Singlet States Open the Way to Longer Time-Scales in the Measurement of Diffusion by NMR Spectroscopy

ABSTRACT: Nuclear magnetic resonance is a powerful nonintrusive technique for measuring diffusion coefficients through the use of pulsed field gradients. The main limitation to the application range of this method is imposed by the relaxation time constants of the magnetization. The recently introduced singlet-state spectroscopy affords obtaining relaxation time constants for pairs of coupled spins which can be longer by more than an order of magnitude than the spin-lattice relaxation time constants. We review in this paper the advantages that are offered by these long relaxation time constants for diffusion measurements. Using experiments that combine singlet-state and diffusion spectroscopy, slower diffusion constants can be determined. The coupling of the two methods constitutes an alternative to the use of special probes equipped with strong gradients for the study of large molecules that diffuse slowly in solution

Proton hyperpolarisation preserved in long-lived states.

International audienceThe polarisation of abundant protons, rather than dilute nuclei with low gyromagnetic ratios, can be enhanced in less than 10 min using dissolution DNP and converted into a long-lived state delocalised over an ensemble of three coupled protons. The process is more straightforward than the hyperpolarisation of heteronuclei followed by magnetisation transfer to protons

Extending Timescales and Narrowing Linewidths in NMR

Among the different fields of research in nuclear magnetic resonance (NMR) which are currently investigated in the Laboratory of Biomolecular Magnetic Resonance (LRMB), two subjects that are closely related to each other are presented in this article. On the one hand, we show how to populate long-lived states (LLS) that have long lifetimes T_LLS which allow one to go beyond the usual limits imposed by the longitudinal relaxation time T_1. This makes it possible to extend NMR experiments to longer time-scales. As an application, we demonstrate the extension of the timescale of diffusion measurements by NMR spectroscopy. On the other hand, we review our work on long-lived coherences (LLC), a particular type of coherence between two spin states that oscillates with the frequency of the scalar coupling constant J_IS and decays with a time constant T_LLC. Again, this time constant T_LLC can be much longer than the transverse relaxation time T_2. By extending the coherence lifetimes, we can narrow the linewidths to an unprecedented extent. J-couplings and residual dipolar couplings (RDCs) in weakly-oriented phases can be measured with the highest precision

Singlet states open the way to longer time-scales in the measurement of diffusion by NMR spectroscopy

Nuclear magnetic resonance is a powerful nonintrusive technique for measuring diffusion coefficients through the use of pulsed field gradients. The main limitation to the application range of this method is imposed by the relaxation time constants of the magnetization. The recently introduced singlet-state spectroscopy affords obtaining relaxation time constants for pairs of coupled spins which can be longer by more than an order of magnitude than the spin-lattice relaxation time constants. We review in this paper the advantages that are offered by these long relaxation time constants for diffusion measurements. Using experiments that combine singlet-state and diffusion spectroscopy, slower diffusion constants can be determined. The coupling of the two methods constitutes an alternative to the use of special probes equipped with strong gradients for the study of large molecules that diffuse slowly in solution. © 2008 Wiley Periodicals, Inc. Concepts Magn Reson Part A 32A: 68-78, 2008

Water proton magnetisation lifetimes in the Earth\u27s magnetic field to follow free-radical formation in real time

Real-time imaging of free-radical formation by experimental methods is important in physical chemistry, biochemistry and radiobiology. Here we show for the first time that the formation of free-radicals during the time course of a chemical reaction can be imaged by monitoring the Earth’s field magnetic resonance of water protons in an open-coil spectrometer. The relaxation rate constants of water magnetisation are enhanced as reactions leading to hydroxyl radicals and subsequent oxygen formation proceed on timescales of tens of minutes. In our work the reaction of iodide-catalysed H2O2 decay was followed by Earth’s field relaxation measurements in real time. The relaxivity of the reaction product and that of several other paramagnetic compounds was measured in water. Spin-trap molecules were used to capture ∙OH radical species, thus altering the reaction rate in proportion to the formation of paramagnetic compounds. Thereby, a new experimental method opening the way for magnetic resonance imaging of reactive oxygen species in the Earth’s magnetic field is proposed, following the formation of intermediate and stable radical species in water

Long-lived coherences for homogeneous line narrowing in spectroscopy.

International audienceLine broadening, which can arise from inhomogeneities or homogeneous relaxation effects that lead to finite lifetimes of quantum states, is the Achilles' heel of many forms of spectroscopy. We show that line broadening may be considerably reduced by exploiting long lifetimes associated with superpositions of quantum states with different symmetry, termed long-lived coherences. In proton NMR of arbitrary molecules (including proteins) in isotropic solution, the slow oscillatory decays of long-lived coherences can yield spectra with very high resolution. This improvement opens the way to high-field magnetic resonance of molecular assemblies that are almost an order of magnitude larger than could be hitherto studied. Coherences between states of different symmetry may be useful in other forms of spectroscopy to cancel unwanted line broadening effects

Long-lived States in Multiple-Spin Systems

Long-lived spin states are excited in molecules featuring more than two isolated coupled spins, including amino acids. The figure shows the exponential recovery with the longest time-constant in aspartic acid, T1max=5.842±0.004 s, and of the decay of the long-lived state, TLLS=10.9±0.2 s). An improvement in spin memory by a factor 2 compared to longitudinal spin-lattice relaxation time constants is obtained for most systems

Measurement of slow diffusion coefficients of molecules with arbitrary scalar couplings via long-lived spin states.

International audienceNew experiments are described for the determination of very slow diffusion constants by nuclear magnetic resonance (NMR) using long-lived (singlet) states. These experiments are suitable for molecules or conformations featuring a wide range of J-couplings

Diffusion Coefficients of Biomolecules Using Long-Lived Spin States

We report the first observation of long-lived states (LLS) having lifetimes TLLS that exceed the corresponding spin−lattice relaxation times T1 by more than a factor 6 in a protein. Slow diffusion coefficients characteristic of large biomolecules can be determined by combining LLS methods with moderate pulsed field gradients (PFGs) available on commercial probeheads, as the extension of spin memory reduces the strain on the duration and/or strength of the PFGs. No isotope labeling of the biomolecule is necessary