Hydrogen bonds lengths in nucleic acids estimated from longitudinal nitrogen-15 relaxation

A new NMR method has been designed for the measurement of the longitudinal relaxation rates of both donor and acceptor nitrogen-15 nuclei in Watson-Crick base pairs in 15N-enriched nucleic acids. The experiment was applied to a 22-nucleotide RNA hairpin. The lengths of four hydrogen bonds could be estimated from the longitudinal relaxation rates.     

The effect of cross relaxation on the longitudinal relaxation times of small ligands binding to macromolecules

The effect of binding on nuclear longitudinal relaxation times of a small ligand interacting with a macromolecule has been studied both theoretically and experimentally. The occurrence of cross relaxation between ligand and protein nuclei is proposed to explain the usually observed decrease in T₁ as resulting from the binding. A simplified model is presented to account for this decrease theoretically. The interaction of α-ketoglutarate with the enzyme glutamate dehydrogenase was studied as an experimental example. The data obtained are in good agreement with the theory. Evidence is presented to show that the observed effects result from binding to one specific site. The consequences of cross relaxation for macromolecular rotational correlation times obtained from nuclear magnetic relaxation data are discussed.     

The limit diffusion mechanism of relaxation for spin systems

The diffusion limit theorem for stochastic differential equations is applied to analyse the dynamical evolutions of spin systems. Bloch equations are derived and the stability of asymptotic evolutions is proved. The theory is applied to nuclear magnetic relaxation of two spins.     

Direct measurement of carrier spin relaxation times in opaque solids using the specular inverse Faraday effect

Using a spectroscopic technique based on the transient specular inverse Faraday effect (SIFE) we found the electron spin relaxation time in bulk GaAs at room temperature to be 11 ± 1 ps. The hole spin dynamics gives a SIFE signal of the opposite sign and may be resolved in the time-domain.     

Spectral distribution of relaxation times in spin glasses

Recent neutron scattering measurements on spin glasses show that the dynamics of the spin systems can be best described in terms of wide spectral distribution of relaxation times evolving continuously with decreasing temperature but which is devoid of any critical behaviour, either speeding up or slowing down, at any finite temperature including the spin glass “freezing temperature T_sg”. It is argued that the latter temperature itself is dependent on the time constant of measurement for all spin glasses in general; the observed variation with frequency being less pronounced in some systems than others owing to some special characteristics of their spin dynamics such as, for example, the presence of parallel channels of rapid relaxation provided by the Korringa coupling in metallic spin glasses. The neutron scattering measurements presented here enable us to propose plausible forms for the density of relaxation times of the spin system and to show that the logarithmic frequency dependence of the freezing temperature observed in low frequency ac susceptibility measurements follows naturally from a uniform density of relaxation times at these frequencies.     

Measurement of spin-lattice relaxation times with longitudinal detection

New experimental schemes to measure spin-lattice relaxation times T₁ on the basis of inversion-recovery and saturation-recovery experiments with longitudinal detection are introduced. With this approach, paramagnetic species with T₁ values as short as 20 ns can be measured. Possibilities to reduce unwanted signals and instrumental artifacts are analyzed. An experiment where the signal is induced directly by the time-dependent M₂ magnetization is also proposed. Experimental results for organic radicals and defect centers are presented and compared with data obtained with conventional techniques, and a metal complex at 250 K is analyzed where it is very difficult to get information about relaxation times with established methods because of fast spin-spin relaxation.     

Measurement of longitudinal relaxation times using surface coils

The poor B₁ field homogeneity associated with surface coils reduces the effectiveness of inversion-recovery techniques for determination of T₁ relaxation times. This paper presents a variation of the saturation-recovery T₁ experiment which introduces periodic phase shifts in the saturating irradiation to achieve rapid and effective saturation of the sample magnetization, thereby avoiding the complications of B₁ field inhomogeneity. Comparison of the presented technique with the inversion-recovery technique utilizing a composite inverting pulse and alternating phase acquisition is provided. A discussion of the relative merits of each technique is presented.     

An MR imaging method for simultaneous measurement of gaseous diffusion constant and longitudinal relaxation time

A magnetic resonance imaging method for simultaneous and accurate determination of gaseous diffusion constant and longitudinal relaxation time is presented. The method is based on direct observation of diffusive motion. Initially, a slice-selective saturation of helium-3 (3He) spins was performed on a 3He/O2 phantom (9 atm/2 atm). A time-delay interval was introduced after saturation, allowing spins to diffuse in and out of the labeled slice. Following the delay interval a one-dimensional (1-D) projection image of the phantom was acquired. A series of 21 images was collected, each subsequent image having been acquired with an increased delay interval. Gradual spreading of the slice boundaries due to diffusion was thus observed. The projection profiles were fit to a solution of the Bloch equation corrected for diffusive motion. The fitting procedure yielded a value of D3He = 0.1562+/-0.0013 cm2/s, in good agreement with a measurement obtained with a modified version of the standard pulsed-field gradient technique. The method also enabled us to accurately measure the longitudinal relaxation of 3He spins by fitting the change of the total area under the projection profiles to an exponential. A value of T1 = 1.67 s (2 T field) was recorded, in excellent agreement with an inversion recovery measurement.     

The measurement of the rotational relaxation times of OCS from the nutation signals

The time dependence of microwave absorption was measured for the J = 2-1 and J = 3-2 transitions of OCS under on- and off-resonant conditions utilizing Stark and source modulation, respectively. The two effective pressure parameters obtained under the two conditions, which correspond to $\text{(T}{}_2{}^{\mathrm{?1}}\text{+ T}{}_1{}^{\mathrm{?1}}\text{)}\text{4πP}$ and $\text{(2πT}{}_2\text{P)}{}^{\mathrm{?1}}$, respectively, according to the Bloch equation, are different beyond experimental error; the difference $\text{(T}{}_2{}^{\mathrm{?1}}\text{? T}{}_1{}^{\mathrm{?1}}\text{)}\text{2πP}$ is 0.94 ± 0.38 (2.5σ) MHz/Torr for J = 2?1. This difference was also determined to be 1.19 ± 0.30 MHz/Torr from the dependence of the nutation frequency on the microwave power.     

Clarification of the measurement of surface spin relaxation via conduction electron spin resonance

We clarify the parameterization of the probability of transverse conduction electron spin relaxation. ?, at the surface of a metal. Using Walker's boundary condition on the transverse spin magnetization, we have calculated the ? and thickness dependence of the spin resonance linewidth. The results are discussed in simple physical terms. The recent work of Allam and Vigouroux is shown to contain errors.     

The determination of the spin diffusion rate from the dipolar relaxation of a rotating sample

It is shown that the observed dipolar spin-lattice relaxation time is shortened by sample rotation. This can be used to determine experimentally the spin diffusion rate.     

Spectrum of relaxation times for ising spin clusters in random fields

Summary Exact results on the single-spin-flip Glauber dynamics of six-coupled random field Ising spins with the coordination number of four are presented. Two distributions of random fields (RF), binary (BD) and Gaussian (GD) ones, are investigated. The effects of the static magnetic field are discussed. In the zero-magnetic-field case, the number of diverging relaxation times is equal to the number of energy minima minus one. This rule breaks in the presence of a magnetic field. The longest relaxation times in the absence of the field verify the Arrhenius law with the energy barrier determined by the energy needed to invert the ground-state spin configuration. At low temperature, according to the Arrhenius law, the spectrum of relaxation times shows a two-peaked distribution on a logarithmic scale. In the GD case of RF, the energy barrier distribution is continuous, while it is quasi-discrete in the BD case.     

Fast and simultaneous measurement of longitudinal and transverse NMR relaxation times in a single continuous wave free precession experiment

The purpose of this communication is to describe a method for rapid and simultaneous determination of longitudinal (T1) and transversel (T2) relaxation times, based on a single continuous wave free precession (CWFP) experiment which employs RF pulses with a pi/2 flip angle. We analyze several examples, involving nuclei such as 1H, 31P, and 19F, where good agreement with T1 and T2 measurements obtained by traditional methods is apparent. We also compare with the more time-consuming steady-state free precession (SSFP) method of Kronenbitter and Schwenk where several experiments are needed to determine the optimum flip angle. The role of an inhomogeneous magnetic field on the observed decays and its effect upon the accuracy of relaxation times obtained by these methods is examined by comparing numerical simulations with experimental data. Possible sources of error and conditions to minimize its effects are described.     

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.     

Methodology for the measurement and analysis of relaxation times in proton imaging

Measurements of proton T1 and T2 were performed on GdCl3 solutions (20 less than T2 less than 500 msec, 90 less than T1 less than 1000 msec) on large-bore NMR imaging systems operating at 1.0T and 1.5T. CPMG multi-echo (ME), multiple saturation recovery (MSR) and modified fast inversion recovery (MFIR) pulse sequences as well as a sequence that combines and interleaves T1 and T2 weighted data acquisition (which we call "multiple saturation-recovery multiple-echo" (MSRME) were used. The relaxation data are compared to those obtained on a small bore NMR spectrometer operated at 1.5T. T1 and T2 values for the solutions were found to be the same within 10% for the two fields. Reproducibility of measurements of T1, T2 and the unnormalized spin density of the solutions was better than 5%. Systematic errors, amenable to correction through calibration, are noted in the imager T1 and T2 values. T1 and T2 values for some typical neural tissues at 1.5T and body tissue at 1.0T for human volunteers were obtained and are tabulated.