We report on the results of a simulation based study of the effect of various experimental artifacts for spin I=1 double quantum filtered NMR. The simulation captures the effects of static field inhomogeneity, finite pulse widths, phase errors, transients and radio frequency inhomogeneity. We simulated the spectral distortions introduced under these errors for four, eight and sixteen step phase cycles that are well known in the NMR community. The dominating pulse errors are radio frequency field inhomogeneity and antisymmetric pulse transients. These errors result in the reduction of signal intensity as well as an introduction of distortions in the detected double quantum filtered spectrum. Using the simulation tool we studied the improvement one obtains when implementing a sixteen step phase cycle over a four step phase cycle. The results indicate that implementing a sixteen step phase cycle over an eight or four step phase cycle does not result in a significant reduction in the DQF intensity loss, or reduction in spectral distortions for antisymmetric transients.
The origin of spin locking image artifacts in the presence of B0 and B1 magnetic field imperfections is shown theoretically using the Bloch equations and experimentally at low (ω1 ≪ Δω0), intermediate (ω1 ~ Δω0) and high (ω1 ≫ Δω0) spin locking field strengths. At low spin locking fields, the magnetization is shown to oscillate about an effective field in the rotating frame causing signature banding artifacts in the image. At high spin lock fields, the effect of the resonance offset Δω0 is quenched, but imperfections in the flip angle cause oscillations about the ω1 field. A new pulse sequence is presented that consists of an integrated spin echo and spin lock experiment followed by magnetization storage along the -z-axis. It is shown that this sequence almost entirely eliminates banding artifacts from both types of field inhomogeneities at all spin locking field strengths. The sequence was used to obtain artifact free images of agarose in inhomogeneous B0 and B1 fields, off-resonance spins in fat and in vivo human brain images at 3T. The new pulse sequence can be used to probe very low frequency (0–400 Hz) dynamic and static interactions in tissues without contaminating B0 and B1 field artifacts.
spin locking; T1ρ; relaxation; off-resonance T1ρ; inhomogeneous B0 and B1 fields
A simple phase error correction technique used for field map estimation with a generally available dual-echo GRE sequence is presented. Magnetic field inhomogeneity maps estimated using two separate GRE volume acquisitions at different echo times are prone to dynamic motion errors between acquisitions. By using the dual-echo sequence the data are collected during two back-to-back readout gradients in opposite polarity after a single RF pulse, and inter-echo motion artifacts and alignment errors in field map estimation can be factored out. Residual phase error from the asymmetric readout pulses is modeled as an affine term in the readout direction. Results from phantom and human data suggest that the first order phase correction term stays constant over time and, hence, can be applied to different data acquired with the same protocol over time. The zero order phase correction term may change with time and is estimated empirically for different scans.
Field-inhomogeneity; Field map; Dual-echo; Phase correction
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 dipolar spectrum (Pake doublet), and the echo envelope can be used to construct the two-dimensional DQC spectrum. The calculations are carried out using the product space spanned by the two electron-spin magnetic quantum numbers m1, m2 and the two nuclear-spin magnetic quantum numbers M1, M2, 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 for both fixed and random orientations of the two 14N (and 15N) nitroxides. Relaxation effects were not included. Several examples of one- and two-dimensional Fourier transforms of the time domain signals vs. 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 ESR spectroscopy, they serve as a standard to evaluate the results of approximate theories, and they can be employed to plan future DQC experiments.
Accurate determination of sample temperatures in solid state nuclear magnetic resonance (NMR) with magic-angle spinning (MAS) can be problematic, particularly because frictional heating and heating by radio-frequency irradiation can make the internal sample temperature significantly different from the temperature outside the MAS rotor. This paper demonstrates the use of 79Br chemical shifts and spin-lattice relaxation rates in KBr powder as temperature-dependent parameters for the determination of internal sample temperatures. Advantages of this method include high signal-to-noise, proximity of the 79Br NMR frequency to that of 13C, applicability from 20 K to 320 K or higher, and simultaneity with adjustment of the MAS axis direction. We show that spin-lattice relaxation in KBr is driven by a quadrupolar mechanism. We demonstrate a simple approach to including KBr powder in hydrated samples, such as biological membrane samples, hydrated amyloid fibrils, and hydrated microcrystalline proteins, that allows direct assessment of the effects of frictional and radio-frequency heating under experimentally relevant conditions.
solid state NMR; magnetic resonance; magic-angle spinning; temperature calibration
Spin-lattice relaxation rates measured by long-pulse saturation recovery in glassy solvents for chlorinated aromatic radicals: perchlorotriphenylmethyl radical, 2,5-dichloro-3,6-dihydroxy-1,4-benzosemiquinone, and tetrachloro-1,4-benzosemiquinone, were compared with relaxation rates for non-chlorinated analogs. The impact of the quadrupolar chlorines is small, and less than the effects of changing the rigidity of the glass. The temperature dependence of relaxation rates below the glass transition temperature could be modeled as the sum of contributions from the direct, Raman, and local mode processes.
We study driven by an external electric field quantum orbital and spin dynamics of electron in a one-dimensional double quantum dot with spin-orbit coupling. Two types of external perturbation are considered: a periodic field at the Zeeman frequency and a single half-period pulse. Spin-orbit coupling leads to a nontrivial evolution in the spin and orbital channels and to a strongly spin- dependent probability density distribution. Both the interdot tunneling and the driven motion contribute into the spin evolution. These results can be important for the design of the spin manipulation schemes in semiconductor nanostructures.
PACS numbers: 73.63.Kv,72.25.Dc,72.25.Pn
In this work, a number of important issues associated with fast spin echo (FSE) imaging of the human brain at 4.7 T are addressed. It is shown that FSE enables the acquisition of images with high resolution and good tissue contrast throughout the brain at high field strength. By employing an echo spacing (ES) of 22 ms, one can use large flip angle refocusing pulses (162°) and a low acquisition bandwidth (50 kHz) to maximize the signal-to-noise ratio (SNR). A new method of phase encode (PE) ordering (called “feathering”) designed to reduce image artifacts is described, and the contributions of RF (B1) inhomogeneity, different echo coherence pathways, and magnetization transfer (MT) to FSE signal intensity and contrast are investigated. B1 inhomogeneity is measured and its effect is shown to be relatively minor for high-field FSE, due to the self-compensating characteristics of the sequence. Thirty-four slice data sets (slice thickness = 2 mm; in-plane resolution = 0.469 mm; acquisition time = 11 min 20 s) from normal volunteers are presented, which allow visualization of brain anatomy in fine detail. This study demonstrates that high-field FSE produces images of the human brain with high spatial resolution, SNR, and tissue contrast, within currently prescribed power deposition guidelines. Magn Reson Med 51:1254-1264, 2004.
high-field FSE; feathering; T2-weighted MRI; structural MRI; high-field MR
Hyperpolarized (hp) 131Xe with up to 2.2% spin polarization (i.e., 5000-fold signal enhancement at 9.4 T) was obtained after separation from the rubidium vapor of the spin-exchange optical pumping (SEOP) process. The SEOP was applied for several minutes in a stopped-flow mode, and the fast, quadrupolar-driven T1 relaxation of this spin I = 3/2 noble gas isotope required a rapid subsequent rubidium removal and swift transfer into the high magnetic field region for NMR detection. Because of the xenon density dependent 131Xe quadrupolar relaxation in the gas phase, the SEOP polarization build-up exhibits an even more pronounced dependence on xenon partial pressure than that observed in 129Xe SEOP. 131Xe is the only stable noble gas isotope with a positive gyromagnetic ratio and shows therefore a different relative phase between hp signal and thermal signal compared to all other noble gases. The gas phase 131Xe NMR spectrum displays a surface and magnetic field dependent quadrupolar splitting that was found to have additional gas pressure and gas composition dependence. The splitting was reduced by the presence of water vapor that presumably influences xenon-surface interactions. The hp 131Xe spectrum shows differential line broadening, suggesting the presence of strong adsorption sites. Beyond hp 131Xe NMR spectroscopy studies, a general equation for the high temperature, thermal spin polarization, P, for spin I ⩾ 1 / 2I⩾1/2 nuclei is presented.
131Xe; Xenon-131; Xe-131; Hyperpolarization; Hyperpolarized; Noble gases; Spin polarization; Spin-exchange optical pumping; Nuclear electric quadrupole moment; Quadrupolar relaxation; 129Xe; Nuclear magnetic resonance; Xenon-129; Krypton-83; 83Kr
The origin of image artifacts in an off-resonance spin-locking experiment is shown to be imperfections in the excitation flip angle. A pulse sequence for off-resonance spin locking is implemented that compensates for imperfections in the excitation flip angle through an off-resonance rotary echo. The off-resonance rotary echo alternates the frequency offset and phase of the RF transmitter during two spin-locking pulses of equal duration. The underlying theory is detailed, and MR images demonstrate the effectiveness of the technique in agarose gel phantoms and in in vivo human brain at 3T.
off-resonance T1ρ; spin locking; T1ρ-weighted imaging; rotary echo; T1ρ relaxation
The anisotropic motion of tightly bound waters of hydration in bovine nuchal ligament elastin has been studied by deuterium Double Quantum Filtered (DQF) NMR. The experiments have allowed for a direct measurement of the degree of anisotropy within pores of elastin over a time scale ranging from 100 μs to 30 ms, corresponding to a tortuous spatial displacement ranging from 0.2 to 7 μm. We studied the anisotropic motion of deuterium nuclei in D2O hydrated elastin over a temperature of −15 °C to 37 °C and in solvents with varying dielectric constants. Our experimental measurements of the residual quadrupolar interaction as a function of temperature are correlated to the existing notion of hydrophobic collapse near 20 °C.
Double Quantum Filter; Quadrupolar interaction; Elastin; Nuchal Ligament; fibers; Deuterium NMR
Selective coherence control and electrically mediated exchange coupling of single electron spin between triplet and singlet states using numerically derived optimal control of proton pulses is demonstrated. We obtained spatial confinement below size of the Bohr radius for proton spin chain FWHM. Precise manipulation of individual spins and polarization of electron spin states are analyzed via proton induced emission and controlled population of energy shells in pure 29Si nanocrystal. Entangled quantum states of channeled proton trajectories are mapped in transverse and angular phase space of 29Si axial channel alignment in order to avoid transversal excitations. Proton density and proton energy as impact parameter functions are characterized in single particle density matrix via discretization of diagonal and nearest off-diagonal elements. We combined high field and low densities (1 MeV/92 nm) to create inseparable quantum state by superimposing the hyperpolarizationed proton spin chain with electron spin of 29Si. Quantum discretization of density of states (DOS) was performed by the Monte Carlo simulation method using numerical solutions of proton equations of motion. Distribution of gaussian coherent states is obtained by continuous modulation of individual spin phase and amplitude. Obtained results allow precise engineering and faithful mapping of spin states. This would provide the effective quantum key distribution (QKD) and transmission of quantum information over remote distances between quantum memory centers for scalable quantum communication network. Furthermore, obtained results give insights in application of channeled protons subatomic microscopy as a complete versatile scanning-probe system capable of both quantum engineering of charged particle states and characterization of quantum states below diffraction limit linear and in-depth resolution.
PACS numbers: 03.65.Ud, 03.67.Bg, 61.85.+p, 67.30.hj
During adiabatic excitation, the nuclear magnetization in the transverse plane is subject to T2 (spin-spin) relaxation, depending on the pulse length τ. Here, this property is exploited in a method of measuring T2 using the ratio of NMR signals acquired with short and long-duration self-refocusing adiabatic pulses, without spin-echoes. This Dual-τ method is implemented with B1-insensitive rotation (BIR-4) pulses. It is validated theoretically with Bloch Equation simulations independent of flip-angle, and experimentally in phantoms. Dual-τ T2 measurements are most accurate at short T2 where results agree with standard spin-echo measures to within 10% for T2 ≤ 100ms. Dual-τ MRI performed with a long 0° BIR-4 pre-pulse provides quantitative T2 imaging of phantoms and the human foot while preserving desired contrast and functional properties of the rest of the MRI sequence. A single 0° BIR-4 pre-pulse can provide T2 contrast-weighted MRI and serve as a “T2-prep” sequence with a lower B1 requirement than prior approaches. Finally, a Tri-τ experiment is introduced in which both τ and flip-angle are varied, enabling measurement of T2, T1 and signal intensity in just three acquisitions if flip-angles are well-characterized. These new methods can potentially save time and simplify relaxation measurements and/or contrast-weighted NMR and MRI.
spin-spin relaxation; measurement; adiabatic pulses; spin-lattice relaxation; MRI; T1; T2
Electron and nuclear spins are very promising candidates to serve as quantum bits (qubits) for proposed quantum computers, as the spin degrees of freedom are relatively isolated from their surroundings and can be coherently manipulated, e.g., through pulsed electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR). For solid-state spin systems, impurities in crystals based on carbon and silicon in various forms have been suggested as qubits, and very long relaxation rates have been observed in such systems. We have investigated a variety of these systems at high magnetic fields in our multifrequency pulsed EPR/ENDOR (electron nuclear double resonance) spectrometer. A high magnetic field leads to large electron spin polarizations at helium temperatures, giving rise to various phenomena that are of interest with respect to quantum computing. For example, it allows the initialization of both the electron spin as well as hyperfine-coupled nuclear spins in a well-defined state by combining millimeter and radio-frequency radiation. It can increase the T2 relaxation times by eliminating decoherence due to dipolar interaction and lead to new mechanisms for the coherent electrical readout of electron spins. We will show some examples of these and other effects in Si:P, SiC:N and nitrogen-related centers in diamond.
A basic requirement for quantum information processing is the ability to universally control the state of a single qubit on timescales much shorter than the coherence time. Although ultrafast optical control of a single spin has been achieved in quantum dots, scaling up such methods remains a challenge. Here we demonstrate complete control of the quantum-dot charge qubit on the picosecond scale, orders of magnitude faster than the previously measured electrically controlled charge- or spin-based qubits. We observe tunable qubit dynamics in a charge-stability diagram, in a time domain, and in a pulse amplitude space of the driven pulse. The observations are well described by Landau–Zener–Stückelberg interference. These results establish the feasibility of a full set of all-electrical single-qubit operations. Although our experiment is carried out in a solid-state architecture, the technique is independent of the physical encoding of the quantum information and has the potential for wider applications.
Universal control of the state of qubits on timescales much shorter than the coherence time is necessary for quantum computation. The authors demonstrate electrical control of a charge qubit in quantum dots on the picosecond scale, which is orders of magnitude faster than previously reported.
The decoherence of quantum objects is a critical issue in quantum science and technology. It is generally believed that stronger noise causes faster decoherence. Strikingly, recent theoretical work suggests that under certain conditions, the opposite is true for spins in quantum baths. Here we report an experimental observation of an anomalous decoherence effect for the electron spin-1 of a nitrogen-vacancy centre in high-purity diamond at room temperature. We demonstrate that, under dynamical decoupling, the double-transition can have longer coherence time than the single-transition even though the former couples to the nuclear spin bath as twice strongly as the latter does. The excellent agreement between the experimental and theoretical results confirms the controllability of the weakly coupled nuclear spins in the bath, which is useful in quantum information processing and quantum metrology.
Quantum objects are subject to decoherence effects due to the surrounding environment. This study demonstrates experimentally a counterintuitive example of anomalous decoherence, in which electron spins residing at nitrogen vacancy centres in diamond display longer coherence times under stronger noises.
Organic light emitting devices (OLED) are becoming important and characterisation of them, in terms of structure, charge distribution, and intermolecular interactions, is important. Tris(8-hydroxyquinolinato)-aluminium(III), known as Alq3, an organomettalic complex has become a reference material of great importance in OLED. It is important to elucidate the structural details of Alq3 in its various isomeric and solvated forms. Solid-state nuclear magnetic resonance (NMR) is a useful tool for this which can also complement the information obtained with X-ray diffraction studies.
We report here 27Al one-dimensional (1D) and two-dimensional (2D) multiple-quantum magic-angle spinning (MQMAS) NMR studies of the meridional (α-phase) and the facial (δ-phase) isomeric forms of Alq3. Quadrupolar parameters are estimated from the 1D spectra under MAS and anisotropic slices of the 2D spectra and also calculated using DFT (density functional theory) quantum-chemical calculations. We have also studied solvated phase of Alq3 containing ethanol in its lattice. We show that both the XRD patterns and the quadrupolar parameters of the solvated phase are different from both the α-phase and the δ-phase, although the fluorescence emission shows no substantial difference between the α-phase and the solvated phase. Moreover, we have shown that after the removal of ethanol from the matrix the solvated Alq3 has similar XRD patterns and quadrupolar parameters to that of the α-phase.
The 2D MQMAS experiments have shown that all the different modifications of Alq3 have 27Al in single unique crystallographic site. The quadrupolar parameters predicted using the DFT calculation under the isodensity polarisable continuum model resemble closely the experimentally obtained values. The solvated phase of Alq3 containing ethanol has structural difference from the α-phase of Alq3 (containing meridional isomer) from the solid-state NMR studies. Solid-state NMR can hence be used as an effective complementary tool to XRD for characterisation and structural elucidation.
SOEs (sulfite-oxidizing enzymes) are physiologically vital and occur in all forms of life. During the catalytic cycle, the five-co-ordinate square pyramidal oxo-molybdenum active site passes through the Mo(V) state, and intimate details of the structure can be obtained from variable frequency pulsed EPR spectroscopy through the hyperfine and nuclear quadrupole interactions of nearby magnetic nuclei. By employing variable spectrometer operational frequencies, it is possible to optimize the measurement conditions for difficult quadrupolar nuclei of interest (e.g. 17O, 33S, 35Cl and 37Cl) and to simplify the interpretation of the spectra. Isotopically labelled model Mo(V) compounds provide further insight into the electronic and geometric structures and chemical reactions of the enzymes. Recently, blocked forms of SOEs having co-ordinated sulfate, the reaction product, were detected using 33S (I = 3/2) labelling. This blocking of product release is a possible contributor to fatal human sulfite oxidase deficiency in young children.
molybdenum centre; pulsed EPR spectroscopy; sulfite-oxidizing enzyme (SOE)
In this paper the authors quantitatively evaluate the combined effect of both flow and diffusion in steady-state free precession (SSFP) imaging. A partition analysis (PA) is used to derive a fourth order approximation (in E2) of the signal in an echo SSFP sequence. The authors also introduce a novel very fast simulation technique, based on a circular convolution, which accurately accounts for both flow and diffusion. A 2D SSFP-echo sequence was implemented to obtain experimental data from a phantom containing three different solutions. Excellent agreement between the theory and the experimental data was found. Then by using the simulation algorithm and experimental measurements of in vivo brain motion, the authors estimated the artifacts to be expected in SSFP diffusion imaging of the brain and found them to be comparable with those of pulsed gradient spin echo. Finally, the authors point out the equivalence between the flow sensitivity of SSFP and RF spoiling commonly used in fast imaging.
flow; diffusion; SSFP; simulation
In this article, both sodium magnetic resonance (MR) and T1ρ relaxation mapping aimed at measuring molecular changes in cartilage for the diagnostic imaging of osteoarthritis are reviewed. First, an introduction to structure of cartilage, its degeneration in osteoarthritis (OA) and an outline of diagnostic imaging methods in quantifying molecular changes and early diagnostic aspects of cartilage degeneration are described. The sodium MRI section begins with a brief overview of the theory of sodium NMR of biological tissues and is followed by a section on multiple quantum filters that can be used to quantify both bi-exponential relaxation and residual quadrupolar interaction. Specifically, (i) the rationale behind the use of sodium MRI in quantifying proteoglycan (PG) changes, (ii) validation studies using biochemical assays, (iii) studies on human OA specimens, (iv) results on animal models and (v) clinical imaging protocols are reviewed. Results demonstrating the feasibility of quantifying PG in OA patients and comparison with that in healthy subjects are also presented. The section concludes with the discussion of advantages and potential issues with sodium MRI and the impact of new technological advancements (e.g. ultra-high field scanners and parallel imaging methods). In the theory section on T1ρ, a brief description of (i) principles of measuring T1ρ relaxation, (ii) pulse sequences for computing T1ρ relaxation maps, (iii) issues regarding radio frequency power deposition, (iv) mechanisms that contribute to T1ρ in biological tissues and (v) effects of exchange and dipolar interaction on T1ρ dispersion are discussed. Correlation of T1ρ relaxation rate with macromolecular content and biomechanical properties in cartilage specimens subjected to trypsin and cytokine-induced glycosaminoglycan depletion and validation against biochemical assay and histopathology are presented. Experimental T1ρ data from osteoarthritic specimens, animal models, healthy human subjects and as well from osteoarthritic patients are provided. The current status of T1ρ relaxation mapping of cartilage and future directions is also discussed.
cartilage; arthritis; spin-lock; T1rho; sodium; MRI
Sodium multiple-quantum filtered (MQF) NMR spectroscopy may potentially be used to measure proteoglycan (PG) depletion in cartilage caused by osteoarthritis (OA). The purpose of this work was to quantify the effect of interleukin-1 (IL-1β)-induced macromolecule depletion on the residual quadrupolar interaction (RQI) of sodium in bovine cartilage plugs.
Materials and Methods
Fifteen 8-mm-diameter cartilage plug specimens were cored from the articular surface of fresh bovine patellae. All plugs were kept in culture media and nine of the plugs were subjected to interleukin-1 (IL-1β)-induced degeneration of cartilage for 4, 6, and 7 days. Sodium NMR spectra were obtained from each sample with a 1-cm-diameter solenoid coil in a 2T whole-body magnet interfaced to a custom-built spectrometer. We employed a previously described theoretical model to analyze triple-quantum filtered (TQF) and double-quantum filtered magic angle (DQFMA) spectra obtained from normal cartilage and cartilage treated with IL-1β. The model assumes a static Gaussian distribution of the RQI frequency, ωQ, in the sample. TQF and DQFMA spectra from each sample were fitted with the appropriate signal expressions to determine σ (the root mean square (RMS) ωQ), T2f, and T2s. An inversion-recovery sequence was used to determine T1 of each plug. A spectrophotometric assay was used to determine the amount of PG depleted from each plug. Histology was performed to visualize the PG loss in cartilage plugs. We defined σ as the measure of changes in macroscopic order in the tissue.
Simulated spectra from the theoretical model were in excellent agreement with the experimental data. We were able to determine the relaxation times as well as σ of each specimen from their corresponding fits. T2f ranged between 2.26–3.50 msec, decreasing with increased PG loss. Over the range of PG depletion investigated, T2s increased from 12.3 msec to 14.9 msec, and T1 increased from 16 msec to 21 msec, while σ decreased from 180 Hz to 120 Hz. The order of macromolecules in the cartilage tissue decreased substantially with PG loss. Histology sections clearly showed qualitative visualization of the PG loss in cartilage following treatment with IL-1β.
We demonstrated that IL-β-induced macromolecule depletion in cartilage not only changes the relaxation characteristics of sodium but also changes RQI of the tissue. Using MQF sodium spectroscopy we quantified the changes in σ and showed that loss of macromolecules reduces the degree of order in the tissue.
sodium; NMR; multiple-quantum filter; cartilage; proteoglycans
To determine the impact of electron-electron spin-spin interactions on electron spin relaxation rates, 1/T1 and 1/Tm were measured for nitroxide monoradical, diradical, and tetraradical derivatives of 1,3-alternate calixarenes, for two pegylated high-spin nitroxide diradicals, and for an azine-linked nitroxide diradical. The synthesis and characterization by SQUID (superconducting quantum interference device) magnetometry of one of the high-spin diradicals, in which nitroxides are conformationally constrained to be coplanar with the m-phenylene unit, is reported. The interspin distances ranged from about 5-9 Å, and the magnitude of the exchange interaction ranged from >150 to >0.1 K. 1/T1 and 1/Tm were measured by long-pulse saturation recovery, three-pulse inversion recovery, and two-pulse echo decay at X-band (9.5 GHz) and Q-band (35 GHz). For a diradical with interspin distance about 9 Å, relaxation rates were only slightly faster than for a monoradical with analogous structure. For interspin distances of about 5-6 Å, relaxation rates in glassy solvents up to 300 K increased in the order monoradical < diradical < tetraradical. Modulation of electron-electron interaction enhanced relaxation via the direct, Raman, and local mode processes. The largest differences in 1/T1 were observed below 10 K, where the direct process dominates. For the three diradicals with comparable magnitude of dipolar interaction, 1/Tm and 1/T1 were faster for the molecules with more flexible structures. Relaxation rates were faster in the less rigid low-polarity sucrose octaacetate glass than in the more rigid 4:1 toluene/chloroform or in hydrogen-bonded glycerol glasses, which highlights the impact of motion on relaxation.
To optimize simulations of CW EPR spectra for high-spin Fe(III) with zero-field splitting comparable to the EPR quantum, information is needed on the factors that contribute to the line shapes and line widths. Continuous wave electron paramagnetic resonance (EPR) spectra obtained for iron transferrin carbonate from 4 to 150 K and for iron transferrin oxalate from 4 to 100 K did not exhibit significant temperature dependence of the line shape, which suggested that the line shapes were not relaxation determined. To obtain direct information concerning the electron spin relaxation rates, electron spin echo and inversion recovery EPR were used to measure T1 and Tm for the high-spin Fe(III) in iron transferrin carbonate and iron transferrin oxalate between 5 and 20–30 K. For comparison with the data for the transferrin complexes, relaxation times were obtained for tris(oxalato)ferrate(III). The relaxation rates are similar for the three complexes and do not exhibit a strong dependence on position in the spectrum. Extrapolation of the observed temperature dependence of the relaxation rates to higher temperatures gives values consistent with the conclusion that the CW line shapes are not relaxation determined up to 150 K.
Hyperpolarized (hp) 129Xe and hp 83Kr for magnetic resonance imaging (MRI) are typically obtained through spin-exchange optical pumping (SEOP) in gas mixtures with dilute concentrations of the respective noble gas. The usage of dilute noble gases mixtures requires cryogenic gas separation after SEOP, a step that makes clinical and preclinical applications of hp 129Xe MRI cumbersome. For hp 83Kr MRI, cryogenic concentration is not practical due to depolarization that is caused by quadrupolar relaxation in the condensed phase. In this work, the concept of stopped flow SEOP with concentrated noble gas mixtures at low pressures was explored using a laser with 23.3 W of output power and 0.25 nm linewidth. For 129Xe SEOP without cryogenic separation, the highest obtained MR signal intensity from the hp xenon-nitrogen gas mixture was equivalent to that arising from 15.5±1.9% spin polarized 129Xe in pure xenon gas. The production rate of the hp gas mixture, measured at 298 K, was 1.8 cm3/min. For hp 83Kr, the equivalent of 4.4±0.5% spin polarization in pure krypton at a production rate of 2 cm3/min was produced. The general dependency of spin polarization upon gas pressure obtained in stopped flow SEOP is reported for various noble gas concentrations. Aspects of SEOP specific to the two noble gas isotopes are discussed and compared with current theoretical opinions. A non-linear pressure broadening of the Rb D1 transition was observed and taken into account for the qualitative description of the SEOP process.
Combined acquisition of gradient-echo and spin-echo signals in MRI time series reveals additional information for perfusion-weighted imaging and functional magnetic resonance imaging due to differences in the sensitivity of gradient-echo and spin-echo measurements to the properties of the underlying vascular architecture. The acquisition of multiple echo trains within one time frame facilitates the simultaneous estimation of the transversal relaxation parameters R2 and R2*. However, the simultaneous estimation of these parameters tends to be incorrect in presence of slice profile mismatches between signal excitation and subsequent refocusing pulses. It is shown here that improvements in pulse design reduced R2 and R2* estimation errors. Further improvements were achieved by augmented parameter estimation through the introduction of an additional parameter δ to correct for discordances in slice profiles to facilitate more quantitative measurements. Moreover, the analysis of time-resolved acquisitions revealed that the temporal stability of R2 estimates could be increased with improved pulse design, counteracting low contrast-to-noise ratios in spin-echo-based perfusion and functional MRI.
spin-echo and gradient-echo EPI; PWI; fMRI; slice profile mismatch; RF pulse design