Nuclear quadrupole resonance echoes from hexamethylenetetramine

We investigated the echo phenomenon of nuclear quadrupole resonance (NQR) from hexamethylenetetramine (HMT). We detected the pure NQR echo signal of HMT with a short pulse interval. The intensity of the echo signal increased as the pulse interval time was decreased. We observed that a clean echo signal was generated even when the pulse interval was shorter than the decay time constant T₂^*. Since the short interval time gives a strong echo, our result insists that shorter interval time is preferred for the NQR detection.     

14N Pulsed nuclear quadrupole resonance. 4. Two-pulse sequences for the determination of T1 and T2 relaxation times

A general theory, based on density matrix calculations, has been developed for the special case of a two-pulse sequence applied to spin 1 (¹⁴N) nuclear quadrupole resonance (NQR) of a powder sample. It is shown that the homolog of the NMR inversion-recovery experiment leads easily to the spin-lattice relaxation time T ₁ (associated with the diagonal elements of the density matrix) provided that an appropriate phase cycling is used. Conversely, in spite of two-step phase cycling schemes adapted to spin-spin relaxation measurements, the homolog of the NMR Hahn spin-echo sequence may pose some problems if the results are displayed in the magnitude mode. First, at short decay times, the echo may be corrupted by unwanted signals. Secondly, in that case, the amplitude of the resulting signal can evolve unexpectedly and differently as a function of the phase of the second pulse. Thirdly, at long decay times, the echo maximum occurs earlier than expected. All these problems in principle disappear with a complete four-step phase cycling scheme and the echo decay curve yields reliably the spin-spin relaxation time T ₂ (associated with off-diagonal elements). This theory allowed the exploitation of many test experiments performed at different frequencies on hexamethylenetetramine (HMT) and sodium nitrite.     

氮-14远程核四极共振谱仪

为了满足检测与探头有一定距离的含氮化合物的核四极共振信号,本文研制了一台结构简单,造价低廉的核四极共振操测仪.它利用了脉冲付里叶变换技术,可将获得的核自由感应衰减信号或者回波信号进行相干累加.整个系统分硬件和软件两大部分.前者由射频脉冲放大器(约500W脉冲输出功率),探头,接收机,MCS-96型单片机和PC机构成.后者由单片机上的脉冲序列程序与PC机上的数值信号处理程序组成.利用这台谱仪,可以在几十秒时间内得到距离探头线圈10cm内的典型¹⁴ N样品的核四极共振谱.     

相位可控的核四极矩共振激励脉冲发生器设计

在核四极矩共振（NQR）领域,射频激励脉冲信号的优劣对NQR响应信号有重要影响.针对常规方法中射频激励脉冲参数不可控的问题,本文基于32位闪存微型控制器STM32和直接数字频率合成（DDS）芯片AD9910设计了一种相位可控激励脉冲发生器.采用STM32控制AD9910产生波形参数（脉冲宽度、脉冲间隔、脉冲个数和共振频率等）可控的射频激励脉冲,利用LabVIEW软件平台设计脉冲参数设置界面,并建立计算机与微控制器通信,实现波形参数的精确优化控制.实验结果表明,该方法实现了相位可控的NQR激励脉冲序列,可为后续NQR信号检测提供有效激励源.     

Cross-polarisation method for improvement of 14N NQR signal detectability

This is a study of the cross-polarization effects in the case of 14N quadrupolar spin-system with a long spin-lattice relaxation time. Two important benefits of the cross-polarization technique were demonstrated for PETN: (i) a polarization transfer resulting in increased NQR single shot signal response and (ii) a dynamic reduction in recovery time of the NQR system allowing scan repetition on a much shorter timescale. It was proved that this technique can reduce the optimal waiting time between pulse sequences up to 60 times through a significant reduction of the relaxation time of the quadrupolar spin-system. All experiments were carried out at room temperature using spin-locking multi-pulse sequences and small external magnetic field.     

Application of the spherical tensor method for Two-Frequency pure NQR of spinI=1 nuclei

The results of a theoretical investigation of two-frequency excitation in pure nuclear quadrupole resonance (NQR) for a spinI=1 nucleus with a nonaxial elecric field gradient are presented. The multipole tensor operator technique is used for the treatment of the one- and two-frequency pulse excitations. The results are applied to the characterization of the two-frequency signal of nitrogen¹⁴N nuclei. The experiments on sodium nitrite, NaNO₂, confirm the presence of additional (two-frequency) echo in the NQR signal. The effect of resonance offsets on two-frequency NQR is also considered.     

Nonstationary effects in nitrogen multipulsed nuclear quadrupole resonance

Multiple echoes in the envelope of the nuclear quadrupole resonance (NQR) signal were obtained in a field of multipulse sequences in powdered nitrogen-containing materials at room temperature. Echo signals were observed over a wide range of pulse rotation angles. It is shown that an analogue of the magic NMR echo can be obtained in the field of multipulse sequence.     

利用核四极矩共振技术探测炸药

介绍了用核四极矩共振的原理进行爆炸危险物品检测的方法及实验测试系统. 该系统运用特殊的激励信号来激发被检测样品中所含的特殊元素¹⁴N（炸药的主要成分）,使其产生核四极矩共振,并产生辐射,从而达到检测的目的. 由于该辐射信号的能量非常小(10 nV量级）,在通常的环境中很难检测该信号, 这就对此弱信号的检测和提取提出了很高的要求. 本测试系统使用了一系列有效的组合激励信号及弱信号采集、处理技术,在通常环境中成功地检测到了RDX（黑索金）信号.     

Optimal filtering in multipulse sequences for nuclear quadrupole resonance detection

The application of the multipulse sequences in nuclear quadrupole resonance (NQR) detection of explosive and narcotic substances has been studied. Various approaches to increase the signal to noise ratio (SNR) of signal detection are considered. We discussed two modifications of the phase-alternated multiple-pulse sequence (PAMS): the 180° pulse sequence with a preparatory pulse and the 90° pulse sequence. The advantages of optimal filtering to detect NQR in the case of the coherent steady-state precession have been analyzed. It has been shown that this technique is effective in filtering high-frequency and low-frequency noise and increasing the reliability of NQR detection. Our analysis also shows the PAMS with 180° pulses is more effective than PSL sequence from point of view of the application of optimal filtering procedure to the steady-state NQR signal.     

Nuclear quadrupole resonance exchange spectroscopy with shaped radiofrequency pulses

Recent work on the nuclear quadrupole resonance (NQR) investigation of molecular dynamics in the solid state has relied on 2D methods. We report our studies of dynamic processes by 1D shaped pulse NQR spectroscopy. Significant advantages include considerably shorter experimental duration, clear definition of the exchange time window, and avoidance of off-resonance effects. The reorientation of the Cl₃C? group in polycrystalline chloral hydrate [Cl₃C–CH(OH)₂] is considered as a test case. This may be modelled as a three-site exchange process. An analysis of the generalised Bloch–McConnell equation is performed to formulate the kinetic matrix. The present approach involves simultaneous excitation of the sites that undergo chemical exchange by employing a suitably modulated shaped RF pulse, followed by a mixing time, and finally a suitable read pulse for signal detection. The experimental signal intensities are plotted against the mixing time to extract the kinetic parameters, i.e. the exchange rate and the spin-lattice relaxation rate. Variable temperature measurements are carried out to determine the activation parameters. Short experiment times are possible in our 1D mode, enabling a large number of runs to be readily performed as a function of mixing time and temperature. The kinetic and activation parameters obtained in the case of chloral hydrate are in good agreement with recent literature values.     

日盲紫外域拉曼激光雷达探测大气水汽技术研究

拉曼激光雷达通过探测与水汽浓度相关的大气水汽振动拉曼散射回波信号,可实现大气水汽混合比廓线的探测。然而由于振动拉曼信号非常微弱,在白天测量时振动拉曼散射光谱会淹没在太阳背景光中,多在夜间测量。为实现大气水汽的全天时测量,设计开发一套日盲紫外波段拉曼激光雷达系统。该系统选择Nd∶YAG脉冲激光器的四倍频输出-266.0 nm日盲紫外波段作为拉曼激光雷达系统的激励波长,采用镀高增益介质膜的牛顿式望远镜作为接收器,同时利用二向色镜和超窄带干涉滤光片设计高效率的高光谱分光系统,实现了大气氧气、氮气和水汽振动拉曼散射回波信号277.5,283.6和294.6 nm的精细提取。计算仿真结果表明,臭氧吸收对日盲紫外域拉曼激光雷达探测存在一定的影响,主要是探测距离的影响;氮气通道不受白天太阳背景光噪声的影响;水汽通道存在少量太阳背景光噪声,对系统探测距离略有影响。而系统信噪比计算结果表明,设计的日盲紫外域拉曼激光雷达系统可实现白天3.5 km大气水汽的探测。实际进行水汽探测时,可利用氮气和氧气通道反演出臭氧浓度廓线,修正臭氧对发射波长、各通道拉曼散射波长的吸收,进一步提升系统的探测能力和探测精度。     

Spin-echoes in nitrogen-14 quadrupolar spin-system with axially symmetric electric field gradient tensor

The behaviour of the magnetisation in the spin-1 system with the axial symmetry of the electric field gradient (EFG) tensor was analysed theoretically. The behaviour of the NQR signals in hexamethylenetetramine (C6H12N4) was also studied experimentally using the pulse NQR technique and sensitive equipment. It was shown that the axial symmetry of the EFG in a sample could not be the reason why spin-echo signals were not observed in conventional pulse experiments for the same type of sample. A very short spin-spin relaxation time T2 seems to be the reason of that. The signal-to-noise ratio was sufficient for measuring T2 in C6H12N4, which had not been reported earlier. Experimental results of applying certain pulse sequences to the 14N NQR in a sample are also presented.     

Calculations of multipulse sequence in NQR of spins 32

The general formalism of the interaction representation with respect to an operator which is its own inverse is developed and applied to pure NQR of spins I = 32. Under the assumption of no relaxation and no dipolar coupling, it is shown that the calculation of the response to pure NQR multipulse sequences can be performed with the same concepts used in high field NMR, such as coherence pathways. All the tools and mathematical expressions to predict the time evolution of the signal created by a pure NQR multipulse sequence are presented explicitly. It takes into account the off-resonance irradiation as well as the angular dependence of the excitation and detection for every value of the electric field gradient asymmetry parameter. Particular attention is devoted to the powder average, which is performed via a probability function derived analytically for the first time, leading to a drastic reduction of simulation times. The theory is illustrated by the study of the optimization and excitation bandwidths of one- to three-pulse sequences and compared to experimental results on Chloranil. We show that the three-pulse "stimulated echo" sequence gives a more uniform excitation profile than the traditional two-pulse echo sequence for powder samples. Thus, the "stimulated echo" sequence could be useful to cover a large spectrum when the experiment duration, or the signal to noise ratio, are not critical parameters. Analytical expressions for the nutation spectra obtained by one or two-pulse sequences are also derived for the first time.     

An exact form for the magnetic field density of states for a dipole

We present an analytical form for the density of states for a magnetic dipole in the center of a spherical voxel. This analytic form is then used to evaluate the signal decay as a function of echo time for different volume fractions and susceptibilities. The decay can be considered exponential only in a limited interval of time. Otherwise, it has a quadratic dependence on time for short echo times and an oscillatory decaying behavior for long echo times.     

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.     

Cross-term-compensated pulsed-gradient stimulated echo MR with asymmetric gradient pulse lengths

The magic asymmetric gradient stimulated echo (MAGSTE) sequence developed to compensate background-gradient cross-terms in the preparation and readout interval independently, assumes identical lengths for the two gradient pulses applied in each interval. However, this approach is rather inefficient if some extra delay time is present in one half of an interval, e.g. as required for special RF excitations or spatial encoding prior to the stimulated echo in MR imaging. Therefore, a generalized version of the sequence is presented that considers different gradient pulse lengths within an interval. It is shown theoretically that (i) for any pulse lengths a "magic" amplitude ratio exists which ensures the desired cross-term compensation in each interval and that (ii) prolonging one of the gradients can deliver a considerably higher diffusion weighting efficiency. These results are confirmed in MR imaging experiments on phantoms and in vivo in the human brain at 3T using an echo-planar trajectory. In the examples shown, typically 10 times higher b values can be achieved or an echo time reduction with a 40% signal gain in brain white matter. Thus, in case of asymmetric timing requirements, the generalized MAGSTE sequence with different gradient pulse lengths may help to overcome signal-to-noise limitations in diffusion weighted MR.     

Modified multipulse technique for the effective detection of pure nuclear quadrupole resonance

Modification of the steady-state free precession (SSFP) multipulse technique for the effective detection of nuclear quadrupole resonance (NQR) signals was studied. This modification is based on the use of the preparatory pulse in the SSFP pulse sequences. It was shown that under certain conditions the total intensity of accumulated NQR signal can be increased. Experimental results of applying the proposed technique to nitrogen-14 NQR in the sample of sodium nitrite (NaNO₂) are presented and convincingly demonstrate the technique’s effectiveness.     

Single-slice mapping of ultrashort T(2)

In this communication we present a method for single-slice mapping of ultrashort transverse relaxation times T(2). The RF pulse sequence consists of a spin echo preparation of the magnetization followed by slice-selective ultrashort echo time (UTE) imaging with radial k-space sampling. In order to keep the minimum echo time as small as possible, avoid out-of-slice contamination and signal contamination due to unwanted echoes, the implemented pulse sequence employs a slice-selective 180° RF refocusing pulse and a 4-step phase cycle. The slice overlap of the two slice-selective RF pulses was investigated. An acceptable Gaussian slice profile could be achieved by adjusting the strength of the two slice-selection gradients. The method was tested on a short T(2) phantom consisting of an arrangement of a roll of adhesive tape, an eraser, a piece of modeling dough made of Plasticine?, and a 10% w/w agar gel. The T(2) measurements on the phantom revealed exponential signal decays for all samples with T(2)(adhesive tape)=(0.5 ± 0.1)ms, T(2)(eraser)=(2.33 ± 0.07)ms, T(2)(Plasticine?)=(2.8 ± 0.06)ms, and T(2)(10%agar)=(9.5 ± 0.83)ms. The T(2) values obtained by the mapping method show good agreement with the T(2) values obtained by a non-selective T(2) measurement. For all samples, except the adhesive tape, the effective transverse relaxation time T(2)(?) was significantly shorter than T(2). Depending on the scanner hardware the presented method allows mapping of T(2) down to a few hundreds of microseconds. Besides investigating material samples, the presented method can be used to study the rapidly decaying MR-signal from biological tissue (e.g.: bone, cartilage, and tendon) and quadrupolar nuclei (e.g.: (23)Na, (35)Cl, and (17)O).