Ergodicity and efficiency of cross-polarization in NMR of static solids

Cross-polarization transfer is employed in virtually every solid-state NMR experiment to enhance magnetization of low-gamma spins. Theory and experiment is used to assess the magnitude of the final quasistationary magnetization amplitude. The many-body density matrix equation is solved for relatively large (up to N=14) spin systems without the spin-temperature assumption for the final spin states. Simulations show that about 13% of the thermodynamic limit is still retained within the proton bath. To test this theoretical prediction, a combination of a reverse cross-polarization experiment and multiple contacts is employed to show that the thermodynamic limit of magnetization cannot be transferred from high- to low-gamma nuclei in a single contact. Multiple contacts, however, fully transfer the maximum magnetization. A simple diffusion on a cone model shows that slow dynamics can affect the build up profile for the transferred magnetization.     

固体核磁共振中膜蛋白双交叉极化效率与动力学参数相关的定量分析

固体核磁共振（NMR）中双交叉极化（DCP）是用于膜蛋白信号指认的多维异核相关实验的基本技术模块.DCP的效率在很大程度上决定了多维异核相关实验的效率.本文分析了3种典型的膜环境中的膜蛋白（AQPZ、DAGK和EV71 2B）的DCP效率及其影响因素.结果显示,在相同的实验条件下,3种蛋白样品的DCP效率存在明显差异：其中AQPZ的DCP效率最高（31%）,DAGK的效率次之（23%）,EV71 2B的效率最低（14%）.通过测量它们在旋转坐标下的自旋-晶格弛豫时间（T_1ρ）和偶极耦合常数（D_HN）,发现膜蛋白的运动会明显缩短T_1ρ,但对D_HN的影响较小.在实验的基础上,建立了T_1ρ与DCP效率相关的模型,并基于DCP动力学的定量分析,证明了运动导致的T_1ρ缩短是降低DCP效率的主要原因.因此,可以通过定量分析未知样品的T_1ρ来预测其DCP的最优效率,为DCP实验的优化提供依据.     

Evaluation of a Shuttle DNP Spectrometer by Calculating the Coupling and Global Enhancement Factors of l-Tryptophan

A liquid state shuttle dynamic nuclear polarization (DNP) spectrometer is presented, featuring several technical modifications that increase stability and improve reproducibility. For the protons of l-tryptophan, the signal enhancement and the DNP spin properties, such as relaxation, were measured and compared with each other. The calculated coupling factors suggest that the proton accessibility for the polarizer molecule has an important influence on the DNP enhancement. In general, short proton spin longitudinal relaxation times without radical reduce the detectable enhancement by decreasing the leakage factor and increasing the relaxation losses during the course of the sample transfer. The usage of a global enhancement factor gives a more complete overview of the capabilities for the described experimental setup. Global enhancements of up to ?4.2 for l-tryptophan protons are found compared to pure Boltzmann enhancements of up to ?2.4.     

Mössbauer study of the fast magnetization reversal in FeBO3 induced by external RF magnetic fields

The effect of fast magnetization reversal induced by external radio frequency (rf) fields has been studied in FeBO₃ using the Mössbauer technique. The rf collapse and sideband effects were investigated as a function of intensity for two rf field frequencies: 62 and 36 MHz. The switching times estimated for magnetization reversal are of the same order of magnitude as in amorphous metals and Fe-Ni alloys. Because of the relatively short switching times the magnetization reversal must be of rotational character.     

Low-power MRI by Frank-sequence excitation

Recently, a new NMR method employing an rf excitation scheme with strongly reduced power has been introduced, which is based on modulating rf pulses according to Frank sequences. For many applications, a reduction of rf power is essential, e.g. to eliminate bulky rf pre-amplifiers or in medical high-field MRI to preserve patient safety. Another benefit of the new scheme are very short dead times allowing for measurements of samples with short relaxation times. In this work, Frank-sequence excitation is used for low-power imaging for the first time. Results of one-, two-, and three-dimensional imaging experiments are presented and compared to conventional images.     

Design of self-refocused pulses under short relaxation times

The effect of using self-refocused RF pulses of comparable duration to relaxation times is studied in detail using numerical simulation. Transverse magnetization decay caused by short T2 and longitudinal component distortion due to short T1 are consistent with other studies. In order to design new pulses to combat short T1 and T2 the relaxation terms are directly inserted into the Bloch equations. These equations are inverted by searching the RF solution space using simulated annealing global optimization technique. A new T2-decay efficient excitation pulse is created (SDETR: single delayed excursion T2 resistive) which is also energy efficient. Inversion pulses which improve the inverted magnetization profile and achieve better suppression of the remaining transverse magnetization are also created even when both T1 and T2 are short. This is achieved, however, on the expense of a more complex B1 shape of larger energy content.     

Rotating-frame spin—lattice relaxation measurements (T 1ρ) with weak spin-locking fields in the presence of homonuclear dipolar coupling

The rotating-frame spin-lattice relaxation time T_1ρ, for two identical protons in the presence of residual dipole-dipole coupling is examined both theoretically and experimentally. The measured T_1ρ, value as well as the amplitude and frequency of the dipolar oscillations are described by a theoretical framework involving three coupled rotating-frame magnetization modes. These modes include the magnetization along the spin-lock field, an antiphase magnetization, and an unobservable form of two-spin order. Inhomogeneity in the spin-locking field decouples the two latter modes resulting in the rapid damping of dipolar oscillations. Both theoretical considerations and experimental observations demonstrate conclusively that whenever the amplitude of the spin-locking field B₁ greatly exceeds the dipolar coupling, the measured T_1ρ, is independent of B₁. Conversely, if B₁ is on the order of the dipolar coupling, the measured T_1ρ, increases as B₁ increases. Dipolar oscillations that are important for times short compared to T_1ρ, are rapidly damped for larger magnitudes of B₁.     

Hydration water dynamics in biopolymers from NMR relaxation in the rotating frame

Assuming dipole-dipole interaction as the dominant relaxation mechanism of protons of water molecules adsorbed onto macromolecule (biopolymer) surfaces we have been able to model the dependences of relaxation rates on temperature and frequency. For adsorbed water molecules the correlation times are of the order of 10(-5)s, for which the dispersion region of spin-lattice relaxation rates in the rotating frame R(1)(ρ)=1/T(1)(ρ) appears over a range of easily accessible B(1) values. Measurements of T(1)(ρ) at constant temperature and different B(1) values then give the "dispersion profiles" for biopolymers. Fitting a theoretical relaxation model to these profiles allows for the estimation of correlation times. This way of obtaining the correlation time is easier and faster than approaches involving measurements of the temperature dependence of R(1)=1/T(1). The T(1)(ρ) dispersion approach, as a tool for molecular dynamics study, has been demonstrated for several hydrated biopolymer systems including crystalline cellulose, starch of different origins (potato, corn, oat, wheat), paper (modern, old) and lyophilized proteins (albumin, lysozyme).     

Magnetization recovery for signal enhancement: a fast imaging DEFT-based technique

This paper describes the development and application of a new fast MRI technique based on the DEFT principle. The sequence named MAgnetization RecoverY for Signal Enhancement (MARYSE) is composed of two completely symmetric gradient echoes separated by a 180 degrees refocusing pulse. The RF pulse scheme, 90 degrees x-180 degrees y-90 degrees -x enables restoration of the transverse magnetization along the longitudinal axis, and consequently artificially increases R1 relaxation rate. In this sequence, the period between the excitation pulse and the restoring pulse (Tem: transverse magnetization evolution time) is very short (< 10 ms). This makes possible a significant increase in signal-to-noise ratio, even with a relatively short repetition time (20 ms). Simulations were performed for different values of Tem and TR at definite T1 and T2 and for different values of T1 and T2 at constant Tem and TR. Relevant signal enhancement for species with long relaxation time constants as compared to classical gradient echo and fast spin-echo imaging was expected. In vitro studies on a fat/water phantom confirmed this simulation. Application of MARYSE to mouse brain imaging permitted to visualize almost completely cerebrospinal fluid of the ventricles, a signal usually partially saturated in fast gradient echo imaging.     

Hydration-optimized oriented phospholipid bilayer samples for solid-state NMR structural studies of membrane proteins

The preparation of oriented, hydration-optimized lipid bilayer samples, for NMR structure determination of membrane proteins, is described. The samples consist of planar phospholipid bilayers, containing membrane proteins, that are oriented on single pairs of glass slides, and are placed in the coil of the NMR probe with the bilayer plane perpendicular to the direction of the magnetic field. Lipid bilayers provide a medium that closely resembles the biological membrane, and sample orientation both preserves the intrinsic membrane-defined directional quality of membrane proteins, and provides the mechanism for resonance line narrowing. The hydration-optimized samples overcome some of the difficulties associated with multi-dimensional, high-resolution, solid-state NMR spectroscopy of membrane proteins. These samples have greater stability over the course of multi-dimensional NMR experiments, they have lower sample conductance for greater rf power efficiency, and enable greater rf coil filling factors to be obtained for improved experimental sensitivity. Sample preparation is illustrated for the membrane protein CHIF (channel inducing factor), a member of the FXYD family of ion transport regulators.     

Decay of dipolar order in diamagnetic and paramagnetic proteins and protein gels

Magnetic relaxation in solids may be complicated by the creation and loss of dipolar order at finite rates. In tissues the molecular and spin dynamics may be significantly different because of the relatively high concentration of water. We have applied a modified Jeneer-Broekaert pulse sequence to measure dipolar relaxation rates in both dry and hydrated protein systems that may serve as magnetic models for tissue. In lyophilized and dry serum albumin, the dipolar relaxation time, T(1D) is on the order of 1 ms and is consistent with earlier reports. When hydrated by deuterium oxide, the dipolar relaxation times measured were on the order of tens of microseconds. When paramagnetic centers are included in the protein, the Jeneer-Broekaert echo decay times became the order of the decay time for transverse magnetization, i.e., the order of 10 micros or less. In the hydrated or paramagnetic systems, the dipolar relaxation times are too short to require inclusion in the quantitative analysis of magnetization transfer experiments.     

Temperature dependence of nuclear magnetization and relaxation

The temperature dependences of nuclear magnetization and relaxation rates are reviewed theoretically and experimentally in order to quantify the effects of temperature on NMR signals acquired by common imaging techniques. Using common sequences, the temperature dependences of the equilibrium nuclear magnetization and relaxation times must each be considered to fully understand the effects of temperature on NMR images. The temperature dependence of the equilibrium nuclear magnetization is negative because of Boltzmann's distribution for all substances at all temperatures, but the combined temperature dependences of the equilibrium magnetization and relaxation can be negative, weak or positive depending on the temperature (T), echo time (T(E)), repetition time (T(R)), and the temperature dependences of the relaxation times T(1)(T) and T(2)(T) in a pulse sequence. As a result, the magnitude of the NMR signal from a given substance can decrease, increase or stay somewhat constant with increasing temperature. Nuclear thermal coefficients are defined and predictions for spin echo and other simple sequences are verified experimentally using a number of substances representing various thermal and NMR properties.     

Kinetics of NMR spin-lock polarization transfer in crystalline glycine and spin-lattice relaxation of amino acids

We report data determined from proton-carbon polarization-transfer kinetics at 23 degrees C for six common solid amino acids. Proton spin-lattice relaxation times in the rotating frame, T(1rhoH), for alpha-glycine, alanine, cysteine, leucine, isoleucine, and valine determined from the long-time decay of the carbon magnetization indicate that the presence of a mobile entity such as a methyl group shortens T(1rhoH) to a few milliseconds. Polarization transfer between protons and carbons in polycrystalline alpha-glycine is analyzed and compared to theoretical models, two of which account for the variation of polarization-transfer rate with orientation of the dipole-dipole vector in the magnetic field. A generalization of a model proposed by Mueller et al. (Phys. Rev. Lett. 32 (1974) 1402) reproduces the observed polarization transfer in alpha-glycine with reasonable accuracy, showing that the early time development reflects orientational variation of dipolar oscillations.     

Dynamics of paramagnetic agents by off-resonance rotating frame technique

Off-resonance rotating frame technique offers a novel tool to explore the dynamics of paramagnetic agents at high magnetic fields (B0 > 3T). Based on the effect of paramagnetic relaxation enhancement in the off-resonance rotating frame, a new method is described here for determining the dynamics of paramagnetic ion chelates from the residual z-magnetizations of water protons. In this method, the dynamics of the chelates are identified by the difference magnetization profiles, which are the subtraction of the residual z-magnetization as a function of frequency offset obtained at two sets of RF amplitude omega(1) and pulse duration tau. The choices of omega(1) and tau are guided by a 2-D magnetization map that is created numerically by plotting the residual z-magnetization as a function of effective field angle theta and off-resonance pulse duration tau. From the region of magnetization map that is the most sensitive to the alteration of the paramagnetic relaxation enhancement efficiency R(1rho)/R1, the ratio of the off-resonance rotating frame relaxation rate constant R(1rho) verse the laboratory frame relaxation rate constant R(1), three types of difference magnetization profiles can be generated. The magnetization map and the difference magnetization profiles are correlated with the rotational correlation time tauR of Gd-DTPA through numerical simulations, and further validated by the experimental data for a series of macromolecule conjugated Gd-DTPA in aqueous solutions. Effects of hydration water number q, diffusion coefficient D, magnetic field strength B0 and multiple rotational correlation times are explored with the simulations of the magnetization map. This method not only provides a simple and reliable approach to determine the dynamics of paramagnetic labeling of molecular/cellular events at high magnetic fields, but also a new strategy for spectral editing in NMR/MRI based on the dynamics of paramagnetic labeling in vivo.     

Observation of a new coherent transient in NMR — Two-pulse nutational stimulated echo in the angular distribution of gamma-radiation from oriented nuclei

A new coherent transient in NMR, the two-pulse nutational stimulated echo is reported for the ferromagnetic system⁵⁰CoFe, observed by monitoring the nuclear spin dynamics as a function of the second pulse duration via anisotropic gamma quanta from thermally oriented radioactive nuclei,⁶⁰Co. The mechanism of echo formation under strong Larmor inhomogeneous broadening and the secondary but important role of inhomogeneity associated with the rf amplitude (Rabi freqeuncy) due to skin-effect are investigated via the method of concatenation of perturbation factors in the statistical tensor formalism. For those experiments performed on time scales short compared with irreversible relaxation the theoretical predictions and subsequent experimental time-domain signals are in excellent accord. Remarkable constancy of amplitude of the new gamma-detected two-pulse echo with increase of interpulse time interval is observed, the longitudinal relaxation being manifest in the off-echo signals. Comparisons are made with NMRON four-pulse stimulated off-echo decay (analogous with conventional NMR three pulse stimulated echo) which is also sensitive to longitudinal relaxation, and with three-pulse on-echo decay (analogous with conventional NMR two-pulse Hahn echo) which measures transverse relaxation.     

High proton polarization by microwave-induced optical nuclear polarization at 77 K

Protons in naphthalene and p-terphenyl doped with pentacene have been polarized up to 32% and 18%, respectively, at liquid nitrogen temperature in a magnetic field of 0.3 T by means of microwave-induced optical nuclear polarization. The polarization was measured by nuclear magnetic resonance as well as by the neutron transmission method. The relaxation time of the proton polarization at 0.0007 T and 77 K was found to be almost 3 h and the polarization enhancement reached a record value of 8x10(4). The usefulness of the method in many areas of physics and chemistry is discussed.     

63Cu NMR evidence for enhanced antiferromagnetic correlations around Zn impurities in YBa2Cu3O6.7

Doping the high- T(c) superconductor YBa2Cu3O6.7 with 1.5% of nonmagnetic Zn impurities in CuO2 planes is shown to produce a considerable broadening of 63Cu NMR spectra, as well as an increase of low-energy magnetic fluctuations detected in 63Cu spin-lattice relaxation measurements. A model-independent analysis demonstrates that these effects are due to the development of staggered magnetic moments on many Cu sites around each Zn and that the Zn-induced moment in the bulk susceptibility might be explained by this staggered magnetization. Several implications of these enhanced antiferromagnetic correlations are discussed.     

Theoretical studies of the effect of the dipolar field in multiple spin-echo sequences with refocusing pulses of finite duration

It has been observed recently that the finite duration of refocusing rf pulses in a multiecho acquisition of the signal formed under the influence of the dipolar field leads to significant signal attenuation [S. Kennedy, Z. Chen, C.K. Wong, E.W.-C. Kwok, J. Zhong, Investigation of multiple-echo spin-echo signal acquisition under distant dipole-dipole interactions, Proc. Int. Soc. Magn. Reson. Med. 13 (2005) 2288]. Hereto, we quantify the phenomenon by evaluating analytically the influences of both the distant dipolar field (DDF) and transverse relaxation T2 on the magnetization in a multiecho pulse sequence based on correlation spectroscopy revamped by asymmetric z-gradient echo detection (CRAZED). Analytic expressions for the magnetization were obtained, which demonstrate explicitly the origin of rephased signal in the presence of the finite pi pulses in the multiecho train. The expressions also explain the effects of the DDF and T2 during the refocusing pulses on the signal strength, and show the substantial signal dependence on the phase of the rf pulses. We show that when the DDF effect during the pulse is canceled, the signal rises primarily during the free evolution time in the acquisition period. This elucidates the signal attenuation when the rf pulses cover a significant proportion of time in the sequence. In addition, we performed an optimization on the number of refocusing pulses that maximizes the total acquired signal using parameters for water, brain white matter, and muscle. We found that maximal signal-to-noise ratio is obtained when the pulse duration approximately equals the free evolution time in the samples with a wide range of T2.     

Pump-probe experiments on the single-molecule magnet Fe8: measurement of excited level lifetimes

We present magnetization measurements on the single-molecule magnet Fe8 in the presence of pulsed microwave radiation. A pump-probe technique is used with two microwave pulses with frequencies of 107 and 118 GHz and pulse lengths of several nanoseconds to study the spin dynamics via time-resolved magnetization measurements using a Hall probe magnetometer. We find evidence for short spin-phonon relaxation times of the order of 1 micros. The temperature dependence of the spin-phonon relaxation time in our experiments is in good agreement with previously published theoretical results. We also established the presence of very short energy diffusion times that act on a time scale of about 70 ns.     

Impact of selective excitation on carbon longitudinal relaxation: Towards fast solid-state NMR techniques

The effect of selective pulses on the apparent carbon longitudinal relaxation is investigated in three fully ¹³C-labeled systems, histidine as a model system and two proteins MerP and YajG. It is shown that the longitudinal relaxation of a selectively excited carbon spin is greatly enhanced, mainly because of fast spin-diffusion. This relaxation enhancement allows reducing the time necessary for polarization recovery between two experiments. This effect can be exploited either to improve the sensitivity of NMR experiments or to reduce the experimental time. Using selective carbon excitation combined with fast pulsing on fully ¹³C-labeled proteins, a sensitivity improvement of 20–45% over standard cross-polarization methods is predicted from the measured relaxation times.