A novel diperoxovanadate complex NH4[OV(O2)2{2-(2'-pyridyl)-imidazole}]

Liquid nuclear magnetic resonance behaviors related to intermolecular dipolar interactions were investigated theoretically and experimentally in highly polarized two-component spin systems. A modified CRAZED pulse sequence was designed to investigate relative signal intensities with considerations of spin transverse relaxation, longitudinal relaxation, molecular diffusion, and optimal radio-frequency flip angles. The dissipation of the demagnetizing field due to relaxation and diffusion processes during the detection period was taken into account as well. For the first time, vigorous analytical expressions of the spin dynamics, including all the effects mentioned above, were derived from the combination of the demagnetizing field model and product operator formalism. In the regime where the linear approximation (γμoMot《1) is valid, these explicit analytical expressions can quantitatively describe the signal behaviors related to intermolecular dipolar interactions. All the theoretical predictions based on the analytical expressions for the directly excited component are in excellent agreement with experimental observations reported previously. Several valuable insights for the indirectly excited component were gained from the analytical expressions and verified by experimental measurements, including optimal radio-frequency flip angles, unusual relative signal intensities for n522 and n52, and unconventional diffusion and multi-exponential longitudinal relaxation processes, where n is the ratio of the coherence-selection gradient areas in the CRAZED pulse sequence. In addition, n-order diffusion coefficients of the directly and indirectly excited spins during the evolution period predicted by the demagnetizing field picture are found to be the same as those obtained with the combination of the intermolecular multiple-quantum picture and Gaussian phase distribution approximation which is valid in the case of unrestricted isotropic diffusion. These results suggest that a combination of the demagnetizing field model and product operator formalism provides excellent predictive power and computational convenience for diffusion and relaxation behaviors in two-component systems. These quantitative studies may also provide an opportunity to probe specific sources of new contrast for medical MR imaging.

The behaviors of molecular self-diffusion were simulated in complex spin systems with both intra-molecular scalar couplings and inter-molecular dipolar couplings in liquid nuclear magnetic resonance (NMR). The simulation algorithm was based on a combination of the non-linear Bloch equations, product operator matrix, and finite difference method. The simulated results reveal different diffusion behaviors of inter-and intra-molecular multiple-quantum coherences, coincident with theoretical predictions and experimental measurements. Compared with the Monte Carlo method, the finite difference method is more precise and efficient for simulating diffusion behaviors of multiple-quantum coherences.

A general analytical expression for intermolecular dipolar effects in liquids under the influence of magnetic field gradients of varying magnitudes, directions, and durations was explicitly derived with the density matrix formalism. We demonstrate that the time-averaged, not instantaneous, orientation of the applied gradients determines the contributions of long-range intermolecular dipole effects to multiple-quantum coherences. Theoretical and experimental results demonstrate, for the first time, that when the time-averaged orientation of a series of gradient pulses during the evolution period is at the magic angle, intermolecular dipolar effects are suppressed. The experimental evidence presented herein strongly supports our theoretical predictions.

A selective 2D intermolecular zero-quantum coherences pulse sequence, SEL-HOMOGENIZED sequence, was developed for high-resolution NMR spectra in inhomogeneous fields. The sequence designed to effectively suppress strong solvent signals and other trivial signals can greatly decrease the t1 noise artifacts. In the homogeneous-like 1D spectrum extracted from the 2D data, chemical shifts, coupling constants, multiplicity patterns, and relative peak areas are almost independent of the magnetic field inhomogeneity. Compared to the HOMOGENIZED sequence, the new sequence provides a total sensitivity enhancement of two times. It was also demonstrated that the theoretical predictions were in excellent agreement with the experimental results.