DNP-EPR多功能谱仪中微波桥的设计与实现

在自主研制的动态核极化（Dynamic Nuclear Polarization,DNP）分子影像装置的基础上,提出了一种集DNP和电子顺磁共振（Electron Paramagnetic Resonance,EPR）于一体的多功能谱仪,并对其中的关键部件之一--微波桥进行了设计.微波桥的引入,实现了DNP微波发射机的集成化,以及在DNP谱仪基础上的EPR功能扩展.通过结构设计、电路仿真及系统测试,完成了高频谱纯度、高动态范围的微波发射机以及低噪声系数的微波检测系统的设计与制作.并通过DNP增强实验以及连续波EPR实验对微波桥的性能进行了验证.     

基于直接数字合成技术的电子自旋-核自旋双共振实验射频信号源设计

为了满足脉冲式电子顺磁共振谱仪中电子自旋-核自旋双共振模块的需要,利用直接数字合成器设计并制作了射频信号源. 该部件产生的射频脉冲具备对频率、幅度和相位快速精确调制的能力,对原子核自旋有较强操控能力.     

一种用于高场MRI的多源射频发射机

介绍了高场磁共振成像（MRI）多源发射技术的原理,提出了一种用于高场MRI系统的多源射频信号发射机.它能并行输出多路频率、相位、幅度,可快速独立调节的射频脉冲信号.该射频发射机的实现基于单片现场可编程门阵列（FPGA）和多通道数模转换器（DAC）芯片,FPGA读取预存于双端口随机存取存储器（RAM）中的射频信号参数,并利用读取的参数分别实现每路信号的直接数字频率合成（DDS）和信号调制等核心功能,获得多路数字射频信号;FPGA输出的数字信号经过高性能DAC转化为模拟信号,即所需要的射频信号.该射频发射机在设计中大量采用软件无线电技术,即利用Xilinx提供的IP核实现DDS和信号调制等主要功能,具有集成度高、体积小、灵活度高的优点,同时,该设计可以大大缩短开发时间,有效降低实现的难度和成本,为高场MRI谱仪的多源射频发射机的设计研制提供了一种低成本、高效、高性价比的方案.     

核磁共振波谱仪用射频功率放大器的设计与实现

介绍了一种应用于核磁共振（Nuclear Magnetic Resonance,NMR）波谱仪的宽频带射频功率放大器的设计与实现,提出了射频功率放大器门控信号的设计,探讨了利用传输线变压器构建功率MOSFET输入输出阻抗匹配网络的方法. 该射频功率放大器采用多级驱动结合功率放大的结构,包含2个工作模块和基于宽频带定向耦合器的辅助电路,支持高带和宽带通道的相关实验. 将该射频功率放大器应用在自主研发的500 MHz高分辨率液体NMR谱仪上,测量射频功放的上升、下降时间及输出线性度,并对比测试¹H和¹³C NMR标样的信噪比,实验结果证明了该设计的可行性.     

DITFB/4-OH-TEMPO体系中卤键作用的19F DNP研究

卤键与氢键相似,是实现分子与分子非共价键连接的作用之一,其广泛地应用于工程材料和生命化学等领域．有关卤键相互作用的动态核极化（DNP）研究还未见报道．本文利用连续波-电子顺磁共振（CW-EPR）谱仪及自主研制的DNP实验平台对存在卤键相互作用的体系——1,4-二碘四氟苯（DITFB）/4-羟基-2,2,6,6-四甲基吡啶-1-氧自由基（4-OH-TEMPO）进行¹⁹F DNP研究,并与无卤键作用对照组——六氟苯（PFB）/4-OH-TEMPO的¹⁹F DNP增强效果进行了比较．结果发现,DITFB/4-OH-TEMPO较PFB/4-OH-TEMPO具有更窄的EPR线宽和更大的¹⁹F DNP增强．这表明自由基与DITFB卤键作用削弱了自由基之间的电子自旋-自旋相互作用,从而使自由基横向弛豫时间（T_2e）增加、线宽变窄,导致DNP饱和因子和增强倍数变大．因此,可以通过卤键调控自由基电子自旋相互作用,以改善核的DNP增强效果．     

基于FPGA的低场核磁共振谱仪脉冲编程器设计与实现

脉冲编程器在核磁共振(NMR) 谱仪中非常重要,具有产生脉冲序列所需的射频脉冲,控制回波信号的同步接收等功能. 基于FPGA的同步性能和时序控制功能,设计了低场NMR谱仪的脉冲编程器,可产生任意脉冲序列,实现脉冲频率、相位、幅度的灵活调节. 利用设计的脉冲编程器在0.540 Tesla均匀磁场下进行了CuSO₄溶液的T₁和T₂测量,得到高信噪比的NMR回波串.     

BESⅢ TOF前端读出电子学系统原型设计和实验结果

作为北京谱仪(Beijing Spectrometer, 简称BES)的改造, BESⅢ将把TOF(time-of-flight)测量精度提高到一个新的水平, 总时间分辨不大于90ps. 其中要求前端电子学(Front End Electronics, FEE)对时间测量的不确定性贡献小于25ps. 本文介绍了TOF前端读出电子学系统原型电路的设计和初步的测试结果.     

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.     

低场核磁共振短死时间射频线圈与射频开关的设计

本文以核磁共振（NMR）射频线圈振铃信号产生原理为对象进行分析研究,提出了一种适用于低场环境下由环状间隙腔线圈与螺线管线圈构成的收发分离式短死时间射频线圈设计方案,采用优化调谐匹配网络提高发射效率;根据射频线圈方案需求设计了快速切换的射频开关及驱动．在此基础上依据仿真结果制作了短死时间射频线圈,并应用于自主研制的低场9.51 MHz便携式NMR谱仪系统,进行NMR实验,结果显示可将收发切换时间缩短至10 μs以内,验证了该设计方案的可行性．     

CAN总线在核磁共振波谱仪中的应用

介绍基于CAN（Controller Area Network,控制器局域网）总线构建核磁共振波谱仪通信系统的方案. 由STM32、FPGA（Field Programmable Gate Array, 现场可编程门阵列）和PCI-104完成CAN总线与以太网之间的通信数据转换,并使用可复用的CAN驱动程序设计方法简化系统设计, 实现了谱仪工作站与各控制器之间高速可靠的通信. 调谐实验过程中的数据通信测试结果表明,CAN总线是构建核磁共振波谱仪通信系统理想的解决方案.     

Effect of various sono-oxidation parameters on the removal of aqueous 2,4-dinitrophenol

The influences of ultrasonic output intensity, solution pH, H₂O₂ concentration and the addition of Fenton reagent on the degradation of 2,4-dinitrophenol (DNP) under ultrasonic irradiation were investigated. It was observed that the degradation of DNP fitted pseudo-first-order dynamics under our experimental conditions. Increasing the ultrasonic output intensity increased the degradation efficiency of DNP and low pH favored the ultrasonic degradation of DNP. The addition of H₂O₂ enhanced the ultrasonic degradation efficiency of DNP. The further addition of Cu²⁺, however, hindered the degradation of DNP. In contrast, sono-oxidation treatment in combination with FeSO₄/H₂O₂ showed a synergistic effect for DNP degradation.     

四硝基并哌嗪(TNAD)与一些含能材料混合体系熔点的分子动力学模拟

利用分子动力学模拟方法预测了TNAD/HMX、TNAD/RDX、TNAD/DINA和TNAD/DNP四种混合体系的熔点, 利用比容与温度的曲线拐点决定了四种混合体系的熔点． 结果是TNAD/HMX、TNAD/RDX、TNAD/DINA的熔点分别为500、536、488 K．而TNAD/DNP体系没有明显的熔点,表明此体系是不相容的．利用熔点进一步预测了四种体系的相容性,分析了它们的径向分布函数．TNAD与HMX、RDX、DINA和DNP之间的分子间相互作用是近距离相互作用,且相容性越好,分子间相互作用越强     

Transfer of1H and13C dynamic nuclear polarization from immobilized nitroxide radicals to flowing liquids

In this study,¹H and¹³C dynamic nuclear polarization (DNP) was generated at a magnetic field strength of 0.33 T utilizing silica phase immobilized nitroxide (SPIN) samples. The polarization was subsequently transferred to flowing liquids and monitored at a magnetic field strength of 4.7 T. These solid/liquid intermolecular transfer (SLIT) experiments provide efficient polarization transfer without the necessity of the free radical system present in the monitoring fluid. Specifically, ultimate¹H SLIT DNP Overhauser enhancements of ?56 and ?110 have been observed for benzene and chloroform in the presence of SPIN system 2, respectively. The¹³C SLIT DNP enhancement for benzene is dominated by three-spin effects and poor leakage factors (f _c). However, a particularly favorable case is the chloroform/SPIN 2 system which exhibits a scalar dominated enhancement. For this case, positive enhancements 40–60 times the¹³C thermal Boltzmann magnetization at 4.7 T have been observed. The large scalar dominated¹³C DNP enhancement for this system represents one of the largest experimental enhancements reported to date. The¹³C DNP spectra for other samples which exhibit favorable scalar¹³C dominated enhancements (e.g., Freon 113) are also presented. Three different SPIN systems were also prepared and characterized in the present study.     

基于散射实验极化靶的2.5T/1.3K的动态核极化(DNP)系统的开发

动态核极化法(Dynamic Nuclear Polarization, DNP)是利用热平衡下的电子在磁场中的高自旋极化率转移到原子核自旋的技术,从而极大的提高原子核自旋极化率。多种动态极化靶材料已广泛的用于自旋物理散射实验。本文介绍一种简单实用,共同开发的日本山形大学DNP系统,包括超导磁场,氦4蒸发恒冷器,微波系统以及NMR核磁共振检测系统,测得中子靶材料氘带丁醇(D-butanol)中氘核的极化率在2.5T/1.3K达到+6.5%。     

Study of natural diamonds by dynamic nuclear polarization-enhanced C nuclear magnetic resonance spectroscopy

The results of a study of two types of natural-diamond crystals by dynamic nuclear polarization (DNP)-enhanced high-resolution solid-state ¹³C nuclear magnetic resonance (NMR) are reported. The home-built DNP magic-angle spinning (MAS) ¹³C NMR spectrometer operates at 54 GHz for electrons and 20.2 MHz for carbons. The power of the microwave source was about 30 W and the highest DNP enhancement factor came near to 10³. It was shown that in the MAS spectra the ¹³C NMR linewidths of the I_b-type diamond were broader than those of I_aB3-type diamond. From the hyperfine structure of the DNP enhancement as a function of frequency, four kinds of nitrogen-centred and one kind of carbon-centred free radicals could be identified in the I_b-type diamond. The hyperfine structures of the DNP enhancement curve that originated from the anisotropic hyperfine interaction between electron and nuclei could be partially averaged out by MAS. The ¹³C polarization time of DNP was rather long, i.e. 1500 s, and the spin—lattice relaxation time (without microwave irradiation) was about 300 s, which was somewhat shorter than anticipated. Discussions on these experimental results have been made in this report.     

Understanding Overhauser Dynamic Nuclear Polarisation through NMR relaxometry

Overhauser dynamic nuclear polarisation (DNP) represents a potentially outstanding tool to increase the sensitivity of solution and solid state NMR experiments, as well as of magnetic resonance imaging. DNP signal enhancements are strongly linked to the spin relaxation properties of the system under investigation, which must contain a paramagnetic molecule used as DNP polariser. In turn, nuclear spin relaxation can be monitored through NMR relaxometry, which reports on the field dependence of the nuclear relaxation rates, opening a route to understand the physical processes at the origin of the Overhauser DNP in solution. The contributions of dipole–dipole and Fermi-contact interactions to paramagnetic relaxation are here described and shown to be responsible to both the relaxometry profiles and the DNP enhancements, so that the experimental access to the former can allow for predictions of the latter.     

A multi-sample 94 GHz dissolution dynamic-nuclear-polarization system

We describe the design and initial performance results of a multi-sample dissolution dynamic-nuclear-polarization (DNP) polarizer based on a Helium-temperature NMR cryostat for use in a wide-bore NMR magnet with a room-temperature bore. The system is designed to accommodate up to six samples in a revolver-style sample changer that allows changing samples at liquid-Helium temperature and at pressures ranging from ambient pressure down to 1 mbar. The multi-sample setup is motivated by the desire to do repetitive in vivo measurements and to characterize the DNP process by investigating samples of different chemical composition. The system can be loaded with up to six samples simultaneously to reduce sample loading and unloading. Therefore, series of experiments can be carried out faster and more reliably. The DNP probe contains an oversized microwave cavity and includes EPR and NMR capabilities for monitoring the DNP process. In the solid state, DNP enhancements corresponding to ～45% polarization for [1-(13)C]pyruvic acid with a trityl radical have been measured. In the initial liquid-state acquisition experiments described here, the polarization was found to be ～13%, corresponding to an enhancement factor exceeding 16,000 relative to thermal polarization at 9.4 T and ambient temperature.     

<Superscript>13</Superscript>C Dynamic Nuclear Polarization Using Derivatives of TEMPO Free Radical

The nitroxide-based 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) free radical is widely used in ¹³C dynamic nuclear polarization (DNP) due to its relatively low cost, commercial availability, and effectiveness as polarizing agent. While a large number of TEMPO derivatives are available commercially, so far, only few have been tested for use in ¹³C DNP. In this study, we have tested and evaluated the ¹³C hyperpolarization efficiency of eight derivatives of TEMPO free radical with different side arms in the 4-position. In general, these TEMPO derivatives were found to have slight variations in efficiency as polarizing agents for DNP of 3 M [1-¹³C] acetate in 1:1 v/v ethanol:water at 3.35 T and 1.2 K. X-band electron paramagnetic resonance (EPR) spectroscopy revealed no significant differences in the spectral features among these TEMPO derivatives. ²H enrichment of the ethanol:water glassing matrix resulted in further improvement of the solid-state ¹³C DNP signals by factor of 2 to 2.5-fold with respect to the ¹³C DNP signal of non-deuterated DNP samples. These results suggest an interaction between the nuclear Zeeman reservoirs and the electron dipolar system via the thermal mixing mechanism.