A simple scheme for probehead background suppression in one-pulse 1H NMR

A very simple method for reducing probehead background signal in one-pulse 1H nuclear magnetic resonance (NMR) spectra is presented. Two one-pulse spectra are recorded, the first with pulse length tp1, the second with an L-times longer pulse, e.g. with L = 2. The second spectrum scaled by 1/L is subtracted from the first. Since the weak pulses experienced by spins outside the coil are in the linear regime, the background from outside the coil is effectively subtracted out. The background suppression efficiency is approximately 1.5b2, where b is the ratio of the B1 field inside the coil relative to that outside the coil. Experimentally, background suppression by at least a factor of 10 was achieved. Examples of background suppression in 1H wideline as well as 1H fast magic-angle spinning (MAS) one-pulse spectra of clay and polymer samples are shown.     

T1ρ-weighted MRI using a surface coil to transmit spin-lock pulses

T1rho-weighted MRI is a novel basis for generating tissue contrast. However, it suffers from sensitivity to B1 inhomogeneity. First, excitation with a spatially varying B1 causes flip-angle artifacts and second, spin locking with an inhomogeneous B1 results in non-uniform T1rho contrast. In this study, we overcome the former complication with a specially designed spin-locking pulse sequence and we successfully obtain T1rho-weighted images with a surface coil. In this pulse sequence, the spin-lock pulse was divided into segments of equal duration and alternating phase. This "self-compensating" T1rho-preparatory pulse sequence was analyzed and the effect of an inhomogeneous B1 field was simulated using the Bloch equations. T1rho-weighted MR images of a phantom and a human knee joint in vivo were obtained on a clinical scanner with a surface coil to demonstrate the utility of the pulse sequence. The self-compensating T1rho-prepared pulses sequence resulted in substantially reduced image artifacts compared to the conventional, single-phase spin-lock pulse.     

Field modulation effects induced by sample spinning: application to high-resolution magic angle spinning NMR

High-resolution magic angle spinning (HRMAS) has become an extremely versatile tool to study heterogeneous systems. HRMAS relies on magic angle spinning of the sample and on pulse sequences originally developed for liquid state NMR. In most cases the outcome of the experiment is conform to what is expected from high-resolution liquid state NMR spectroscopy. However in some instances, experiments run under MAS can produce some very puzzling results. After reviewing the basic hardware which is at the heart of HRMAS spectroscopy, we show that the origin of this behavior lies in the natural time-dependence of some physical quantities imparted by the rotation. We focus in particular on the effects of B1 inhomogeneities on the nutation, the (90 degrees)+x-t-(90 degrees )-x and the MLEV16 experiments. Different models of radiofrequency distribution of B1 fields in a solenoidal coil are derived from simple geometrical considerations. These models are shown by NMR spin dynamics calculations to reproduce the experimental NMR results. They are also consistent with electromagnetic simulations of the B1 field distribution inside a solenoidal coil.     

Incorporating homonuclear polarization transfer into PRESS for proton spectral editing: illustration with lactate and glutathione

A proton spectral editing pulse sequence for the detection of metabolites with spin systems that involve weak coupling is presented. The sequence is based on homonuclear polarization transfer incorporated into the standard PRESS (Point RESolved Spectroscopy) sequence, which is a volume-selective double spin echo method, to enable spatial localization. All peaks in the region of interest are initially suppressed whether they are peaks from the target metabolite or from contaminating background. The target signal is then restored by polarization transfer from a proton that has a resonance outside the suppressed region and to which the target spins are weakly coupled. This is achieved by the application of a 90 degrees hard pulse with phase orthogonal to that of the PRESS excitation pulse at the location of the first echo in PRESS and by optimizing the two PRESS timings, TE(1) and TE(2), for most efficient yield. Background signal not coupled to any protons outside the initially saturated region remains suppressed. The advantage of this sequence compared to multiple quantum filters is that signal from singlet peaks outside the suppressed area are preserved and can thus be used as a reference. The efficacy of the sequence was verified experimentally on phantom solutions of lactate and glutathione at 3.0 T. For the AX(3) spin system of lactate, the sequence timings were optimized by product operator calculations whereas for the ABX spin system of the cysteinyl group of glutathione numerical calculations were performed for sequence timing optimization.     

Artifacts in T1 rho-weighted imaging: compensation for B(1) and B(0) field imperfections

The origin of spin locking image artifacts in the presence of B(0) and B(1) magnetic field imperfections is shown theoretically using the Bloch equations and experimentally at low (omega(1) < Delta omega(0)), intermediate (omega(1) approximately Delta omega(0)) and high (omega(1) > Delta omega(0)) 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 Deltao mega(0) is quenched, but imperfections in the flip angle cause oscillations about the omega(1) 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 B(0) and B(1) fields, off-resonance spins in fat and in vivo human brain images at 3 T. The new pulse sequence can be used to probe very low frequency (0-400 Hz) dynamic and static interactions in tissues without contaminating B(0) and B(1) field artifacts.     

T1rho-weighted MRI using a surface coil to transmit spin-lock pulses

T1rho-weighted MRI is a novel basis for generating tissue contrast. However, it suffers from sensitivity to B1 inhomogeneity. First, excitation with a spatially varying B1 causes flip-angle artifacts and second, spin locking with an inhomogeneous B1 results in non-uniform T1rho contrast. In this study, we overcome the former complication with a specially designed spin-locking pulse sequence and we successfully obtain T1rho-weighted images with a surface coil. In this pulse sequence, the spin-lock pulse was divided into segments of equal duration and alternating phase. This "self-compensating" T1rho-preparatory pulse sequence was analyzed and the effect of an inhomogeneous B1 field was simulated using the Bloch equations. T1rho-weighted MR images of a phantom and a human knee joint in vivo were obtained on a clinical scanner with a surface coil to demonstrate the utility of the pulse sequence. The self-compensating T1rho-prepared pulses sequence resulted in substantially reduced image artifacts compared to the conventional, single-phase spin-lock pulse.     

Measurement of electron spin lifetime and optical orientation efficiency in germanium using electrical detection of radio frequency modulated spin polarization

We propose and demonstrate a technique for electrical detection of polarized spins in semiconductors in zero applied magnetic fields. Spin polarization is generated by optical injection using circularly polarized light which is modulated rapidly using an electro-optic cell. The modulated spin polarization generates a weak time-varying magnetic field which is detected by a sensitive radio-frequency coil. Using a calibrated pickup coil and amplification electronics, clear signals were obtained for bulk GaAs and Ge samples from which an optical spin orientation efficiency of 4.8% could be determined for Ge at 1342 nm excitation wavelength. In the presence of a small external magnetic field, the signal decayed according to the Hanle effect, from which a spin lifetime of 4.6±1.0 ns for electrons in bulk Ge at 127 K was extracted.     

NMR strong off-resonance irradiation without sample overheating

A prototype NMR probe for long RF pulse has been constructed. Its main elements are two coils mounted in the concentric position. The first bigger coil is wound around a glass dewar tube and the second smaller coil is placed inside the dewar. These two coils are thermally isolated by the dewar. A long and strong RF pulse is applied to the bigger coil. The smaller detection coil inside the dewar contains a sample and to this coil a short RF pulse is applied. The two coils are independently tuned and electrically isolated. During the operation of the strong RF pulse the smaller coil has a high resistance to ground (very low Q factor) and does not absorb energy from the bigger coil. During the operation of the short on-resonance RF pulse the bigger coil is detuned to a higher frequency, but the resonance circuit with the small coil is in the electrical resonance. The NMR probe may be used in off-resonance experiments in which long and strong RF pulses are applied to the bigger coil and thereby the problem of the sample overheating is avoided.     

Nuclear quadrupole resonance of explosives: Simultaneous detection of RDX and PETN in semtex

We have used nuclear quadrupole resonance (NQR) for the detection of¹⁴N in explosives and introduce a new method for the simultaneous detection of the explosives cyclotrimethylene trinitramine (RDX) and pentaerythritol tetranitrate (PETN). We have developed an interleaved pulse sequence, which provides efficient excitation of both RDX and PETN, to drive a solenoid coil that is doubly resonant at 3.41 and 0.89 MHz (suitable resonant frequencies of RDX and PETN, respectively). The excitation of RDX and PETN is carried out alternately within the pulse sequence via frequency hops in the spectrometer; no electronic switching is required to alternately returne the doubly resonant probe to the resonant frequency of each material. The signals from RDX and PETN, which are separated by about 2.52 MHz, are brought into the same audio window by mixing with a suitable intermediate frequency. We have tested the doubly resonant probe and interleaved pulse sequence on plastic formulations of RDX and PETN, on their own (PE-4 and Detasheet respectively) and as a mixture in Semtex.     

Discrimination of C NMR signals in solid material with liquid-like behavior presenting residual dipolar proton–proton homonuclear interactions: application on seeds

In this communication, we propose, a modified spin echo fourier transform (SEFT) experiment run under magic angle spinning (MAS) to obtain structural informations of the liquid-like domains inside complex organic materials. It includes a proton-proton dipolar decoupling such as BLEW12 or Lee-Goldburg sequence just after the 180 degrees 13C refocusing pulse and short echo delays are used in order to overcome T(2) relaxation. This very easy implemented sequence allows a clear discrimination among fast relaxing 13C signals between those with a pure liquid-like behavior and those presenting residual proton-proton dipolar coupling. The interests of the sequence, combined with other classical NMR experiments, are illustrated on whole vegetable seeds that represent an example of a complex material.     

Discrimination of 13C NMR signals in solid material with liquid-like behavior presenting residual dipolar proton-proton homonuclear interactions: application on seeds

In this communication, we propose, a modified spin echo fourier transform (SEFT) experiment run under magic angle spinning (MAS) to obtain structural informations of the liquid-like domains inside complex organic materials. It includes a proton-proton dipolar decoupling such as BLEW12 or Lee-Goldburg sequence just after the 180 degrees 13C refocusing pulse and short echo delays are used in order to overcome T(2) relaxation. This very easy implemented sequence allows a clear discrimination among fast relaxing 13C signals between those with a pure liquid-like behavior and those presenting residual proton-proton dipolar coupling. The interests of the sequence, combined with other classical NMR experiments, are illustrated on whole vegetable seeds that represent an example of a complex material.     

利用相位步进脉冲消除探头13C NMR背景信号

由静态探头线圈外有机材料产生的¹³C NMR背景信号强度大，化学位移范围广（δ_C 20~250），此背景信号在交叉极化实验中还可被增强，并随着样品信号的累积而累积，严重影响谱图分析.将相位步进脉冲引入交叉极化实验（称为PIPCP）中可以有效去除经交叉极化增强的¹³C NMR背景信号，但样品信号不受影响.这是由于经过相位步进脉冲后，线圈外相位严重畸变，而且线圈外锁定场强度急剧降低，来自探头材料的¹³C NMR背景信号无法有效地进行交叉极化.而对于被测样品甘氨酸来说，由于I核和S核之间强烈的偶极耦合作用，所加相位步进脉冲对锁定场强度的影响只有1.4%.     

Counterintuitive Gaussian pulse sequence in three-level ladder scheme

In a recent publication we have studied counterintuitive pulse sequence applied to a three level ladder scheme, utilizing rectangular-shaped pulses. In this research we investigate amplification without population inversion in a three level ladder system interacting with two electromagnetic fields, namely, the probe and coupling fields. We take both probe and drive fields in the form of Gaussian shaped pulses. In a counterintuitive sequence scheme, the short probe pulse is introduced prior to the application of the coupling field, in contrast to a regular sequence scheme, where both fields are introduced at the same time. The influence of varying the probe pulse width and time delay between the initiation times of the probe and coupling fields on transient probe gain is investigated. It is found that the system exhibits a kind of memory about previously applied weak probe pulse. This may allow for detection of the past event by applying a strong drive pulse in the future.     

High-field cooperative transport phenomena and screening in phase-separated degenerate antiferromagnetic semiconductors

Response to a strong electric field is investigated of degenerate antiferromagnetic semiconductors EuTe spontaneously separated into antiferromagnetic and ferromagnetic phases. Whereas in weak fields their response is Ohmic, in strong fields a sequence of very high peaks appears over the Ohmic-type background beginning from a certain threshold field strength. Their spacing decreases with increasing field strength. These peaks are explained by cooperative motion of charged ferromagnetic microregions inside the antiferromagnetic host. The screening by these microregions is investigated theoretically.     

C–H dipolar recoupling under very fast magic-angle spinning using virtual pulses

A new solid-state NMR pulse sequence for recoupling ¹³C–¹H dipolar interactions under magic-angle spinning is proposed, which works under a spinning speed of a few to several tens kilohertz. The sequence is composed of two different frequency switched Lee–Goldburg sequences, and the modulation of the spin part of the ¹³C–¹H dipolar interaction is introduced by a virtual pulse sequence consisting of unitary operators connecting the rotating frame and the tilted rotating frame. When the cycle time of the spinning is equal to or twice the cycle time of the sequence, the ¹³C–¹H dipolar interactions can be recoupled. The sequence is insensitive to experimental imperfections such as rf inhomogeneity or frequency offset, and the resulting lineshape can be represented by a simple analytical equation based on the zeroth-order average Hamiltonian. Experimental results for [2-¹³C] -valine·HCl are reported.     

Detection of ammonium nitrate inside vehicles by nuclear quadrupole resonance

The development of a system for the detection of ammonium nitrate (AN) in vehicles by nuclear quadrupole resonance (NQR) is described. The results from studies of the penetration of radiofrequency (RF) magnetic fields inside certain metal enclosures, including full-scale vehicles, were critical in the design of a novel high-Q resonant probe. The probe was shaped not only for optimal penetration of RF magnetic fields into vehicles, but also for optimal rejection of RF interference and ease of shielding. A full-scale technical demonstrator was designed, built and successfully demonstrated, using novel pulse sequences to generate and detect NQR signals from AN concealed within the boot (trunk) of a car and in the loading bay of a (metal-sided) van. Among the key technical advances that made possible the effective operation of this system was the development of pulse sequences that generate detectable NQR responses for RF magnetic fields that are both very weak and very inhomogeneous.     

Controllable beating signal using stored light pulse

We experimentally study the controllable generation of a beating signal using stored light pulses based on electromagnetically induced transparency(EIT) in a solid medium. The beating signal relies on an asymmetric procedure of light storage and retrieval. After storing the probe pulse into the spin coherence under the EIT condition, two-color control fields with opposite detunings instead of the initial control field are used to scatter the stored spin coherence. The controllable beating signal is generated due to alternative constructive and destructive interferences in the retrieved signal intensities. The beating of the two-color control fields is mapped into the beating of weak probe fields by using atomic spin coherence. This beating signal will be important in precise atomic spectroscopy and fast quantum limited measurements.     

Magnetic-grating free-induction decay and magnetic-grating echo using ultrafast excitation pulses

The interaction of atoms with ultrafast, counterpropagating optical fields is considered. The magnetic degeneracy and hyperfine splitting of the atomic levels are included in the calculations, which are carried out for arbitrary polarizations of the incident fields. The counterpropagating fields produce spatial harmonics in the ground state density matrix (gratings) which can be monitored by backscattering of a traveling wave probe pulse. Two types of excitation schemes are analyzed. The Magnetic-Grating Free-Induction Decay (MGFID) consists of excitation with a single counterpropagating wave field, while the Magnetic-Grating Echo (MGE) involves excitation by two counterpropagating wave fields, separated in time by T. The atomic response to the probe pulse is calculated in lowest-order perturbation theory for atoms cooled below the Doppler limit of laser cooling. Both the MGFID and MGE signals consist of pulses having a duration of order of the excited state lifetime, modulated at frequencies corresponding to the various hyperfine transitions. As a function of the delay between pulses, the signals oscillate at frequencies determined by the ground state hyperfine splittings. General expressions for the MGFID and MGE signals are derived and specific results are presented for the D₂ line in Na.     

Enhanced suppression of residual water in a "270" WET sequence

In certain water suppression experiments, the residual water, which comes from a region away from the center of the RF coil and experiences a much smaller flip angle than the designed one, may appear. The residual water in the WET sequence can be reduced significantly by using a composite 90(x)( degrees )90(y)( degrees )90(-x)( degrees )90(-y)( degrees ) pulse, which de-excites molecules experiencing a small flip angle. The composite pulse, however, has two null excitation points near on resonance, causing a severe loss of spectrum intensity and baseline distortion toward the null points. Since the residual water experiences a very small flip angle, it can be treated as a linear spin system; i.e., the intensity of the residual water is proportional to the pulse strength and width. Based on this principle, the residual water can be reduced dramatically by replacing the 90 degrees pulse in the "270" WET sequence with a 270 degrees pulse for one out of every four scans, without noticeable loss of intensity and baseline distortion.     

混沌噪声背景下微弱脉冲信号的检测及恢复

构建了一种在混沌噪声背景下检测并恢复微弱脉冲信号的模型.首先,基于混沌信号的短期可预测性及其对微小扰动的敏感性,对观测信号进行相空间重构、建立局域线性自回归模型进行单步预测,得到预测误差,并利用假设检验方法从预测误差中检测观测信号中是否含有微弱脉冲信号.然后,对微弱脉冲信号建立单点跳跃模型,并融合局域线性自回归模型,构成双局域线性(DLL)模型,以极小化DLL模型的均方预测误差为目标进行优化,采用向后拟合算法估计模型的参数,并最终恢复出混沌噪声背景下的微弱脉冲信号.仿真实验结果表明本文所建的模型能够有效地检测并恢复出混沌噪声背景中的微弱脉冲信号.