Low-Field, Time-Resolved Dynamic Nuclear Polarization with Field Cycling and High-Resolution NMR Detection

Dynamic nuclear polarization (DNP) effects in aqueous solutions of stable 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPOL) radicals were studied in a pulsed mode of pumping the electron paramagnetic resonance (EPR) transitions. Our fast field cycling setup allowed us to perform the EPR pumping at low magnetic fields and to detect the enhanced nuclear magnetic resonance signals at 7 T with high spectral resolution. Pumping was performed at two different frequencies, 300 MHz and 1.4 GHz, corresponding to magnetic fields around 10 and 48.6 mT, respectively. For both frequencies, the DNP enhancements were close to the limiting theoretical values of ?110 (¹⁴N TEMPOL) and ?165 (¹⁵N TEMPOL). Our pulsed experiments exploit coherent motion of the electronic spins in the radio-frequency field as seen by an oscillatory component in the dependence of the DNP effect on the radio-frequency pulse duration. The DNP enhancement was studied in detail as a function of the pulse length, duty cycle, delay between the pulses, and applied power. The analysis of the results shows that pulsed DNP experiments provide an opportunity to achieve enhancements of about ?110 with relatively low applied power as compared to the standard continuous-wave DNP experiments. An adequate theoretical approach to the problem under study is suggested.     

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.     

Theoretical treatment of pulsed Overhauser dynamic nuclear polarization: Consideration of a general periodic pulse sequence

A general theoretical approach to pulsed Overhauser-type dynamic nuclear polarization (DNP) is presented. Dynamic nuclear polarization is a powerful method to create non-thermal polarization of nuclear spins, thereby enhancing their nuclear magnetic resonance signals. The theory presented can treat pulsed microwave irradiation of electron paramagnetic resonance transitions for periodic pulse sequences of general composition. Dynamic nuclear polarization enhancement is analyzed in detail as a function of the microwave pulse length for rectangular pulses and pulses with finite rise time. Characteristic oscillations of the DNP enhancement are found when the pulse-length is stepwise increased, originating from coherent motion of the electron spins driven by the pulses. Experimental low-field DNP data are in very good agreement with this theoretical approach.     

Analysis of tunable picosecond pulse generation from a distributed feedback Ti：sapphire laser

A distributed feedback Ti:sapphire laser (DFTL) pumped by a 532nm Q-switched pulse is proposed for the generation of tunable picosecond pulses. With coupled rate equation model, the temporal characteristics of DFTL are obtained. The numerical solutions show that the DFTL pulse with a 50-ps pulse duration and as much as 3.SmJ pulse energy can be obtained under 40-m J, 5-ns pulse pumping. The dependence of output pulse width on the laser crystal‘s length, pumping pulse duration, and pumping rate is also discussed in detail.     

Pump pulse characteristics of quasi-continuous-wave diode-side-pumped Nd:YAG laser

The influence of pumping laser pulse on the property of quasi-continuous-wave (QCW) diode-side-pumped Nd:YAG laser is investigated theoretically and experimentally. Under remaining a fixed duty cycle, the average output power increases, and the corresponding thermal focal length shorten with the increase of the pump pulse duration, which attributes to the decrease of the ratio of pulse buildup time to the pulse duration. At a pump power of 146 W, the laser output power changes from 65.1 W to 81.2 W when the pulse duration is adjusted from 150 μ s to 1000 μ s, confirming a significant enhancement of 24.7%. A laser rate equation model incorporating the amplified spontaneous emission is also utilized and numerically solved, and the simulated results agree well with the experimental data.     

Liquid State DNP on Metabolites at 260?GHz EPR/400?MHz NMR Frequency

We have performed liquid state (“Overhauser”) dynamic nuclear polarization (DNP) experiments at high magnetic field (9.2?T, corresponding to 260?GHz EPR and 400?MHz ¹H-NMR resonance frequency) on solutions of pyruvate, lactate and alanine in water with TEMPOL nitroxide radicals as polarizing agent. We present experimental results showing DNP enhancement on metabolite methyl protons, varying for the different target metabolites. It is shown that the enhancements are achieved through direct coupling between the radicals and the target metabolites in solution, i.e., the effect is not mediated by the solvent water protons. The coupling factors between the TEMPOL radicals and the metabolites observed are a factor of 3–5 smaller compared to direct polarization transfer from TEMPOL to water protons.     

动态核极化谱仪的技术改造

介绍了动态核极化(DNP)谱仪数字系统的改造和一套的射频发射和接收系统的建立.谱仪射频通道的90°脉冲宽度为5μs,能完全满足固体交叉极化和大功率去耦的实验要求.实现了DNP增强曲线的自动测量     

掺Er3+飞秒光纤放大器的特性研究

依据二能级速率方程和光传输方程,理论计算了Er3+光纤放大器中Er3+光纤的最佳长度Lc. 以全光纤飞秒激光器输出的孤子脉冲作为种子源,以理论值Lc作为实际采用的光纤长度,实验测量了Er3+光纤放大器在同向泵浦和反向泵浦下信号光的输出功率,得到同向泵浦的增益为20.0dB, 反向泵浦的增益为20.2 dB.同时测量了脉冲宽度随泵浦功率的变化,实验结果表明,随着泵浦功率的增大,输出光脉冲的宽度的压缩效应经历逐渐增强后逐渐减弱的过程.在同向泵浦方式下,可以得到更短的输出脉宽,其最短脉冲宽度为260 fs.     

Comparison of Overhauser DNP at 0.34 and 3.4?T with Frémy’s Salt

Dynamic nuclear polarization (DNP) is investigated in the liquid state using a model system of Frémy's salt dissolved in water. Nuclear magnetic resonance signal enhancements at 0.34 and 3.4?T of the bulk water protons are recorded as a function of the irradiation time and the polarizer concentration. The build-up rates are consistent with the T(1n) of the observed water protons at room temperature (for 9?GHz/0.34?T) and for about 50?±?10?°C at 94?GHz/3.4?T. At 94?GHz/3.4?T, we observe in our setup a maximal enhancement of -50 at 25?mM polarizer concentration. The use of Frémy's salt allows the determination of the saturation factors at 94?GHz by pulsed ELDOR experiments. The results are well consistent with the Overhauser DNP mechanism and indicate that higher enhancements at this intermediate frequency require higher sample temperatures.     

Effect of Pumping Pulse Duration on Echo Signal Amplitude in Four-Pulse PELDOR

The impact of pumping pulse duration on four-pulse pulsed electron?Celectron double resonance (PELDOR) data was experimentally studied. For biradicals with known distances between two spin labels, it is shown that refocused echo amplitude decreases with increasing the pumping pulse duration and decreasing the distance between spin labels. The effect becomes substantial when the pumping pulse duration is comparable or exceeds the inverse value of the dipole?Cdipole interaction between spin labels. This effect is essential for determination of distance distribution between labels in double-labeled molecules and for determination of the number of labels in clusters of spin-labeled molecules. PELDOR signal distortion was observed when the pumping pulse position in the time scale coincided with those of the detecting pulses. An approach of signal correction to eliminate this distortion is proposed.     

A review of Ni-like X-ray laser experiments undertaken using the VULCAN laser at the Rutherford Appleton Laboratory

Recent progress using the VULCAN laser at the Rutherford Appleton Laboratory to pump X-ray lasing in nickel-like ions is reviewed. Double pulse pumping with ∼100 ps pulses has been shown to produce significantly greater X-ray laser output than single pulses of duration 0.1–1 ns. With double pulse pumping, the main pumping pulse interacts with a pre-formed plasma created by a pre-pulse. The efficiency of lasing increases as there is a reduced effect of refraction of the X-ray laser beam due to smaller density gradients and larger gain volumes, which enable propagation of the X-ray laser beam along the full length of the target. The record shortest wavelength saturated laser at 5.9 nm has been achieved in Ni-like dysprosium using double pulse pumping of 75 ps duration from the VULCAN laser. A variant of the double pulse pumping using a single ∼100 ps laser pulse and a superimposed short ∼1 ps pulse has been found to further increase the efficiency of lasing by reducing the effects of over-ionisation during the gain period. The record shortest wavelength saturated laser pumped by a short ∼1 ps pulse has been achieved in Ni-like samarium using the VULCAN laser operating in chirped pulse amplified (CPA) mode. Ni-like samarium lases at 7.3 nm.     

基于半导体断路开关的8 MW,10 kHz脉冲发生器

 功率器件半导体断路开关具有高重复频率工作能力。采用高速绝缘栅双极晶体管组件作为初级充电回路的主开关,建立了一台工作频率为10 kHz的脉冲发生器。脉冲发生器采用磁饱和脉冲变压器、磁开关及高压脉冲电容器组等固态器件进行两级脉冲压缩,产生小于100 ns的电流脉冲,对半导体断路开关进行泵浦,半导体断路开关反向截断泵浦电流在负载上产生高压脉冲输出。实验装置在电阻负载上得到了脉冲输出功率约为8.6 MW,脉冲宽度约10 ns,重复频率10 kHz的高压脉冲输出。     

脉冲激光二极管泵浦调Q激光器泵浦时间特性研究

从调Q激光器的速率方程出发,对脉冲激光二极管泵浦的调Q激光器在不同泵浦功率及不同透过率情况下的最佳泵浦时间进行了理论分析。计算结果表明,在透过率为20%,腔内损耗为0.05的条件下,1—3倍阈值泵浦功率时,最高效率对应的最佳泵浦时间为1—1.5倍Nd∶YAG荧光寿命;7倍阈值泵浦功率及以上时,最佳泵浦时间约为荧光寿命的一半或者更短。在脉冲泵浦能量相同时,采用较短的泵浦时间(即泵浦功率较高),调Q输出的能量转换效率较高。     

Theoretical investigation on temporal properties of random lasers pumped by femtosecond-lasing pulses

Pulsing random lasing property has been investigated in both one- and two-dimensional random medium by numerically solving Maxwell’s equations and rate equations in which the pumping rate is described by a time function with duration of 10s or 100s of femtoseconds. The peak intensity, width and delay time of a random lasing pulse are traced with the variation of the peak intensity, duration, shape and numbers of a pumping pulse. Results show that the behavior of random lasing depends strongly on the pumping process, some of which are in agreement with previously reported experiments pumped by femtosecond-lasing pulses. The present work enriches the knowledge about random lasers, especially in temporal regime, and could offer more guidance for relevant experiments.     

脉冲LDA泵浦Nd∶YVO4/GaAs被动调Q锁模激光器

用脉冲激光二极管阵列（LDA）作为泵浦源、微柱透镜阵列和透镜导管作为耦合系统,以As＋注入GaAs可饱和吸收片作为被动调Q锁模元件,实现了Nd∶YVO4激光器调Q锁模运转.调Q运转阶段,激光器每泵浦脉宽内输出一个调Q脉冲,调Q脉宽7ns.调Q锁模运转阶段,初始透过率60％的GaAs晶片对调Q包络内的锁模脉冲的调制深度达到95％以上,锁模脉冲重复频率991 MHz.研究了加在LDA上的电压、方波脉冲的脉宽和重复频率对调Q锁模脉冲特性的影响,并对实验结果进行了讨论.     

Signal enhancement using 45 degrees water flipback for 3D 15N-edited ROESY and NOESY HMQC and HSQC.

A novel implementation of the water flipback technique employing a 45 degrees flip-angle water-selective pulse is presented. The use of this water flipback technique is shown to significantly enhance signal in 3D 15N-edited ROESY in a 20 kDa complex of the vnd/NK-2 homeodomain bound to DNA. The enhancement is seen relative to the same experiment using weak water presaturation during the recovery delay. This enhancement is observed for the signals from both labile and nonlabile protons. ROESY and NOESY pulse sequences with 45 degrees water flipback are presented using both HMQC and HSQC for the 15N dimension. The 45 degrees flipback pulse is followed by a gradient, a water selective 180 degrees pulse, and another gradient to remove quadrature images and crosspeak phase distortion near the water frequency. Radiation damping of the water magnetization during the t1 and t2 evolution periods is suppressed using gradients. Water resonance planes from NOESY-HMQC and NOESY-HSQC spectra show that the HMQC version of the pulse sequences can provide stronger signal for very fast exchanging protons. The HSQC versions of the ROESY and NOESY pulse sequences are designed for the quantitative determination of protein-water crossrelaxation rates, with no water-selective pulses during the mixing time and with phase cycling and other measures for reducing axial artifacts in the water signal.     

Low Field (10 mT) Pulsed Dynamic Nuclear Polarization

EPR irradiation by a train of inverting pulses has potential advantages over continuous-wave EPR irradiation in DNP applications; however, it has previously been used only at high field (5 T). This paper presents the design and testing of an apparatus for performing pulsed DNP experiments at 10 mT with large samples (17 ml). Experimental results using pulsed DNP with an aqueous solution of a narrow-linewidth paramagnetic probe are presented. A maximum DNP enhancement of about -36 with a train of inverting pulses (width 500 ns, repetition time 4 micros) was measured. A preliminary comparison showed that, when the same enhancement value is considered, the pulsed DNP technique requires an average power that is about three times higher than that required with the CW irradiation. However, for in vivo DNP applications it is very important to minimize the average power deposited in the sample. From the experimental results reported in this work, when considering the maximum enhancement, the pulsed technique requires only 2% of the average power necessary with the CW DNP technique. We believe that this reduction in the average power can be important for future DNP studies with large biological samples.     

脉冲动态核极化增强的NMR 和MRI 系统研究

该文介绍了一种自行设计和构建的可扩展脉冲动态核极化谱仪,可以实现核磁共振波谱与磁共振成像的功能．该仪器的新颖设计主要有：1) 采用基于PCIe 的分布式总线结构,能够极大地提高数据传输效率和通信可靠性,实现精确控制脉冲序列;2) 采用外部高速的DDR 芯片存储脉冲序列元素和FID 数据,可以极大的提高脉冲序列的执行速度,减少快速成像序列的TR 时间间隔;3) 采用时钟移相技术,可以精确产生分辨率为纳秒级别的数字脉冲．最后对该仪器的动态核极化-磁共振波谱与核磁共振成像功能进行了实验验证．     

Difference-Frequency Generation Among Ultrashort Optical Pulses in Quasi-Phase-Matching Waveguides

A theoretical model of ultrashort pulse difference-frequency generation (DFG) is presented and developed with quasi-phase matching (QPM) gratings in the undepleted-pump, unamplified-signal approximation. An analytic solution to a case of ultrashort pulse pumped DFG process, including group-velocity mismatching effects and input pulses with frequency chirp and time delay, is obtained. The influences of group-velocity mismatching effects and input signal pulse parameters on the conversion efficiency and output converted pulse characteristics are analyzed and discussed. The results indicate that the conversion efficiency is increased due to the enhancement of pump and signal interaction. The output pulse is inevitable compressed under pulsed pumping and can be compensated by introducing the initial frequency chirp and time delay.     

A dynamic nuclear polarization strategy for multi-dimensional Earth's field NMR spectroscopy

Dynamic nuclear polarization (DNP) is introduced as a powerful tool for polarization enhancement in multi-dimensional Earth’s field NMR spectroscopy. Maximum polarization enhancements, relative to thermal equilibrium in the Earth’s magnetic field, are calculated theoretically and compared to the more traditional prepolarization approach for NMR sensitivity enhancement at ultra-low fields. Signal enhancement factors on the order of 3000 are demonstrated experimentally using DNP with a nitroxide free radical, TEMPO, which contains an unpaired electron which is strongly coupled to a neighboring ¹⁴N nucleus via the hyperfine interaction. A high-quality 2D ¹⁹F–¹H COSY spectrum acquired in the Earth’s magnetic field with DNP enhancement is presented and compared to simulation.