Non-CPMG Fast Spin Echo with full signal

The standard Fast Spin Echo sequence used in MR imaging relies on the CPMG condition. A consequence of this condition is that only one component of the transverse magnetization can be measured. To counter this, some phase modulation schemes (XY, MLEV.) for the pulse train have been proposed, but they are useful only over a very restricted range, close to pi, of the refocusing pulse rotation angle. Some other solutions not relying on phase modulation have also been suggested, but they destroy one half the available signal. Revisiting the phase modulation approach, J. Murdoch ("Second SMR Scientific Meeting," p. 1145, 1994) suggested that a quadratic phase modulation could generate a train of classical echoes. We show here that indeed a quadratic phase modulation has a very suitable property: after an adequate change of frame, the dynamic of the system composed of all the protons situated in one pixel can be seen as stationary. If the parameter of the quadratic phase modulation is well chosen, it is then possible to put the dynamic system in a combination of two suitable states and obtain a signal identical to the signal of a classical spin echo, at least for nutation of the refocusing pulse higher than, approximately, two radians.     

X- and Q-Band Electron Spin Echo Study of Stochastic Molecular Librations of Spin Labels in Lipid Bilayers

Electron spin echo (ESE) of nitroxide spin labels allows detecting fast nanosecond stochastic restricted rotations (stochastic molecular librations), which is a common property of molecules in disordered media including biological systems. Under the typical experimental conditions, the anisotropic electron paramagnetic resonance (EPR) spectrum of a nitroxide is only partly excited by microwave pulses, which allows selecting an anisotropic contribution to the transverse spin relaxation by comparing echo decays at different spectral positions. On the other hand, for low-amplitude orientational motion, the excitation bandwidth is large enough to cover the range of spectral diffusion occurring during the echo formation. To verify that the two-pulse echo decay is indeed related to fast motions, the stimulated electron spin echo can be used. In addition, theory predicts an increase of the relaxation rates at higher microwave resonance frequency. To check this prediction, in the present work we performed a comparative study of ESE decays at microwave X- and Q-bands, for spin-labeled lipids in the gel phase of a 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) bilayer. A good agreement found between experimental data and computer simulation provides additional justification for the model of fast stochastic molecular librations.     

核磁共振测井受激回波校正方法研究

核磁共振测井中,受激回波导致CPMG序列中前2个回波与期望值存在较大差异,严重影响仪器信噪比和储层评价效果. 为进一步改善核磁共振测井仪性能,通过探究受激回波产生机理,揭示其对CPMG回波串作用规律,提出了受激回波的校正方法. 同时针对仪器负载不同,相同发射功率产生射频场强度各异的特性,建立受激回波校正系数与射频场强的数学关系,在不同应用环境中实现对CPMG测量结果的校正. 实验表明,在信噪比较低的应用环境中,采用传统的舍去前2个回波的方法误差达24.58%,而该文设计的校正算法误差仅为4.9%.     

Spin echo SPI methods for quantitative analysis of fluids in porous media

Fluid density imaging is highly desirable in a wide variety of porous media measurements. The SPRITE class of MRI methods has proven to be robust and general in their ability to generate density images in porous media, however the short encoding times required, with correspondingly high magnetic field gradient strengths and filter widths, and low flip angle RF pulses, yield sub-optimal S/N images, especially at low static field strength. This paper explores two implementations of pure phase encode spin echo 1D imaging, with application to a proposed new petroleum reservoir core analysis measurement.In the first implementation of the pulse sequence, we modify the spin echo single point imaging (SE-SPI) technique to acquire the k-space origin data point, with a near zero evolution time, from the free induction decay (FID) following a 90° excitation pulse. Subsequent k-space data points are acquired by separately phase encoding individual echoes in a multi-echo acquisition. T₂ attenuation of the echo train yields an image convolution which causes blurring. The T₂ blur effect is moderate for porous media with T₂ lifetime distributions longer than 5 ms. As a robust, high S/N, and fast 1D imaging method, this method will be highly complementary to SPRITE techniques for the quantitative analysis of fluid content in porous media.In the second implementation of the SE-SPI pulse sequence, modification of the basic measurement permits fast determination of spatially resolved T₂ distributions in porous media through separately phase encoding each echo in a multi-echo CPMG pulse train. An individual T₂ weighted image may be acquired from each echo. The echo time (TE) of each T₂ weighted image may be reduced to 500 μs or less. These profiles can be fit to extract a T₂ distribution from each pixel employing a variety of standard inverse Laplace transform methods. Fluid content 1D images are produced as an essential by product of determining the spatially resolved T₂ distribution. These 1D images do not suffer from a T₂ related blurring.The above SE-SPI measurements are combined to generate 1D images of the local saturation and T₂ distribution as a function of saturation, upon centrifugation of petroleum reservoir core samples. The logarithm mean T₂ is observed to shift linearly with water saturation. This new reservoir core analysis measurement may provide a valuable calibration of the Coates equation for irreducible water saturation, which has been widely implemented in NMR well logging measurements.     

Spin Echo Attenuation of Restricted Diffusion as a Discord of Spin Phase Structure

By using the particle probability density we analyze the spin echo attenuation of particles, diffusing in a bounded region. It provides a means to expand a nonuniform spin phase distribution into a series of waves that characterize the geometry and boundary conditions of confinement. Random motion disrupts the initial phase structure created by applied gradients and consequently discords its structure waves. By assuming the spin phase fluctuation and/or the randomness of spin phase distribution in the subensemble as a Gaussian stochastic process, we derive a new analytical expression for the echo attenuation related to the particle velocity correlation. For a diffusion in porous structure we get the expression featuring the same “diffusive diffraction” patterns as those being found and explained by P. T. Callaghan and A. Coy (“Principles of Nuclear Magnetic Resonance Microscopy,” Oxford Univ. Press, Oxford (1991);J. Chem. Phys.101, 4599–4609 (1994)) with the use of propagator theory. With the new approach we cast a new light on the phenomena and derive analitically how the diffusive diffractions appear when the sequence of finite or even modulated gradients are applied. The method takes into account the non-Markovian character of restricted diffusion, and therefore the echo dependence on the diffusion lengths and on the strength of applied gradient differs from the results of authors assuming the Markovian diffusion either by dealing with the diffusion propagators or by the computer simulation of Fick's diffusion.     

Counting Spins with a New Spin Echo Double Resonance

In traditional spin echo double resonance (SEDOR), the echo amplitudeMis decreased when the observed spinsSare flipped by π together with the π refocusing pulse on the observed spinsI; the dependence on τ is then determined. In the new version of SEDOR, the echo amplitude is measured as a function of theSspin flip angle θ at a constant pulse spacing τ. The analysis is simple and powerful for long τ, where the strong collision limit applies. There, the variation ofMwith θ can be fit, yielding the numbernof spinsSto which each spinIis coupled. Data from amorphous silicon with¹H and²D show the described effect. A MAS version of the new method is used on multiply labeled alanine and urea, with results in good agreement with the predictions forn= 2, as expected. By Fourier transformingMwith respect to the flip angle θ, a stick spectrum results; the largest numbered non-vanishing stick yields the numbernof spinsScoupled to each spinI.Simulations are presented for ann= 2 system. The present technique is compared to the multiple-quantum spin-counting method.     

Secondary Nuclear Spin Echo Signals in Thin Yttrium Iron Ferrite Garnet Films

The results are presented of experimental and theoretical study of the phenomenon of secondary nuclear spin echo in magnetically ordered materials in which the formation of additional echo signals is due to dynamic hyperfine coupling. Numerical simulation of the effect of the amplitude (ω1) and the durations of the first (t1) and the second (t2) exciting pulses on the echo signals is performed. It is found that the maximum amplitude of the secondary echo is formed under the conditions ω1t1 = 0.5π and ω1t2 ≈ 0.6π. It is shown that secondary echo signals can be observed upon inhomogeneous excitation of the spectral line ω1 ≤ Δω, where Δω is the inhomogeneous spectral line width. At a temperature of T = 4.2 K, additional double-pulse spin 3τ-echo signals from iron nuclei are experimentally observed in an epitaxial yttrium ferrite garnet film enriched with 57Fe magnetic isotope to 96%. The experimentally observed phase relationships between the primary and secondary echo signals, as well as the dependence of the echo signal amplitude on the amplitude and duration of the exciting pulses, are in good agreement with the results of numerical simulation of the dynamics of nuclear magnetization with regard to the dynamic hyperfine coupling. It is shown that the secondary echo exhibits the effect of spectral line narrowing, and the amplitude of the secondary echo is proportional to the nuclear magnetic resonance (NMR) enhancement factor in magnets, η. In the case of 57Fe NMR in an yttrium iron garnet (YIG) film, the amplitude of the 3τ-echo is two to three orders of magnitude smaller than the amplitude of the primary 2τ-echo, which corresponds to η ≈ 440. The detection of weak secondary echo signals proves to be possible due to the use of a phase-coherent NMR spectrometer with digital quadrature detection at the carrier frequency and signal accumulation.     

Spin echo formation in the presence of stochastic dynamics

Spin echo formation in magnetic field gradients in the presence of fast stochastic motion is studied for hyperpolarized 3He gas at different diffusivities. The fast translational motion leads to frequency shifts already during echo formation, which can be described analytically for a linear gradient. Despite complete signal loss at the position of the spin echo itself, considerable intensity can be preserved at an earlier time (sqrt[2]tau rather than 2tau, where tau is the pulse delay). Hence, the phenomenon is designated as a pseudo spin echo.     

Accurate measurements of small J coupling constants under inhomogeneous fields via intermolecular multiple-quantum coherences

Two new NMR pulse sequences, based on intermolecular multiple-quantum coherences (iMQCs), were developed to obtain apparent J coupling constants with a scaling factor from one to infinity relative to the conventional J coupling constants. Here the apparent J coupling constants were defined as apparent peak separations in unit of Hz in a reconstructed spectrum for a coupled spin system. Except for the adjustable scaling factor for apparent J coupling constants, the sequences hold the advantage of high acquisition efficiency, and retain the spectral information such as chemical shifts, multiplet patterns, and relative peak areas under inhomogeneous fields. For spin systems with small scalar coupling constants, well-resolved J-spectra can be achieved by selecting a proper scaling factor. Theoretical predictions are in good agreement with simulation results and experimental observations.     

Spin Echo Analysis of Restricted Diffusion under Generalized Gradient Waveforms: Planar, Cylindrical, and Spherical Pores with Wall Relaxivity

A simple matrix formalism presented by Callaghan [J. Magn. Reson.129, 74–84 (1997)], and based on the multiple propagator approach of Caprihanet al.[J. Magn. Reson. A118, 94–102 (1996)], allows for the calculation of the echo attenuation,E(q), in spin echo diffusion experiments, for practically all gradient waveforms. We have extended the method to the treatment of restricted diffusion in parallel plate, cylindrical, and spherical geometries, including the effects of fluid–surface interactions. In particular, theq-space coherence curves are presented for the finite-width gradient pulse PGSE experiment and the results of the matrix calculations compare precisely with published computer simulations. It is shown that the use of long gradient pulses (δ a²/D) create the illusion of smaller pores if a narrow pulse approximation is assumed, while ignoring the presence of significant wall relaxation can lead to both an underestimation of the pore dimensions and a misidentification of the pore geometry.     

Sensitivity Enhancement by Matched Microwave Pulses in One- and Two-Dimensional Electron Spin Echo Envelope Modulation Spectroscopy

The concept of microwave pulse matching is applied to three-pulse electron spin echo envelope modulation and sublevel correlation (HYSCORE) spectroscopy. Matched pulses enhance the efficiency of forbidden transfers and may drastically increase the signal intensity of basic frequency and combination frequency transitions in these conventional pulse EPR experiments. The theory of matched pulses is extended to the case of strong and largely isotropic hyperfine interactions, and numerical simulations are presented to gain a deeper insight into the inner working of the matched-pulse approach. It is shown that the enhancement of combination frequencies in matched HYSCORE can be used to determine the relative sign of hyperfine coupling constants as well as the number of equivalent nuclei. The enormous capacity of the approach is demonstrated on ordered and disordered systems. In particular, it is shown that in HYSCORE experiments the signal-to-noise ratio improvement for strongly coupled nitrogens and for proton combination peaks may be considerably larger than one order of magnitude, corresponding to a reduction in measuring time of more than a factor of 100.     

The modulation of coupled relaxation in porous media.

This work investigates the effects of modulation of the transverse and longitudinal relaxation of the surface-fluid/pore-fluid spin system in porous media. Important new NMR well logging applications identify pore fluids by varying the CPMG T(2) pulse spacing to discriminate on the basis of fluid diffusivities in applied and local static magnetic field gradients. However, anomalous laboratory CPMG T(2) results have been reported repeatedly over 25 years for various porous media filled with a single fluid. In relatively large pores, at near bulk conditions, the transverse relaxation of diffusing molecular spins should be proportional to the square of the CPMG pulse spacing tau, the susceptibility contrast at the pore wall and the applied gradient. Observed is a markedly linear tau dependence that saturates at a plateau for large tau. The effect is not quadratic in applied gradient or susceptibility. For large pores, the tau dependence and the saturation value are proportional to the surface-to-volume ratio of the pores. This is in distinct contrast to the behavior observed by Borgia, Brown and Fantazzini for systems with much smaller pores at higher magnetic fields. The large-pore anomalous behaviors can be explained as a modulation of the exchange between surface-fluid and pore-fluid spins, such as observed by Luz and Meiboom in 1963 for water enriched with quadrupolar 17O. Scalar coupling of the solid-surface spins to the fluid-surface spins was postulated by Kleinberg, Kenyon and Mitra as a dominant relaxation mechanism for the surface fluid. The CPMG tau effect can be described as the modulation of the exchange coupling by the CPMG pi pulses, which mix the magnetizations between the exchanging, strongly coupled spin systems of the pore-fluid and the surface-fluid, which is, in turn, weakly coupled by scalar or pseudo-scalar interactions to the fast-relaxing solid surface.     

Carr-Purcell-Meiboom-Gill imaging of prostate cancer: quantitative T2 values for cancer discrimination

Quantitative, apparent T(2) values of suspected prostate cancer and healthy peripheral zone tissue in men with prostate cancer were measured using a Carr-Purcell-Meiboom-Gill (CPMG) imaging sequence in order to assess the cancer discrimination potential of tissue T(2) values. The CPMG imaging sequence was used to image the prostates of 18 men with biopsy-proven prostate cancer. Whole gland coverage with nominal voxel volumes of 0.54 x 1.1 x 4 mm(3) was obtained in 10.7 min, resulting in data sets suitable for generating high-quality images with variable T(2)-weighting and for evaluating quantitative T(2) values on a pixel-by-pixel basis. Region-of-interest analysis of suspected healthy peripheral zone tissue and suspected cancer, identified on the basis of both T(1)- and T(2)-weighted signal intensities and available histopathology reports, yielded significantly (P<.0001) longer apparent T(2) values in suspected healthy tissue (193+/-49 ms) vs. suspected cancer (100+/-26 ms), suggesting potential utility of this method as a tissue specific discrimination index for prostate cancer. We conclude that CPMG imaging of the prostate can be performed in reasonable scan times and can provide advantages over T(2)-weighted fast spin echo (FSE) imaging alone, including quantitative T(2) values for cancer discrimination as well as proton density maps without the point spread function degradation associated with short effective echo time FSE sequences.     

Fast 3D echo planar SSFP-based 1H spectroscopic imaging: demonstration on the rat brain in vivo

A fast proton spectroscopic imaging pulse sequence based on the condition of steady-state free precession is presented. High 3D spatial and temporal resolution is achieved using simultaneous detection of both one spatial and one spectral dimension, with a time-dependent gradient cycle known from echo planar imaging. Additionally, in order to increase the spectral width of the measurement, an interleaved acquisition scheme is shown either for systems with limited gradient switching capabilities or applications with a wide chemical shift range. The pulse sequence is implemented on a standard 4.7-T nuclear magnetic resonance animal imaging system. Measurements with a total measurement time of less than 2.5 min and a nominal voxel size of 6.75 microl using a total of 64 x 32 x 16 voxels are performed on phantoms and healthy rat brain in vivo allowing the rapid detection of signals from both uncoupled and J-coupled spin systems with high signal-to-noise ratio.     

Self-Diffusion Imaging by Spin Echo in Earth's Magnetic Field

The NMR of the Earth's magnetic field is used for diffusion-weighted imaging of phantoms. Due to a weak Larmor field, care needs to be taken regarding the use of the usual high field assumption in calculating the effect of the applied inhomogeneous magnetic field. The usual definition of the magnetic field gradient must be replaced by a generalized formula valid when the strength of a nonuniform magnetic field and a Larmor field are comparable (J. Stepišnik,Z. Phys. Chem.190, 51–62 (1995)). It turns out that the expression for spin echo attenuation is identical to the well-known Torrey formula only when the applied nonuniform field has a proper symmetry. This kind of problem may occur in a strong Larmor field as well as when the slow diffusion rate of particles needs an extremely strong gradient to be applied. The measurements of the geomagnetic field NMR demonstrate the usefulness of the method for diffusion and flow-weighted imaging.     

Spin Echo Spectrometry Using Very Cold Neutrons

Concept of spin echo spectrometer on very cold neutrons (wavelengths λ ~ 10?30 nm) to provide extra high resolution in energy transfer (ΔE ~ 10^–13 eV) has been proposed. Simultaneous measurements of spin echo signals at different wavelengths will be realized using broadband spin flippers in combination with Fourier-analysis of λ-spectrum. The application of very cold neutrons should extend the spin echo time diapason radically, t ~ 10^–12?10^–3 s. This promises to open a set of novel scientific areas including the spectroscopy of chemical reactions and catalytic processes, conformational transitions in polymers and biological molecules, dynamic modes in carbon structures (fullerenes, nanotubes, graphenes) at scales from few nanometers to microns. Presently, the development of NSE-spectrometer on VCN becomes relevant since the project of ultra cold neutron source at WWR-M reactor (PNPI) is in progress.     

在辐射阻尼存在下有效横向弛豫时间T*2的快速测定

利用CPMG自旋回波技术,通过一连串180°脉冲抑制辐射阻尼效应,让磁化矢量经过横向弛豫T₂过程大幅度衰减后再检测回波信号的线宽,该方法可直接获得有效横向弛豫时间T*₂,并可在CPMG测试T₂值的同时进行. 另外,当饱和恢复法用于估计T*₂值时,信号检测必须使用小角度脉冲.所有结果已进行了实验验证.     

Electron Spin Echo of Photoinduced Spin-Correlated Polaron Pairs in P3HT:PCBM Composite

A variation of the electron spin echo (ESE) signal caused by laser pulse in a blend of [6,6]-phenyl C₆₁ butyric acid methyl ester and poly(3-hexylthiophene) (P3HT:PCBM) was detected. This variation was attributed to light-generated paramagnetic species in P3HT:PCBM blend, with non-equilibrium spin polarization. The echo-detected electron paramagnetic resonance (EPR) spectrum of these species closely resembles the time-resolved EPR spectrum of spin-correlated polaron pair PCBM^?/P3HT⁺ (Behrends et al. in Phys. Rev. B 85:125206, 2012) and was assigned to this pair. The characteristic times for polarization and coherence decay (9 ± 1 and 1.0 ± 0.2 μs, respectively) were measured for the PCBM^?/P3HT⁺ pair at 77 K. These times are long enough, which shows the possibility of the application of the ESE technique for studying spin evolution of light-generated charge transfer intermediates in composites of fullerenes and conductive polymers.     

Spin-lock techniques and CPMG imaging sequences: a critical appraisal of T1p contrast at 0.15 T

The addition of a spin-lock preparatory sequence to a Carr-Purcell-Meiboom-Gill (CPMG) imaging sequence provides a method which allows an accurate and simple comparison of T1p and T2 contrast. Sagittal and axial brain images, produced with the application of a three pulse preparatory spin-lock sequence prior to a sixteen-echo CPMG imaging sequence, are compared with images acquired without the spin-lock sequence. The CPMG sequence uses non-selective refocusing pulses. Therefore, observed echo signals accurately reflect T2 relaxation. This allows a convenient method for assessing the degree to which T1p and T2 contrast differ. The spin-lock CPMG (SL-CPMG) images were acquired with a spin-locking field amplitude of 0.4 G and resemble heavily T2-weighted images at 0.15 T. Quantitative analyses of signal intensities from edema and normal brain tissue confirm the qualitative observations. This in vivo method should prove useful for determining when the additional RF power deposition associated with spin-locking techniques will provide an alternate form of tissue contrast than that available from additional echo collection.