Nuclear quadrupole resonance echoes from hexamethylenetetramine

We investigated the echo phenomenon of nuclear quadrupole resonance (NQR) from hexamethylenetetramine (HMT). We detected the pure NQR echo signal of HMT with a short pulse interval. The intensity of the echo signal increased as the pulse interval time was decreased. We observed that a clean echo signal was generated even when the pulse interval was shorter than the decay time constant T₂^*. Since the short interval time gives a strong echo, our result insists that shorter interval time is preferred for the NQR detection.     

14N Pulsed nuclear quadrupole resonance. 4. Two-pulse sequences for the determination of T1 and T2 relaxation times

A general theory, based on density matrix calculations, has been developed for the special case of a two-pulse sequence applied to spin 1 (¹⁴N) nuclear quadrupole resonance (NQR) of a powder sample. It is shown that the homolog of the NMR inversion-recovery experiment leads easily to the spin-lattice relaxation time T ₁ (associated with the diagonal elements of the density matrix) provided that an appropriate phase cycling is used. Conversely, in spite of two-step phase cycling schemes adapted to spin-spin relaxation measurements, the homolog of the NMR Hahn spin-echo sequence may pose some problems if the results are displayed in the magnitude mode. First, at short decay times, the echo may be corrupted by unwanted signals. Secondly, in that case, the amplitude of the resulting signal can evolve unexpectedly and differently as a function of the phase of the second pulse. Thirdly, at long decay times, the echo maximum occurs earlier than expected. All these problems in principle disappear with a complete four-step phase cycling scheme and the echo decay curve yields reliably the spin-spin relaxation time T ₂ (associated with off-diagonal elements). This theory allowed the exploitation of many test experiments performed at different frequencies on hexamethylenetetramine (HMT) and sodium nitrite.     

Application of the spherical tensor method for Two-Frequency pure NQR of spinI=1 nuclei

The results of a theoretical investigation of two-frequency excitation in pure nuclear quadrupole resonance (NQR) for a spinI=1 nucleus with a nonaxial elecric field gradient are presented. The multipole tensor operator technique is used for the treatment of the one- and two-frequency pulse excitations. The results are applied to the characterization of the two-frequency signal of nitrogen¹⁴N nuclei. The experiments on sodium nitrite, NaNO₂, confirm the presence of additional (two-frequency) echo in the NQR signal. The effect of resonance offsets on two-frequency NQR is also considered.     

Magnetic resonance investigations of phase transitions and modulation wave motions in incommensurate solids

We measured⁸⁷Rb nuclear magnetic resonance (NMR) and³⁵Cl nuclear quadrupole resonance (NQR) Hahn spin-echo magnetization decays in the incommensurate (I) phase of Rb₂ZnCl₄ and, in each case, obtained a Hahn echo decay that was shorter than the Carr-Purcell-Meiboom-Gill decay and one which decayed with a time constant proportional to the cube of the echo time. From these measurements we obtained from both the⁸⁷Rb NMR and³⁵Cl NQR measurements values for the diffusion coefficients that are comparable in magnitude, a fact that strongly supports the existence of slow modulation wave diffusionlike motions in the I phase, since such motions should affect both Rb and Cl ions similarly. In addition, we used⁸⁷Rb two-dimensional exchange-difference NMR to study atomic motions in the incommensurate (I) and paraelectric (P) phases to elucidate the nature of the I-P transition. We measured as a function of the mixing time the frequency shifts of the cross peaks from the main diagonal and observed a gradual increase towards an asymptotic value in the I phase but a sudden jump to the final value in the P phase. We interpreted the motions observed in the P phase as normal modes arising from simultaneous reorientations of ZnCl₄ tetrahedra and corresponding Rb ions displacements between two sites. These normal modes freeze out in the I phase and change to the diffusionlike motion of the modulation wave. We also performed³⁵Cl NQR lineshape andT ₁ measurements in K₂ZnCl₄ and obtained conclusive evidence for the presence of a narrow 1q (singly modulated) I phase between 146 and 149 K.     

Three-Frequency Composite Multipulse Nuclear Quadrupole Resonance Technique for Explosive Detection

New method of multifrequency nuclear quadrupole resonance (NQR) for the explosive detection has been proposed. This technique consists of application of the series of composite excitation circles, each consisting of two or three successive pulses of different frequencies. In this work, we study in detail the multipulse sequence consisting of n excitation sets, each set consists of three pulses. The first pulse is applied with frequency ?? _?, the second pulse with frequency ?? ₀, and the third pulse with frequency ?? _?C, but with a shifted phase. The NQR signal is detected at the frequency ?? ₊. The maximal amplitude of the detected signal is obtained by tuning the pulse parameters at frequencies ?? _? and ?? ₀. We have shown that the phase of the NQR signal at the frequency ?? ₊ second part of the composite pulse with the frequency ?? ₀ the signals with different phases to suppress the spurious signals. The method could be used for increasing the NQR signal, avoiding the spurious signals and improving the reliability of NQR detection. Possible applications of the method for the explosive detection are also discussed.     

Study of 14N NQR response to SORC pulse sequence

The behavior of nuclear quadrupole resonance (NQR) signals between RF pulses of the strong off-resonance comb (SORC) as well as the spin-locking spin-echo (SLSE) pulse sequences was studied as for ¹⁴N NQR line ν _?+? of dimethylnitramine (CH₃)₂NNO₂ at 77 K. The periodic variation of the signal amplitude observed by using SORC pulse sequence could be reasonably explained by the theoretical expression reported in the literature.     

Self-induced three-level echo

A new type of three-level photon echo has been predicted and analytically described. In contrast to the conventional three-level echo, whose formation involves three resonant ultrashort excitation pulses spaced in time, two of which are resonant to different optically allowed and adjacent transitions with different frequencies, the echo predicted arises under the conditions of formation of the conventional two-pulse echo and requires only two pump pulses of the same frequency. A theory is developed for the conditions of experiments on generation of a superradiance pulse at the ³ P ₀-³ H ₆ transition in impurity praseodymium ions in the LaF₃ matrix upon ultrashort coherent excitation of the adjacent optically allowed ³ H ₄-³ P ₀ transition in praseodymium. It is shown that the superradiance pulse after its deexcitation does not polarize the medium at the ³ P ₀-³ H ₆ generation transition and completely eliminates polarization at the ³ H ₄-³ P ₀ excitation transition. However, simultaneously, the superradiance pulse transfers the optical coherence from the excitation transition to the optically forbidden ³ H ₆-³ H ₄ transition. Thus, the phase memory about the effect of the excitation superradiance pulse is retained in the medium within a time interval that is shorter than the irreversible relaxation time of the optically forbidden transition.     

Modulation of the shape of the photon echo pulse by a pulsed magnetic field: Zeeman splitting in LuLiF4:Er3+ and YLiF4:Er3+

A spectroscopy method has been proposed involving a change in the time shape of the echo signal in the presence of a perturbation, which splits the frequencies of the transitions of two or more ion subgroups of the echo-active ions. This method has been applied to optical systems in which the Zeeman effect is manifested. The ion transition frequencies of ions are switched by a weak pulsed magnetic field acting during the time of the radiation of the photon echo pulse. The modulation of the photon echo signal shape was observed in LuLiF₄:Er³⁺ and YLiF₄:Er³⁺. The time interval between the two nearest minima corresponds to the accumulated phase of the electric dipole moment ?? and makes it possible to determine the difference of the g factors of the ground and excited ⁴ F _9/2(I) states of the Er³⁺ ion in the LuLiF₄ the YLiF₄ matrices for the known amplitude of the pulsed magnetic field. It has been shown that the echo response of the system can be programmed by the weak magnetic field pulses.     

Optimized gradient spoiling of UTE VFA-AFI sequences for robust T1 estimation with B1-field correction

Quantifying T₁ relaxation times is a challenge because inhomogeneities of the B₁ field have to be corrected to obtain proper values. It is a particular challenge in tissues with short T₂^⁎ values, for which conventional MRI techniques do not provide sufficient signal. Recently, a B₁-field correction technique called AFI (Actual Flip angle Imaging) has been introduced that can be combined with UTE (ultra-short echo-time) sequences, which have much shorter echo times compared to conventional MRI techniques, allowing quantification of signal in short T₂^⁎ tissues. A disadvantage of AFI is that it requires very long relaxation delays between repetitions to minimize the influence of imperfect spoiling of transverse magnetization on signal behavior. In this work, we propose a novel spoiling scheme for the AFI sequence that efficiently provides accurate B₁ correction maps with strongly reduced acquisition time. We validated the method with both phantom and preliminary in vivo results.     

Influence of molecular motions on NQR echoes

The influence of thermal molecular motions on spin echo decay in pure nuclear quadrupole resonance (NQR) is considered. Our calculations show that the Hahn echo decay is caused by dipole-dipole interaction of the nuclear spins and is strongly affected by molecular mobility that can lead to the shortening of the echo decay with increased temperature. Slow molecular motion yields an exponential τ₃ time dependence, while fast motion yields an exponential decay. The outlined theory allows us to explain an unusual shortening of the³⁵Cl NQR echo decay on heating in thiourea-C₂Cl₆ inclusion compound.     

Magnetic resonance imaging of cortical bone with ultrashort TE pulse sequences

PurposeNormal adult cortical bone has a very short T₂ and characteristically produces no signal with pulse sequence echo times (TEs) routinely used in clinical practice. We wished to determine whether it was possible to use ultrashort TE (UTE) pulse sequences to detect signal from cortical bone in human subjects and use this signal to characterise this tissue.Subjects and MethodsSeven volunteers and 10 patients were examined using ultrashort TE pulse sequences (TE=0.07 or 0.08 ms). Short and long inversion as well as fat suppression pulses were used as preparation pulses. Later echo images were also obtained as well as difference images produced by subtracting a later echo image from a first echo image. Saturation pulses were used for T₁ measurement and sequences with progressively increasing TEs for T₂* measurement. Intravenous gadodiamide was administered to four subjects.ResultsSignal in cortical bone was detected with UTE sequences in children, normal adults and patients. This signal was usually made more obvious by subtracting a later echo image from the first provided that the signal-to-noise ratio was sufficiently high.Normal mean adult T₁s ranged from 140 to 260 ms, and mean T₂*s ranged from 0.42 to 0.50 ms. T₁ increased significantly with age (P<.01).Increased signal was observed after contrast enhancement in the normal volunteer and the three patients to whom it was administered.Reduction in signal from short T₂ components was seen in acute fractures, and increase in signal in these components was seen with new bone formation after fracture malunion. In a case of osteoporosis, bone cross-sectional area and signal level appeared reduced.ConclusionSignal can be detected from normal and abnormal cortical bone with UTE pulse sequences, and this can be used to measure its T₁ and T₂* as well as observe contrast enhancement. Difference images are of value in increasing the conspicuity of cortical bone and observing abnormalities in disease.     

Application of the Wavelet Transform for Detecting Signals of Nuclear Quadrupole Resonance

In the present study, the wavelet transform is used to increase the signal-to-noise ratio of nuclear quadrupole resonance (NQR) signals in the direct pulse method. The efficiency of the wavelet and Fourier transforms used for detecting the NQR signal component is compared. The signal consists of noise, magnetoacoustic and piezoelectric signals, noise from external sources, and NQR signal. Signals from ¹⁴ N nuclei in hexahydro-1,3,5-trinitro-s-triazine C₃H₆N₆O₆ (RDX) are investigated at a temperature of 298 K.__________Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 47–50, January, 2005.     

Nuclear quadrupole resonance exchange spectroscopy with shaped radiofrequency pulses

Recent work on the nuclear quadrupole resonance (NQR) investigation of molecular dynamics in the solid state has relied on 2D methods. We report our studies of dynamic processes by 1D shaped pulse NQR spectroscopy. Significant advantages include considerably shorter experimental duration, clear definition of the exchange time window, and avoidance of off-resonance effects. The reorientation of the Cl₃C? group in polycrystalline chloral hydrate [Cl₃C–CH(OH)₂] is considered as a test case. This may be modelled as a three-site exchange process. An analysis of the generalised Bloch–McConnell equation is performed to formulate the kinetic matrix. The present approach involves simultaneous excitation of the sites that undergo chemical exchange by employing a suitably modulated shaped RF pulse, followed by a mixing time, and finally a suitable read pulse for signal detection. The experimental signal intensities are plotted against the mixing time to extract the kinetic parameters, i.e. the exchange rate and the spin-lattice relaxation rate. Variable temperature measurements are carried out to determine the activation parameters. Short experiment times are possible in our 1D mode, enabling a large number of runs to be readily performed as a function of mixing time and temperature. The kinetic and activation parameters obtained in the case of chloral hydrate are in good agreement with recent literature values.     

Effect of <Superscript>14</Superscript>N Nucleus Capture in Nuclear Quadrupole Resonance at Small Relaxation Parameters

Experiments on detecting induction signals of nuclear quadrupole resonance (NQR) on ¹⁴N nuclei in hexahydro-1,3,5-trinitro-s-triazine C₃H₆N₆O₆ (RDX) with preliminary changed population densities of NQR energy levels upon exposure to a saturating pulse are described. It is demonstrated that this actually causes the induction signal amplitude to change; however, complete saturation of the transition cannot be reached because of the NQR relaxation time. It is also demonstrated that the results of calculations without regard for the relaxation processes in RDX lack experimental support. Experimental data demonstrate the feasibility of application of the methods of preliminary change of the population densities (by pumping) for multifrequency experiments in NQR and explosive detection.__________Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 4, pp. 49–52, April, 2005.     

Microstructure and Mössbauer studies on magnetostrictive Tb0.3Dy0.7Fe1.95 − x Nb x (x = 0, 0.025, 0.05 and 0.075)

³⁵Cl NQR measurements were carried out between 77 and 209 K for 3-chlorothiophene, which has a glass transition in a stable crystalline state. An NQR signal with full widths of about 100 kHz at half maximum was observed in this temperature range. The spin-lattice relaxation time T ₁ was measured at the peak frequencies. The activation energy Δε _a obtained from the results of the T ₁ measurements showed a good agreement with those estimated from calorimetric measurements.     

Multifrequency photon echo generated by extremely short pulses

A photon echo in a multilevel quantum medium excited by two extremely short pulses with durations of less than one period of oscillation of the light is investigated theoretically. It is shown thatQ echo signals (Q is the number of allowed transitions) can form at each frequency of the allowed transitions, and the number of echo responses for all the allowed transitions equalsQ ². Of these,Q(Q?1) signals are separated in both time and space. The otherQ echo signals of all the allowed frequencies all arise at the time 2τ ₂₁ (τ ₂₁ is the time interval between application of the first and second pulses to the medium) and are collinear with one another.     

Pulse EPR, ENDOR, and ELDOR Study of Anionic Flavin Radicals in Na+-Translocating NADH:Quinone Oxidoreductase

The Na⁺-translocating nicotinamide adenine dinucleotide (NADH):quinine oxidoreductase (Na⁺–NQR) is a component of respiratory chain of various bacteria and it generates a redox-driven transmembrane electrochemical Na⁺ potential. It contains four different flavin prosthetic groups, including two flavin mononucleotide (FMN) residues covalently bound to the subunits NqrB and NqrC. Na⁺–NQR from Vibrio harveyi was poised at different redox potentials to prepare two samples, containing either both FMN_NqrB and FMN_NqrC or only FMN_NqrB in a paramagnetic state. These two samples were comparatively studied using pulse electron paramagnetic resonance (EPR), electron-nuclear double resonance (ENDOR), and electron-electron double resonance (ELDOR) spectroscopy. The echo-detected EPR spectra and electron spin relaxation properties were very similar for flavin radicals in both samples. The splitting of the outer peaks in the proton ENDOR spectra, assigned to the C(8α) methyl protons, allows to identify both radicals as anionic flavosemiquinones. The mean interspin distance of 20.7 Å between these radicals was determined by pulse ELDOR experiment, which allows to estimate the edge-to-edge distance (r _e) between these flavin centers as: 11.7 Å < r _e < 20.7 Å. The direct electron transfer between FMN_NqrB and FMN_NqrC during the physiological turnover of the Na⁺–NQR complex is suggested.     

Calculation of Double-Quantum-Coherence Two-dimensional Spectra: Distance Measurements and Orientational Correlations

The double-quantum-coherence (DQC) echo signal for two coupled nitroxides separated by distances ?10 Å, is calculated rigorously for the six-pulse sequence. Successive application of six pulses on the initial density matrix, with appropriate inter-pulse time evolution and coherence pathway selection leaves only the coherent pathways of interest. The amplitude of the echo signal following the last π pulse can be used to obtain a one-dimensional (1D) dipolar spectrum (Pake doublet), and the echo envelope can be used to construct the 2D DQC spectrum. The calculations are carried out using the product space spanned by the two electron-spin magnetic quantum numbers m ₁, m ₂ and the two nuclear-spin magnetic quantum numbers M ₁, M ₂, describing, e.g. two coupled nitroxides in bilabeled proteins. The density matrix is subjected to a cascade of unitary transformations taking into account dipolar and electron exchange interactions during each pulse and during the evolution in the absence of a pulse. The unitary transformations use the eigensystem of the effective spin Hamiltonians obtained by numerical matrix diagonalization. Simulations are carried out for a range of dipolar interactions, D, and microwave magnetic field strength B ₁ for both fixed and random orientations of the two ¹⁴N (and ¹⁵N) nitroxides. Relaxation effects were not included. Several examples of 1D and 2D Fourier transforms of the time-domain signals versus dipolar evolution and spin-echo envelope time variables are shown for illustration. Comparisons are made between 1D rigorous simulations and analytical approximations. The rigorous simulations presented here provide insights into DQC electron spin resonance spectroscopy, they serve as a standard to evaluate the results of approximate theories, and they can be employed to plan future DQC experiments.