Anomalous pulse-angle and phase dependence of Hahn’s electron spin echo and multiple-quantum echoes of the spin correlated radical pair P700+A 1 − in photosystem I

In a spin-correlated radical pair system, anomalous pulse-angle and phase dependence of electron spin echo and multiple-quantum echoes were theoretically calculated by Tanget al. (J. Chem. Phys.106, 7471 (1997)). The maximum intensity of the out of phase signal at 45 degree of spin rotation angle was experimentally verified in two-pulse echoes of the light-induced P700⁺A ₁ ^? radical pair in Photosystem I. The values,D = 1.64 G andJ = 0.00 G, fit well with the experimental ESEEM spectra. Single and double quantum echoes were observed at the value oft = τ andT = 2τ with the laser flash-t-P1_70,ζ1-τ-P2_{140, ζ2}-T pulse sequence, which led to determination of the relaxation time T₂₃ between the singlet and triplet ¦T₀〉 states. The relaxation times of the zero and single quantum transitions were determinedT ₂₃ ≈ 100 ns andT ₂ = 1000 ns, respectively. The field sweep ESE signal shape can be fitted with the hyperfine inhomogeneities of 7 G for P700⁺ and of 10 G for A ₁ ^? .     

Large angle spin-echo imaging

A study was undertaken to assess the use of excitation flip angles greater than 90° for T₁ weighted spin-echo (SE) imaging with a single 180° refocusing pulse and short TR values. Theoretical predictions of signal intensity for SE images with excitation pulse angles of 90–180° were calculated based on the Bloch equations and then measured experimentally from MR images of MnCl₂ phantoms of various concentrations. Liver signal-to-noise ratios (SNR) and liver-spleen contrast-to-noise ratios (CNR) were measured from breathhold MR images of the upper abdomen in 16 patients using 90 and 110° excitation flip angles. The theoretical predictions showed significant improvements in SNR with excitation flip angles >90°, which were more pronounced at small TR values. The phantom studies showed reasonably good agreement with the theoretical predictions in correlating the excitation pulse angle with signal intensity. In the human imaging studies, the 110° excitation pulse angle resulted in a 7.4% (p < .01) increase in liver SNR and an 8.2% (p = .2) increase in liver-spleen CNR compared to the 90° pulse angle at TR = 275 ms. Increased signal intensity resulting from the use of large flip angle excitation pulses with a single echo SE pulse sequence was predicted and confirmed experimentally in phantoms and humans.     

Optimization of the refocusing flip angle in the characterization of cerebrospinal fluid dynamics using multi-spin echo acquisition cine imaging (MUSACI)

PurposeMulti-spin echo acquisition cine imaging (MUSACI) is a method used for cerebrospinal fluid (CSF) dynamics imaging based on the proton phase dispersion and flow void using 3D multi-spin echo imaging. In a previous study, the refocusing flip angle of MUSACI was set at a constant 80°. We conducted the present study to investigate the preservation the CSF signal intensity even in a long echo train and improve the ability to visualize CSF movement by modifying the refocusing flip angle in MUSACI.MethodsThe MUSACI images were acquired in 10 healthy volunteers (7 men and 3 women; age range 24–44 years; mean age 29.4 ± 6.2 years) with a 3.0 Tesla MR scanner. Five refocusing flip angle sets were applied: constant 30°, constant 50°, constant 80°, pseudo-steady state (PSS) 50°–70°–100° (PSS 50°), and PSS 80°–100°–130° (PSS 80°). In all sequences, the in-plane spatial resolution was 0.58 × 0.58 mm², and the CSF movement for one heartbeat was drawn at 80-msec intervals. The signal intensity (SI) of CSF in the lateral ventricle, the foramen of Monro, the third ventricle, the fourth ventricle, and the pons was measured on MUSACI. Pearson's correlation coefficient was calculated between the CSF SI and effective echo time (TE; TE_eff) in the lateral ventricle.ResultsBoth antegrade and retrograde CSF movements on the midsagittal MUSACI images and the retrograde CSF movement in the foramen of Monro was observed in all sequences with the constant flip angles. A strong reverse correlation between the CSF SI in the lateral ventricle and TE_eff values was observed with constant 30° (r = −0.96, p < 0.01), constant 50° (r = −0.97, p < 0.01) and constant 80° (r = −0.88, p < 0.01). A weak positive correlation was observed with PSS 50° (r = 0.28, p = 0.43), and a moderate reverse correlation was observed at PSS 80° (r = −0.60, p = 0.07). The SI values of the foramen of Monro, the third ventricle, and the fourth ventricle were significantly lower than that of the lateral ventricle, and those values were higher than that of the pons in both the constant 80° sequence and the PSS 50° sequence.ConclusionPSS 50° could be the optimal flip angle scheme for MUSACI, because the SI changes due to CSF movement and the SI preservation due to a long echo train were large due to the use of the refocusing flip angle method.     

Introduction of fast MR imaging in the assessment of hepatic steatosis

We determined the utility of fast gradient echo techniques (modified Dixon method) in the assessment of hepatic fat content. Fast spoiled gradient echo was performed on bovine liver/corn oil homogenates with known fat fractions (FF_E) to assess the accuracy of fat quantitation (FF_MRI). The pulse sequence was manipulated via alterations in TE (echo time), TR (repetition time), and α (flip angle). In vivo studies were then performed using breath-holding maneuvers on normal adult volunteers and subjects at risk to develop hepatic steatosis, with cystic fibrosis or morbid obesity. At out-of-phase, TE, TR, and α were 2.1 ms, 7.3 ms, and 30–50° and in-phase TE, TR, and α were 4.2 ms, 9.3 ms, and 30–50°; FF_MRI correlated well with FF_E. An elevated fat fraction was observed in a high percentage of subjects with cystic fibrosis and morbid obesity. Fast gradient echo techniques were used successfully in the assessment of hepatic steatosis. The reduced acquisition times permitted in vivo analysis on adults and children using breath hold maneuvers.     

三种测量橡胶交联密度的核磁共振方法比较

核磁共振（NMR）技术已经成为测量橡胶交联密度的一种常用技术手段．该文探讨了用于测量橡胶交联密度的三种NMR方法：¹H双量子（DQ）NMR、¹H Hahn回波和¹H CPMG回波,讨论了这些方法测量值差异的来源．在此基础上进一步研究了¹H CPMG回波方法中回波时间对测量值的影响,探讨了改善¹H CPMG回波方法的方案．     

Improved J-Compensated Apt Experiments

The derivation and investigation of two new J-compensated attached-proton-test experiments, CAPT2 and CAPT3, are presented. These methods incorporate fewer pulses than CAPT and are shown to be more effective over a wider range of ¹J_CH than spin flip, APT, and CAPT for CH, CH₂, and CH₃ spin systems. In addition, the magnitude of the flip angle of the initial pulse which creates transverse carbon magnetization is unrestricted in CAPT2 and CAPT3. The compensated CAPT3 sequence, which is patterned after the 90°_x90°_y90°_x composite pulse, is found to be excellent for routine use in ¹³C spectroscopy.     

Conventional and collision photon echo in ytterbium vapor

The polarization properties of the photon echo generated by two linearly polarized pulses of resonant radiation at the (6s6p)³ P ₁ ? (6s ²)¹ S ₀ transition of ¹⁷⁴Yb are investigated. A complicated polarization behavior of the photon echo versus an angle between the polarization vectors of the excitation pulses is revealed in a mixture of ytterbium vapor with inert gas. For the angles ranging from 0° to 75°, a conventional echo with its linear polarization coinciding with the second excitation pulse dominates and the echo amplitude decreases with an increasing angle. For the angles ranging from 75° to 89°, the photon echo is elliptically polarized. Finally, for an angle of 90°, the conventional echo disappears and the collision echo becomes linearly polarized along the first excitation pulse.     

Knee osteochondral junction imaging using a fast 3D T1-weighted ultrashort echo time cones sequence at 3T

The osteochondral junction (OCJ) of the knee joint is comprised of multiple tissue components, including a portion of the deep layer cartilage, calcified cartilage, and subchondral bone. The OCJ is of increasing radiological interest as it may be relevant in the early pathogenesis of osteoarthritis (OA). Due to its short transverse relaxation, the OCJ is invisible to clinical MR sequences. The purpose of this study was to develop a fast 3D T₁-weighted ultrashort echo time cones sequence with fat saturation (FS-UTE-Cones) for high resolution and high contrast imaging of the OCJ on a clinical 3T scanner. First, numerical simulations were performed to investigate how the flip angle affected the signal intensities and contrasts of both short and long T₁ tissues. The results from these simulations demonstrated that higher short T₁ contrast could be achieved with higher flip angle. Next, T₁ relaxation was measured for the different layers of a human patellar cartilage sample, and the results showed that the deepest layer had a significantly shorter T₁ value than other layers. Finally, a healthy knee joint was scanned with different flip angles and the OCJ was highlighted in the T₁-weighted FS-UTE-Cones sequence using a flip angle greater than 20°. The clinical T₂-weighted and proton density-weighted FSE sequences were also included for comparison, revealing a dark OCJ region. Representative T₁-weighted FS-UTE-Cones images of the whole knee of a healthy volunteer showed high signal intensity bands in the OCJ regions of the patella, femur, and tibia. On the other hand, T₁-weighted FS-UTE-Cones imaging of the knee joints of OA patients revealed regions with reduction or loss of these high signal intensity bands in the OCJ regions, indicating abnormal OCJ tissue composition. The proposed 3D T₁-weighted FS-UTE-Cones sequence with a 3-min scan time may be very useful for demonstrating the involvement of the OCJ regions in early OA.     

粉末样品中氘核NMR的回波序列

本文提出一个回波序列,它由四个90和一个45脉冲构成,具有较宽的激发带宽和较短的激发时间,可用于氘核NMR固体线型的测量之中,数值计算结果表明该回波序列的激发带宽几乎比传统的四极回波宽一倍。²D-PMMA粉末样品的实验结果证实了本文设计的回波序列的优越性。     

Influence of Cholesterol on Molecular Motions in Spin-Labeled Lipid Bilayers Observed by Stimulated ESE

Electron spin echo (ESE) study was performed for spin-labeled lipids 1-palmitoyl-2-stearoyl-(5-d)-sn-glycero-3-phosphocholine in 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine phospholipid bilayer. Recently (Isaev and Dzuba in J Phys Chem B 112:13285–13291, 2008), three-pulse stimulated ESE was shown to be sensitive to two types of orientational motion of spin labels in phospholipid bilayers at low temperatures (~100–150 K). The first one is fast stochastic libration, with correlation time on the nanosecond time scale. The second one is slow rotational motion, developing on the accessible for measurements microsecond time scale in a small range of reorientation angles, ~0.1°–1°. These two types of motions may be easily discriminated by dependences of the echo decay rates on the time delays between the pulses. The presence of cholesterol in lipid bilayers is found to suppress remarkably rotational motions, while on the contrary stochastic librations seem to become somewhat enhanced. These results evidence that cholesterol increases the long-time stability of lipid orientations in the bilayer, with simultaneous increase of fast fluctuations of these orientations. The former may be related to the known condensing effect of cholesterol and to raft formations, while the latter to the ordering effect.     

Flip Angle for the Optimal <Emphasis Type="Italic">T</Emphasis><Subscript>1</Subscript>-weighted Image in the 3-D Volumetric Interpolated Breath-hold Examination Abdominal Magnetic Resonance Imaging Technique

The purpose of this study was to determine an optimal flip angle for T ₁-weighted images on abdominal examination by comparing the signal-to-noise ratio (SNR) and contrast-to-noise ratio (CNR) depending on the change in flip angle based on the volumetric interpolated breath-hold examination (VIBE) technique. The subjects in this study included 50 patients (20 men and 10 women; average age, 60 years) who visited the hospital between October 2009 and March 2010 to receive an abdominal magnetic resonance imaging (MRI) examination. Among the 50 patients, there were 27 patients with hypervascular hepatocellular carcinomas (HCCs) and 23 patients with hemorrhagic HCCs. A 3 T MR scanner (Magnetom Tim Trio; Siemens, Germany) with a 12-channel body coil was used. For the pulse sequence, the VIBE (time of repetition TR, 3.18 ms; time of echo TE, 1.16 ms; matrix, 384 × 307; slice thickness, 3 mm; field of view FOV, 380 mm; bandwidth BW, 720 Hz) and breath-hold examination with an examination time of 19 s were used. Images of the axial and coronal planes at three flip angles (10°, 25°, and 35°) were obtained. Based on the images obtained, the signal intensities of the liver, lesions, and background noise were measured and the SNR and CNR were calculated. For evaluation of the optimal flip angle, SPSS for Windows (version 17.0) was used to conduct the non-parametric Kruskal–Wallis test. The SNRs for hypervascular and hemorrhagic HCCs, depending on changes in flip angle of the VIBE, were 11.12 ± 0.98, 10.83 ± 1.44, and 9.61 ± 1.66, and 76.00 ± 6.43, 43.32 ± 5.89, and 30.45 ± 4.27 at angles of 10°, 25°, and 35°, respectively. The CNRs were 14.83 ± 0.12, 7.38 ± 0.41, and 5.70 ± 0.66, and 3.95 ± 0.21, 2.42 ± 0.58, and 1.69 ± 0.93, respectively (p < 0.05). At a flip angle of 10°, the SNR and CNR were the highest. When the flip angles were 25° and 35°, the contrast of the image, as well as the SNR, were shown to have a downward trend (p < 0.05). A flip angle of 10° is considered to be useful for the optimal T ₁-weighted image to detect HCC in the three-dimensional VIBE abdominal MRI technique.     

Reducing bias in DREAM flip angle mapping in human brain at 7T by multiple preparation flip angles

DREAM (Dual Refocusing Echo Acquisition Mode) is an ultra-fast multi-slice B₁⁺-mapping technique based on the single-shot STEAM sequence. To study systematic errors at high actual flip angles (FA) and low SNR, DREAM B₁⁺ maps at 3.75×3.75×3.50 mm³ resolution were acquired at 7T in phantoms and human brain in vivo with nominal FAs between 20° and 90° for the two STEAM preparation pulses. Predicted B₁⁺ estimates were underestimated at actual FAs above 50° while noise was prominent below 20°. With a reliable interval of the actual FA between 20° and 50° identified, a B₁⁺ range of 33% - 200% of nominal FA is covered by varying the nominal preparation angle through 25°, 40°, and 60°. Individual B₁⁺ maps are thresholded according to the identified interval and combined into a single map. We demonstrate the benefit of the combined low-noise, low-bias B₁⁺ maps for dual flip angle T₁-mapping.     

Electron spin-echo experiments in photo-excited triplet states in an external magnetic field

Electron spin-echo experiments in the photo-excited triplet states of quinoxaline-d₆ and naphthalene-d₈ at 1·2 K in an external magnetic field are presented. These include two-pulse Hahn echoes, three-pulse stimulated echoes and Carr-Purcell pulse-echo trains. The decay of the Hahn and stimulated echoes as a function of pulse interval yields measures of the spin relaxation times. Furthermore, the Hahn echo is used to obtain E.P.R. line shapes and the dynamics of the triplet sublevel populations. The angular dependence of the Hahn echo is also investigated. The Hahn echo decay time and decay modulation suggest the kind of role played by nuclear spins in the loss of electron spin phase coherence. Some promising characteristics of the pulse method are discussed.     

Abnormal electron spin echo and multiple-quantum coherence in a spin-correlated radical pair system

The phenomena of the abnormal “out-of-phase” electron spin echo in a photo-induced spin-correlated radical pair system are examined theoretically. It is shown that such abnormal phenomena are a consequence of initial non-Boltzmann distribution and zero-quantum coherence produced by laser excitation. The analysis of echo amplitude versus the pulse-angle of the microwave pulse reveals two sources for the formation of the echo. The method of excitation and detection of multiple-quantum coherence using a phase-cycled 2-pulse sequence is also discussed. Such a technique is complementary to the ESE method.     

Correlation between Hepatic Fat Content Using 3-Echo 3-D Dixon Method and Intravoxel Incoherent Motion (IVIM) Perfusion MR Imaging

Fat accumulates as droplets in the hepatocyte swelling, distortion of microcirculatory anatomy and compression of sinus. This study aims to investigate the correlation between the T2*-corrected fat fraction (FF) value acquired via gradient echo with a low flip angle and parenchymal pseudorandom blood perfusion (P _fraction), microcirculation (D _fast), and slow component of diffusion (D _slow), acquired via intravoxel incoherent motion (IVIM), and to investigate the blood microcirculation and diffusion components of liver parenchyma, according to fat deposition. A total of 126 patients underwent 3-T magnetic resonance imaging, including a 3-echo three-dimensional (3-D) gradient echo sequence with T2*-corrected Dixon reconstruction and IVIM sequence. Pearson’s correlation analysis was conducted to investigate the correlation of the FF obtained via the Dixon method with the apparent diffusion coefficient (ADC), D _slow, P _fraction, and D _fast obtained via IVIM. Correlation analysis was also conducted for the IVIM mapping images. A confidence level of p < 0.05 was set. A negative correlation was found between the T2*-corrected FF acquired using the 3-echo 3-D Dixon method and D _slow acquired via IVIM (r = ?0.181, p < 0.05). It was likely due to the increased extracellular collagen deposition and increased intracellular fat droplets during the progression of liver fibrosis.     

Double-quantum nutations in a two-level spin system

We report experimental results of the oscillatory response of a two-level spin system (E'₁ centres in glassy silica) excited by a step-modulated radiation tuned to the double-quantum (DQ) resonance. On the basis of a semiclassical calculation of the transient regime, the observed oscillations are ascribed to the nutations of the DQ transitions.     

Low-Temperature Molecular Motions in Phospholipid Bilayers in Presence of Glycerol as Studied by Spin-Echo EPR of Spin Labels

Glycerol is used as a cryoprotective agent to protect biological systems under freezing conditions. Electron spin echo (ESE) spectroscopy, a pulsed version of EPR, is capable of studying low-temperature molecular motions of nitroxide spin labels. ESE technique was applied to study molecular motions in phospholipid bilayers prepared from 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) with added spin-labeled lipids 1-palmitoyl-2-stearoyl-(n-DOXYL)-sn-glycero-3-phosphocholine (n-PCSL, n was optionally 5 or 16). Bilayers were hydrated (solvated) either in pure water or in a 1:1 v/v water–glycerol mixture. In the used ESE approach, there were studied stochastic (or diffusive) orientational vibrations of the molecule as a whole (i.e., stochastic molecular librations). The anisotropic contribution to the echo decay rate, W _anis, was measured, which is proportional, according to theory, to the product of the mean-squared angular amplitude \(\langle \alpha^{ 2} \rangle\) and the correlation time τ _c. W _anis was found to be small below and to sharply increase above 200 K, for the both types of solvents and the both label positions. As compared with hydration by pure water, in presence of glycerol W _anis was larger for the 5th label position while for the 16th one it did not change. Also, for the 5th label position W _anis values were found to be nearly the same as those for a polar spin probe 3,4-dicarboxy-PROXYL which was separately added to the bilayer as a reference and which is assumed to be partitioned only into the solvating shell. These results indicate that motions at the surface of bilayer are governed by the motion of solvating shell while motions in the bilayer interior occur independently. The relation of the obtained data with the dynamical transition phenomenon that is known for biological substances near 200 K from neutron scattering and Mössbauer absorption is discussed.     

Improved SNR in linear reordered 2D bSSFP imaging using variable flip angles

This article presents a variable flip-angle approach for balanced steady-state free precession (bSSFP) imaging, which allows increases in signal-to-noise ratio (SNR) and contrast-to-noise ratio (CNR) while keeping specific absorption rate (SAR) constant or reduces SAR for given CNR and SNR. The gain in SNR is achieved by utilizing the higher signal in the transient phase. Flip-angle variation during the echo train is realized using a trigonometric function with M steps (ramp length). Variation is combined with a linear k-space reordering such that outer parts of k-space are sampled using a lower flip angle α_min, while the central part of k-space is acquired with a higher flip angle α_max. No additional preparation or dummy cycles are applied prior to data acquisition. Several variation schemes with different starting flip angles α_min and ramp length M are considered. For example, using α_min=1° and M=96, α_max can be set to 47° without exceeding SAR limits at 3 T and gaining up to 50% in SNR, while, conventionally, α=34° is the maximal possible flip angle. Resolution seems unaffected in volunteer imaging. In all cases, no transient artifacts due to flip-angle variation were observed. This article demonstrates the use of flip-angle variations in bSSFP to increase SNR and CNR while keeping SAR constant, which is especially important at higher field strengths. Flip-angle variation can also be combined with other methods such as parallel imaging techniques for further SAR reduction.     

Heteronuclear intermolecular single-quantum coherences in liquid nuclear magnetic resonance

This paper analyses the heteronuclear Cosy Revamped by Asymmetric Z-gradient Echo Detection pulse sequence. General theoretical expressions of the pulse sequence with arbitrary flip angles were derived by using dipolar field treatment and signals originating from heteronuclear intermolecular single-quantum coherences （iSQCs） in highly-polarized two spin-1/2 systems were mainly discussed in order to find the optimal flip angles. The results show that signals from heteronuclear iSQCs decay slower than those from intermolecular double-quantum coherences or intermolecular zero-quantum coherences. Magical angle experiments validate that the signals are from heteronuclear iSQCs and insensitive to the imperfection of radio-frequency flip angles. All experimental observations are in excellent agreement with theoretical predictions. The quantum-mechanical treatment leads to similar predictions to the dipolar field treatment.