiabaticity is novel and distinct from previously predicted mixing of the singlet and one of the triplet states of quarkonia in the presence of a static and homogeneous magnetic field.     

Gradient- and Sensitivity-Enhanced TOCSY Experiments

A pulsed field gradient version of the sensitivity-enhanced 2D TOCSY experiment is proposed which yields high-quality spectra with improved sensitivity and a minimum of two scans pert₁increment. For rapid acquisition of 1D TOCSY spectra, the 1D DPFGSE–TOCSY experiment was modified to include phase-encoded multiple-selective excitation followed by a simple spectral editing. Combination of these two building blocks is used in a sensitivity-enhanced 2D analog of the 3D TOCSY–TOCSY experiment which provides an efficient tool for resolving severely overlapped signals of oligomers in short experimental time.     

A comparison of NCO and NCA transfer methods for biological solid-state NMR spectroscopy

Three different techniques (adiabatic passage Hartman-Hahn cross-polarization, optimal control designed pulses, and EXPORT) are compared for transferring (15)N magnetization to (13)C in solid-state NMR experiments under magic-angle-spinning conditions. We demonstrate that, in comparison to adiabatic passage Hartman-Hahn cross-polarization, optimal control transfer pulses achieve similar or better transfer efficiencies for uniformly-(13)C,(15)N labeled samples and are generally superior for samples with non-uniform labeling schemes (such as 1,3- and 2-(13)C glycerol labeling). In addition, the optimal control pulses typically use substantially lower average RF field strengths and are more robust with respect to experimental variation and RF inhomogeneity. Consequently, they are better suited for demanding samples.     

Composite pulses for RF phase encoded MRI: A simulation study

BackgroundIn 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.MethodsRF 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.ResultsRoot mean square reconstruction errors varied from 6% (for an asymmetric composite pulse) to 9.7% (for an antisymmetric composite pulse).ConclusionAn 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.     

Spin-state-selective excitation in selective 1D inverse NMR experiments

A general and very simple strategy for achieving clean spin-state-selective excitation with full sensitivity in carbon-selective gradient-enhanced 1D HMQC and HSQC pulse schemes is presented. The incorporation of an additional hard 90 degrees (13)C pulse applied along a specific orthogonal axis just prior to acquisition into the conventional sequences allows us to select a simultaneous coherence transfer pathway which usually is not detected. The superimposition of this resulting antiphase magnetization to the conventional in-phase magnetization gives the exclusive excitation of the directly attached proton showing only the alpha or beta spin state of the passive (13)C nucleus. The propagation of this particular spin state to other protons can be accomplished by adding any homonuclear mixing process just after this supplementary pulse. Such an approach affords a suite of powerful selective 1D (13)C-edited NMR experiments which are helpful for resonance assignment purposes in overcrowded proton spin systems and also for the accurate determination of the magnitude and sign of long-range proton-carbon coupling constants in CH spin sytems for samples at natural abundance. Such measurements are performed by measuring the relative displacement of relayed signals in the corresponding alpha and beta 1D subspectra.     

Applications of DNP-NMR for the measurement of heteronuclear T1 relaxation times

Measurement of heteronuclear spin-lattice relaxation times is hampered by both low natural abundance and low detection sensitivity. Combined with typically long relaxation times, this results in extended acquisition times which often renders the experiment impractical. Recently a variant of dynamic nuclear polarisation has been demonstrated in which enhanced nuclear spin polarisation, generated in the cryo-solid state, is transferred to the liquid state for detection. Combining this approach with small flip angle pulse trains, similar to the FLASH-T(1) imaging sequence, allows the rapid determination of spin-lattice relaxation times. In this paper we explore this method and its application to the measurement of T(1) for both carbon-13 and nitrogen-15 at natural abundance. The effects of RF inhomogeneity and the influence of proton decoupling in the context of this experiment are also investigated.     

Improved Broadband Inversion Performance for NMR in Liquids

New NMR broadband inversion pulses that compensate both for resonance offset and radiofrequency (RF) inhomogeneity are described. The approach described is a straightforward computer optimization of an initial digitized waveform generated from either a constant-amplitude frequency sweep or from an existing composite inversion pulse. Problems with convergence to local minima are alleviated by the way the optimization is carried out. For a given duration and maximum allowable RF field strength B₁ (but not necessarily given RMS power deposition), the resultant broadband inversion pulse (BIP) shows superior inversion compared to inversion pulses obtained from previous methods, including adiabatic inversion pulses. Any existing BIP can be systematically elaborated to build up longer inversion pulses that perform over larger and larger bandwidths. The resulting pulse need not be adiabatic throughout its duration or across the entire operational bandwidth.     

J-ONLY-TOCSY: efficient suppression of RDC-induced transfer in homonuclear TOCSY experiments using JESTER-1-derived multiple pulse sequences

The main purpose of homonuclear Hartmann-Hahn or TOCSY experiments is the assignment of spin systems based on efficient coherence transfer via scalar couplings. In partially aligned samples, however, magnetization is also transferred via residual dipolar couplings (RDCs) and therefore through space correlations can be observed in COSY and TOCSY experiments that make the unambiguous assignment of covalently bound spins impossible. In this article, we show that the JESTER-1 multiple pulse sequence, originally designed for broadband heteronuclear isotropic Hartmann-Hahn transfer, efficiently suppresses the homonuclear dipolar coupling Hamiltonian. This suppression can be enhanced even further by variation of the supercycling scheme. The application of the resulting element in homonuclear TOCSY periods results in coherence transfer via J-couplings only. As a consequence, the assignment of scalar coupled spin systems is also possible in partially aligned samples. The bandwidth of coherence transfer for the JESTER-1-derived sequences is comparable to existing TOCSY multiple pulse sequences. Results are demonstrated in theory and experiment.     

Multiple-Pulse Mixing Sequences That Selectively Enhance Chemical Exchange or Cross-Relaxation Peaks in High-Resolution NMR Spectra

Rotating-frame NMR experiments which either emphasize or suppress cross relaxation, and which simultaneously suppress TOCSY, COSY, and zero-quantum peaks in NMR spectra, are presented and analyzed. The new experiments rely on mixing sequences which follow naturally from thetransverse-ROESY (Tr-ROESY) sequence of Hwang and Shaka, and which are applicable to larger molecules in solution (spin diffusion limit). In the first variant a modified Tr-ROESY sequence, called multiple-pulse ROESY (MP-ROESY), is used to enhance cross-relaxation peak intensity compared to Tr-ROESY; in the second, called phase-modulated CLEAN chemical exchange (CLEANEX-PM), cross-relaxation peaks are greatly attenuated. The two methods are thus complementary: MP-ROESY is used to observe Overhauser peaks, and CLEANEX-PM is used to eliminate them, permitting clear observation of chemical exchange peaks alone. The new techniques are examined by theory and experiment. Practical guidelines that will result in high-quality spectra are given, including the judicious use of continuous weak static magnetic field gradients.     

Radiofrequency pulse sequences which compensate their own imperfections. 1980

Radiofrequency pulse sequences are described which have the same overall effect as a single 90° or 180° pulse but which compensate the undesirable effects of resonance offset and spatial inhomogeneity of the radiofrequency field H₁. These “composite” pulses are built up from a small number of conventional pulses which rotate the nuclear magnetization vectors about different axes in the rotating frame, while in the intervals between pulses a limited amount of free precession may be allowed to occur. Insight into the way in which pulse imperfections are compensated is obtained by computer simulation of trajectories of families of nuclear spin “isochromats” representing a distribution of H₁ intensity or resonance offset. Composite 90° pulses are suggested as a method of reducing systematic errors in spin-lattice relaxation times derived from progressive saturation or saturation-recovery experiments, and as the preparation pulse of a spin-locking experiment. A test of the effectiveness of the composite 180° pulse sequence has been made by using it for population inversion in a spin-lattice relaxation measurement, where T₁ is derived from the null point in the recovery curve, a technique known to be very sensitive to pulse imperfections.     

Discerning the degenerate transitions of scalar coupled H NMR spectra: Correlation and resolved techniques at higher quantum

The blend of spin topological filtering and the spin state selective detection of single quantum transitions by the two dimensional multiple quantum-single quantum correlation and higher quantum resolved techniques have been employed for simplifying the complexity of scalar coupled ¹H NMR spectra. The conventional two dimensional COSY and TOCSY experiments, though identify the coupled spin networks, fail to differentiate them due to severe overlap of transitions. Non-selective excitation of homonuclear higher quantum of protons results in filtering of spin systems irrespective of their spin topologies. The spin state selection by passive ¹⁹F spins provides fewer transitions in each cross section of the single quantum dimension simplifying the analyses of the complex spectra. The degenerate single quantum transitions are further discerned by spin selective double and/or triple quantum resolved experiments that mimic simultaneous heteronuclear and selective homonuclear decoupling in the higher quantum dimension. The techniques aided the determination of precise values of spectral parameters and relative signs of the couplings.     

Simulation of CPMAS Signals at High Spinning Speeds

The spin dynamics of anS( )I_Nsystem during the CP mixing time of continuous wave and variable amplitude cross-polarization magic angle spinning (CWCPMAS and VACPMAS) experiments is discussed. The signal enhancement of a low abundantSspin, coupled to a set ofN= 6 coupled spins withI= , is evaluated as a function of the length of the mixing time. For CWCPMAS this signal is first evaluated in the frequency domain and then transformed to the time domain. These calculations provide some additional insight into the CP spin dynamics and enable a practical approach toward the evaluation of CP signals of large spin systems. In addition the adiabatic character of the ramped VACPMAS experiments is discussed andS-spin signals of a spin system withN= 6 are simulated. Estimates of the upper bounds of the CP signals as a function of the number ofIspins in anS( )I_Nsystem are given and compared with the calculated values.