Chemical shift referencing in MAS solid state NMR

Solid state 13C magic angle spinning (MAS) NMR spectra are typically referenced externally using a probe which does not incorporate a field frequency lock. Solution NMR shifts on the other hand are more often determined with respect to an internal reference and using a deuterium based field frequency lock. Further differences arise in solution NMR of proteins and nucleic acids where both 13C and 1H shifts are referenced by recording the frequency of the 1H resonance of DSS (sodium salt of 2,2-dimethyl-2-silapentane-5-sulphonic acid) instead of TMS (tetramethylsilane). In this note we investigate the difficulties in relating shifts measured relative to TMS and DSS by these various approaches in solution and solids NMR, and calibrate adamantane as an external 13C standard for solids NMR. We find that external chemical shift referencing of magic angle spinning spectra is typically quite reproducible and accurate, with better than +/-0.03 ppm accuracy being straight forward to achieve. Solid state and liquid phase NMR shifts obtained by magic angle spinning with external referencing agree with those measured using typical solution NMR hardware with the sample tube aligned with the applied field as long as magnetic susceptibility corrections and solvent shifts are taken into account. The DSS and TMS reference scales for 13C and 1H are related accurately using MAS NMR. Large solvent shifts for the 13C resonance in TMS in either deuterochloroform or methanol are observed, being +0.71 ppm and -0.74 ppm from external TMS, respectively. The ratio of the 13C resonance frequencies for the two carbons in solid adamantane to the 1H resonance of TMS is reported.     

一体化NMR波谱仪梯度-场频联锁-匀场系统设计

介绍一体化核磁共振波谱仪梯度-场频联锁-匀场系统的设计方案. 该方案使用嵌入式以太网、FPGA(Field Programmable Gate Array,现场可编程门阵列)、EMI(External Memory Interface, 外部存储器接口)和高速串行总线等技术构建了基于以太网的通信系统和使用并行运算的控制系统, 并具备CAN(Controller Area Network,控制器局域网)总线通信的能力. 梯度放大器通过LVDS(Low-Voltage Differential Signaling,低压差分信号传输)接口与主控系统的梯度波形发生器连接,实现与谱仪工作站的交互. 系统采用插板式结构和通用性电路的设计方法,具有很好的扩展能力和适应性,能够满足不同谱仪的需求. 系统在11.7 T(500 MHz)NMR系统中进行了有效的锁场、匀场和梯度特性的测试,证明了该方案的可行性.     

Towards beyond-1 GHz solution NMR: internal 2H lock operation in an external current mode

We have commenced a project to develop a beyond-1 GHz solution NMR spectrometer using a HTS coil. Due to a small residual resistance present in the HTS conductor and joint resistance between conductors, a stable persistent current sufficient for NMR measurements is unlikely. Therefore, a current has to be supplied to the HTS coil from an external power supply. The ripple of an external power supply causes a field fluctuation which must be stabilized. In this study we show results of NMR measurements using a 500-600 MHz NMR in such an external current mode: the field fluctuations are stabilized by an internal 2H lock. The field fluctuation from the external power supply comprises a major field fluctuation component at low frequencies, 0.003-0.005 Hz, and superimposed minor field ripples at 2 Hz and 50 Hz. The former limits the time interval of the internal 2H lock, while the latter generates sidebands in the NMR spectrum. Sideband and baseline noise are controlled by appropriate selection of the feedback loop parameters of the lock. The quality of the 1D-solution NMR spectra observed in external current mode is equivalent to that obtained in persistent current mode. However, if the feedback loop time is as short as the gradient pulse width, refocusing of the NMR signal is lost and NMR peaks disappear. The 2D-NOESY and the 2D-HSQC spectra of ubiquitin in an external current mode have been acquired. The quality of the 2D spectra is equivalent to those obtained in persistent current mode; i.e. the internal 2H lock operates stably over an experimental time interval of 40-50 min. To realize a beyond-1 GHz NMR spectrometer, further investigations must be made of (i) the long term stability of a DC power supply, (ii) the enhancement of the compensation field limit for the internal 2H lock, (iii) the extension of the helium refill time interval, and (iv) a method to correct the field homogeneity in the external current mode.     

Compensation of Magnetic Field Instabilities in Field Cycling NMR by Reference Deconvolution

Performing a nuclear magnetic resonance (NMR) experiment in an unstable magnetic field causes fluctuations in the NMR frequency, leading to a loss of reproducibility and an effective shortening of the free induction decay after data averaging. Reference deconvolution allows the compensation of field fluctuations via simultaneous measurement of an internal or external reference signal. The technique was applied to compensate the effect of field fluctuations in a resistive electromagnet used for fast field cycling NMR. An external sample was chosen as the reference.     

NMR studies of interfaces,strain and anisotropy in Co/Cu multilayers

⁵⁹Co NMR studies of multilayers are able to give three direct pieces of information: (i) the crystal phase of Co, fcc (217.4 MHz), hcp (220–228 MHz) and in exotic cases bcc (198 MHz) for films measured at T= 4.2 K, (ii) the nature of the interfaces from low frequency satellite lines, and (iii) the strain state deduced from small changes in the line positions. Extensive studies of Co/Cu multilayer interfacial structures as a function of deposition technique, layer thickness, substrate/buffer layer structure and annealing temperature have been undertaken. This work has shed new light on the relationship between interfacial structure and magnetoresistance and in particular has demonstrated that flat, atomic scale, interfaces lead to greater magnetoresistance. The difference between the Co and Cu lattice constant results in an extensive, tensile in-plane strain developing in Co layers provided that some epitaxial registry is present. Information on strain effects can be obtained from the position and width of the NMR lines. The magnetic anisotropy field can be determined by measuring the field dependence of the enhancement effect due to electronic magnetisation. This provides unique insight into the distribution of magnetic anisotropy within the Co layers, as the enhancement can be investigated independently for each NMR line and, hence, provides environment specific information on magnetic anisotropy at the interfaces and in the interior of the layers. This revised version was published online in August 2006 with corrections to the Cover Date.     

固态样品中扩散的核磁共振测量

用脉冲梯度切核磁共振测量固态样品中的扩散遇到很多困难,对于一个不用内锁的电磁体系统,观测到脉冲场梯度过后涡流造成样品处的磁场强度的强烈振荡.提出了一个用该系统测量凝胶聚合物中锂离子扩散可获得较好结果的脉冲序列.     

Two-Dimensional Dynamic-Director C NMR of Liquid Crystals

A novel nuclear magnetic resonance (NMR) experiment for facilitating the resolution and assignment of liquid crystalline ¹³C NMR spectra is described. The method involves the motor-driven reorientation of the liquid crystalline director, in synchrony with the acquisition of a 2D chemical shift correlation spectrum. By monitoring in this fashion the ¹³C NMR evolution of spins in the liquid crystal at two different director orientations with respect to the magnetic field, the method distinguishes anisotropic from isotropic displacements and can be utilized for assigning the resonances and estimating local degrees of order. Of various potential pairs of angles suitable for such a correlation, the (0°, 90°) choice was found to be most convenient, as it avoids line broadening complications that may otherwise originate from heterogeneities of the oriented phase. The technique thus derived was employed in the analysis of a series of monomeric and polymeric liquid crystal systems.     

基于磁通门和时域数字鉴频的磁场锁定系统

永磁型磁共振仪器的磁体易受温度和其他环境磁场干扰,造成主磁场波动,进而影响仪器测量的重复性和准确性．本文讨论了两种解决磁场波动的锁定方法：一方面,通过磁通门传感器对环境波动引起的瞬态磁场进行高灵敏探测,然后采用现场可编程门阵列进行实时处理并计算磁场补偿量;另一方面,针对环境温度变化引起的缓慢磁场偏移,则采用时域数字鉴频锁场方法,在对锁样品进行射频激发后,将磁共振信号通过混频变换到较低的频率范围,再转换为方波,然后直接送入现场可编程门阵列进行周期测量,并计算磁场补偿量．将两种方法获得的磁场补偿量叠加后,再转换为电流信号驱动安装在磁体上的B₀补偿线圈,并研制了一套磁场锁定系统,以实现对磁场的锁定.在0.5 T食品快检磁共振分析仪上进行测试验证,结果显示当受到瞬态干扰时,可将磁场稳定在±4 Hz(对应磁场为±0.093 9μT)范围内,同时也可以精准测量温度造成的磁场偏移,该结果验证了本文磁场锁定方法的可行性．     

Towards beyond 1 GHz NMR: Mechanism of the long-term drift of screening current-induced magnetic field in a Bi-2223 coil

The screening current-induced magnetic field in the (Bi,Pb)₂Sr₂Ca₂Cu₃O_x (Bi-2223) insert coil proposed for a beyond 1 GHz nuclear magnetic resonance (NMR) spectrometer may generate a long-term field drift, resulting in a loss of field-frequency lock operation and an inability to make high resolution NMR measurements. The measured screening current-induced magnetic field of a Bi-2223 double-pancake coil exhibits a hysteresis effect at 4.2 K that is reproduced by a numerical simulation based on a finite thickness rectangular superconductor bar model. The screening current-induced field at the coil center is of opposite polarity to that generated by the coil current, and thus the apparent field intensity shows a positive drift with time. On the contrary, the field at a coil end is of the same polarity as the coil field, and the apparent field intensity decreases with time. If we wait for ∼1000 h after coil excitation, the field drift rate approaches the field decay rate of the persistent current of 10⁻⁸ h⁻¹, suitable for a long-term NMR measurement in a beyond 1 GHz NMR spectrometer.     

超强磁场中核磁共振信号与屏蔽效应的理论研究

研究了超强磁场对于核磁共振样品中双原子分子中电子系统的哈密顿量的影响,并且给出了磁共振信号中由于外磁场与氢原子电子系统相互作用所产生的含有B02的修正项.基于核磁共振原理,获得了利用氢的NMR谱对超强磁场进行精确测量的理论依据,推导出了一种基于核磁共振技术的超强磁场测量公式,从而在理论上证明了对超强磁场进行精确测量是可行的.     

Structural, static and dynamic magnetic properties of dextran coated γ-Fe(2)O(3) nanoparticles studied by (57)Fe NMR, M?ssbauer, TEM and magnetization measurements

The structural and magnetic properties and spin dynamics of dextran coated and uncoated γ-Fe(2)O(3) (maghemite) nanoparticles have been investigated using high resolution transmission electron microscopy (HRTEM), (57)Fe nuclear magnetic resonance (NMR), M?ssbauer spectroscopy and dc magnetization measurements. The HRTEM observations indicated a well-crystallized system of ellipsoid-shaped nanoparticles, with an average size of 10 nm. The combined M?ssbauer and magnetic study suggested the existence of significant interparticle interactions not only in the uncoated but also in the dextran coated nanoparticle assemblies. The zero-field NMR spectra of the nanoparticles at low temperatures are very similar to those of the bulk material, indicating the same hyperfine field values at saturation in accord with the performed M?ssbauer measurements. The T(2) NMR spin-spin relaxation time of the nanoparticles has also been measured as a function of temperature and found to be two orders of magnitude shorter than that of the bulk material. It is shown that the thermal fluctuations in the longitudinal magnetization of the nanoparticles in the low temperature limit may account for the shortening and the temperature dependence of the T(2) relaxation time. Thus, the low temperature NMR results are in accord with the mechanism of collective magnetic excitations, due to the precession of the magnetization around the easy direction of the magnetization at an energy minimum, a mechanism originally proposed to interpret M?ssbauer experiments in magnetic nanoparticles. The effect of the surface spins on the NMR relaxation mechanisms is also discussed.     

Noninvasive (1)H and (23)Na nuclear magnetic resonance imaging of ancient Egyptian human mummified tissue

Historic mummies are a unique example of the human desire for immortality. Therefore, it is not surprising that modern diagnostic imaging has been widely applied to study them. Yet, magnetic resonance imaging (MRI) of such old remains has never been successfully achieved in a noninvasive way without rehydration. Furthermore, the impact of artificial mummification as done in ancient Egypt by natron (a blend of NaCl, Na(2)CO(3), NaHCO(3) and NaP(2)SO(4)) on human tissue with a particular focus on the sodium spatial distribution has never been addressed. Here, we show for the very first time completely noninvasive (1)H and (23)Na imaging of an ancient Egyptian mummified finger by nuclear magnetic resonance (NMR). Protons could be visualized by NMR only in the tissue close to surface and sodium primarily in the bone, while computer tomography images both, soft tissue and bone but does not distinguish between different chemical elements. The selective enrichment of sodium in the bone may by due to postmortem incorporation of (23)Na into the tissue by natron-based mummification because our reference measurement of a historical finger not subjected to artificial mummification showed no sodium signal at all. Our results demonstrate not only the general feasibility of nonclinical MRI to visualize historic dry human tissues but also shows the specific (1)H and (23)Na spatial distributions in such mummy tissue, which is particularly interesting for archeology and may open up a new application for MRI.     

NMR永磁体精密温度控制器的设计与实现

低场核磁共振（low-field NMR）谱仪常采用钕铁硼（NdFeB）永磁体提供静磁场.NdFeB对温度非常敏感，磁体温度变化会引起磁场漂移，影响NMR实验的可靠性.为提高低场磁共振谱仪的稳定性，本文提出了一种基于双回路控制算法的磁共振永磁体精密温度控制方案，并在0.06 T磁共振谱仪上进行验证.结果表明：24 h内控温精度达到±0.005℃；相比无温控时，质子共振频率0.5 h内漂移量由255 Hz减小至15 Hz，24 h内漂移量由4 950 Hz减小至145 Hz，有效提高了低场磁共振谱仪永磁体的稳定性.     

GAMMA simulations of stray field responses: slice thickness and pulse calibration

A stray field (STRAFI) module has been added to the GAMMA magnetic resonance simulation platform in order to facilitate computational investigations of NMR experiments in large static field gradients that are on the order of 50 T/m. The package has been used to examine system response during echo trains generated by the application of shaped pulses. The associated echo amplitude maxima and effective slice thickness are presented. A new accurate method for STRAFI pulse calibration based on relative echo amplitudes is proposed.     

Effect of the degree of crosslinking on the interfacial layer structure of poly(vinyl chloride) dispersed with crosslinked poly(n-butyl methacrylate) particles

The interfacial layer structure of a model incompatible polymer blend system was analyzed using ¹H pulse nuclear magnetic resonance (pulse NMR) spectroscopy. Non-crosslinked and crosslinked poly(n-butyl methacrylate) particles with a mean size of ca. 0.9 μm were prepared by seeded emulsion polymerization, and the degree of crosslinking was varied. The particles were powdered using a freeze-dry method and dispersed in poly(vinyl chloride) by melt blending. Dynamic mechanical analysis indicated that the non-crosslinked particles were completely compatible. In contrast, mutual diffusion of the polymer chains in the crosslinked particles was restricted within the particle/matrix interfacial layer. As a result, an incompatible phase structure in which the crosslinked particles were dispersed in the continuous phase was formed. Pulse NMR analysis indicated that the interfacial layer thickness was in the range of 17–98 nm. The thickness decreased with an increase in the degree of crosslinking in the particles. The interfacial layer thickness in the particles was approximately 10 times larger than that for the incompatible polymer pair. Tensile test results indicated that the elongation at break was dependent on the thickness of the interfacial layer. The yield stress was developed for the particles with high hardness that was independent of the interfacial thickness.     

High-field NMR using resistive and hybrid magnets

Resistive and resistive-superconducting hybrid magnets can generate dc magnetic fields much higher than conventional superconducting NMR magnets but the field spatial homogeneity and temporal stability are usually not sufficient for high-resolution NMR experiments. Hardware and technique development addressing these issues are presented for high-resolution NMR at magnetic fields up to 40T. Passive ferromagnetic shimming and magic-angle spinning are used effectively to reduce the broadening from inhomogeneous magnetic field. A phase correction technique based on simultaneous heteronuclear detection is developed to compensate magnetic field fluctuations to achieve high spectral resolution.     

Magnetic properties and Fe NMR studies of U-type hexaferrites

U-type hexaferrites with compositions Ba₄Me₂Fe₃₆O₆₀ (Me=Cu, Fe, Co, Mn and Mg) have been synthesized and characterized by magnetization measurements and zero field ⁵⁷Fe nuclear magnetic resonance (NMR) spectra. The NMR spectra show resonance peaks corresponding to different crystallographic sites of iron (tetrahedral, octahedral and trigonal bipyramidal) with integral intensities according to their site multiplicity. In comparison with the NMR spectrum of M-type barium hexaferrite the intensities of some of the peaks arising due to iron sublattices (f_IV, a and b sites) are different, though there is no difference in peak positions indicating the same local hyperfine field strength at Fe nuclei. The maximum saturation magnetization at room temperature was found in Cu₂U (70 emu/g) and Fe₂U (67 emu/g). The Curie temperatures, saturation magnetizations and coercitivities for the U-type hexaferrites are given.     

Easy-axis kagome antiferromagnet: local-probe study of Nd3Ga5SiO14

We report a local-probe investigation of the magnetically anisotropic kagome compound Nd3Ga5SiO14. Our zero-field muon spin relaxation (muSR) results provide direct evidence of a fluctuating collective paramagnetic state down to 60 mK, supported by a wipeout of the Ga nuclear magnetic resonance (NMR) signal below 25 K. At 60 mK a dynamics crossover to a much more static state is observed by muSR in magnetic fields above 0.5 T. Accordingly, the NMR signal is recovered at low T above a threshold field, revealing a rapid temperature and field variation of the magnetic fluctuations.     

Nuclear spin resonance of (129)Xe doped with O(2)

Spin-lattice relaxation of (129)Xe nuclei in solid natural xenon has been investigated in detail over a large range of paramagnetic O(2) impurity concentrations. Direct measurements of the ground state magnetic properties of the O(2) are difficult because the ESR (electron spin resonance) lines of O(2) are rather unstructured, but NMR measurements in the liquid helium temperature region (1.4-4 K) are very sensitive to the effective magnetic moments associated with the spin 1 Zeeman levels of the O(2) molecules and to the O(2) magnetic relaxation. From these measurements, the value of the D[Sz(2)-(1/3)S(2)] spin-Hamiltonian term of the triplet spin ground state of O(2) can be determined. The temperature and magnetic field dependence of the measured paramagnetic O(2)-induced excess line width of the (129)Xe NMR signal agree well with the theoretical model with the spin-Hamiltonian D=0.19 meV (2.3 K), and with the reasonable assumption that the E[S(x)(2)-S(y)(2)] spin-Hamiltonian term is close to 0 meV. An anomalous temperature dependence between 1.4 K and 4.2K of the (129)Xe spin-lattice relaxation rate, T(1n)(-1)(T), is also accounted for by our model. Using an independent determination of the true O(2) concentration in the Xe-O(2) solid, the effective spin lattice relaxation time (which will be seen to be transition dependent) of the O(2) at 2.3 K and 0.96 T is determined to be approximately 1.4 x 10(-8)s. The experimental results, taken together with the relaxation model, suggest routes for bringing highly spin-polarized (129)Xe from the low temperature condensed phase to higher temperatures without excessive depolarization.