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.     

Low temperature probe for dynamic nuclear polarization and multiple-pulse solid-state NMR

Here, we describe the design and performance characteristics of a low temperature probe for dynamic nuclear polarization (DNP) experiments, which is compatible with demanding multiple-pulse experiments. The competing goals of a high-Q microwave cavity to achieve large DNP enhancements and a high efficiency NMR circuit for multiple-pulse control lead to inevitable engineering tradeoffs. We have designed two probes-one with a single-resonance RF circuit and a horn-mirror cavity configuration for the microwaves and a second with a double-resonance RF circuit and a double-horn cavity configuration. The advantage of the design is that the sample is in vacuum, the RF circuits are locally tuned, and the microwave resonator has a large internal volume that is compatible with the use of RF and gradient coils.     

Dynamic tunneling polarization as a quantum rotor analogue of dynamic nuclear polarization and the NMR solid effect

The populations of the tunneling states of CH(3) are manipulated by rf irradiation of weakly allowed sideband transitions within the manifold of tunneling-magnetic levels. Substantial positive and negative CH(3) tunneling polarizations are observed, providing a quantum rotor analogue of dynamic nuclear polarization and the solid effect in NMR. The field-cycling NMR technique used in the experiments employs level crossings between tunneling and Zeeman systems to report on the tunneling polarization. The tunneling lifetimes are measured and the field dependence investigated.     

High capacity production of >65% spin polarized xenon-129 for NMR spectroscopy and imaging

A rubidium spin exchange optical pumping system for high capacity production of >65% spin polarized 129Xe gas is described. This system is based on a fiber coupled multiple laser diode array capable of producing an unprecedented 210 W of circularly polarized light at the pumping cell with a laser line width of 1.6 nm. The 129Xe nuclear spin polarization is measured as a function of flow rate, pumping cell pressure, and laser power for varying pumping gas compositions. A maximum 129Xe nuclear polarization of 67% was achieved using a 0.6% Xe mixture at a Xe flow rate of 2.45 sccm. The ability to generate 12% polarized 129Xe at rates in excess of 1L-atm/h is also demonstrated. To achieve production of 129Xe gas at even higher polarization will rely on further optimization of the pumping cell and laser beam geometries in order to mitigate problems associated with temperature gradients that are encountered at high laser power and Rb density.     

Polarizing agents and mechanisms for high-field dynamic nuclear polarization of frozen dielectric solids

This article provides an overview of polarizing mechanisms involved in high-frequency dynamic nuclear polarization (DNP) of frozen biological samples at temperatures maintained using liquid nitrogen, compatible with contemporary magic-angle spinning (MAS) nuclear magnetic resonance (NMR). Typical DNP experiments require unpaired electrons that are usually exogenous in samples via paramagnetic doping with polarizing agents. Thus, the resulting nuclear polarization mechanism depends on the electron and nuclear spin interactions induced by the paramagnetic species. The Overhauser Effect (OE) DNP, which relies on time-dependent spin–spin interactions, is excluded from our discussion due the lack of conducting electrons in frozen aqueous solutions containing biological entities. DNP of particular interest to us relies primarily on time-independent, spin-spin interactions for significant electron–nucleus polarization transfer through mechanisms such as the Solid Effect (SE), the Cross Effect (CE) or Thermal Mixing (TM), involving one, two or multiple electron spins, respectively. Derived from monomeric radicals initially used in high-field DNP experiments, bi- or multiple-radical polarizing agents facilitate CE/TM to generate significant NMR signal enhancements in dielectric solids at low temperatures (<100 K). For example, large DNP enhancements (∼300 times at 5 T) from a biologically compatible biradical, 1-(TEMPO-4-oxy)-3-(TEMPO-4-amino)propan-2-ol (TOTAPOL), have enabled high-resolution MAS NMR in sample systems existing in submicron domains or embedded in larger biomolecular complexes. The scope of this review is focused on recently developed DNP polarizing agents for high-field applications and leads up to future developments per the CE DNP mechanism. Because DNP experiments are feasible with a solid-state microwave source when performed at <20 K, nuclear polarization using lower microwave power (<100 mW) is possible by forcing a high proportion of biradicals to fulfill the frequency matching condition of CE (two EPR frequencies separated by the NMR frequency) using the strategies involving hetero-radical moieties and/or molecular alignment. In addition, the combination of an excited triplet and a stable radical might provide alternative DNP mechanisms without the microwave requirement.     

Magnetocapacitance study of the fractional-quantum-Hall effect: Quasiparticle charge and spin polarization

By the method of capacitance spectroscopy and of magnetotransport we have investigated the and fractional-quantum-Hall-effect (FQHE) states in gated GaAs AlGaAs heterojunctions with tuned electron areal density. Our experimental results confirm the theoretical prediction of the fractional quasiparticle charge in the FQHE state and of the existence of spin-aligned quasiholes and spin-reversed quasielectrons in the fully spin-polarized FQHE state.     

Dynamic nuclear polarization properties of nitroxyl radicals used in Overhauser-enhanced MRI for simultaneous molecular imaging

DNP parameters relevant to Overhauser-enhanced magnetic resonance imaging (OMRI) are reported for a few nitroxyl radicals and their corresponding (15)N and (2)H enriched analogues, used in simultaneous imaging by OMRI. DNP enhancement was measured at 14.529 mT, using a custom-built scanner operating in a field-cycled mode, for different concentrations, ESR irradiation times and RF power levels. DNP enhancements increased with agent concentration up to 2.5 mM and decreased above 3 mM, in tune with ESR line broadening measured at X-band as a function of the agent concentration. The proton spin-lattice relaxation times (T(1)) measured at very low Zeeman field (14.529 mT) and the longitudinal relaxivity parameters were estimated. The relaxivity parameters were in good agreement with those independently computed from the linear region of the concentration dependent enhancement. The leakage factor showed an asymptotic increase with increasing agent concentration. The coupling parameters of (14)N- and (15)N-labeled carbamoyl-PROXYL showed the interaction between the electron and nuclear spins to be mainly dipolar in origin. Upon (2)H labeling, about 70% and 40% increases in enhancement for (15)N- and (14)N-labeled nitroxyl agents were observed, respectively. It is envisaged that the results reported here may enable better understanding of the factors determining DNP enhancement to design suitable 'beacons' for simultaneous molecular imaging by OMRI.     

A computer algorithm for the simulation of any nuclear magnetic resonance (NMR) imaging method

More than a dozen Nuclear Magnetic Resonance (NMR) imaging methods have been described using different radio-frequency pulse sequences, magnetic field gradient variations, and data processing. In order to have a theoretical understanding in the most general case, we have conceived a computer program for the simulation of NMR imaging techniques. The algorithm uses the solution of the Bloch equations at each point of a simulated object. The direction of every elementary magnetic moment is computed at each instant, and stored in an array giving the global signal to be processed, whatever the pulse and gradient sequence. To test the validity of this program, we have simulated some well-known experimental results. Some applications are presented which contribute to the understanding of image distortions and to techniques such as selective radio-frequency pulse or oscillating gradients. This program can be used to unravel physical and technological causes of image distortions, to have a "microscopic" look at any parameter of an experiment, and to study the contrast given by various NMR imaging techniques as a function of the three NMR parameters, i.e., the hydrogen nuclei density rho and the relaxation times T1 and T2.     

Combination of doppler-free polarization spectroscopy and magnetic rotation for the example of IBr

We describe a spectroscopic method which combines for the first time Doppler-free laser polarization spectroscopy with the magnetic rotation technique. This is achieved by the application of a modulating weak magnetic field to the overlap region of modulated pump and probe beam. By the double modulation, molecular levels with effectiveg-factors as low as 0.05 Gm_B can easily be detected and distinguished from diamagnetic levels. This is demonstrated for the molecule IBr where theB'0⁺ state is perturbed by a repulsive = 1 state which leads to increasingg-factors with increasing vibrational levels. With the normal polarization spectroscopy, several of these levels are not detectable within the manifold of overlapping lines from I₂ and Br₂ which are always present in this chemical system. The new method is well suited for characterizing perturbed molecular levels.Dedicated to Prof. Dr. Herbert Welling on the occasion of his 60th birthday     

1H NMR spectroscopy with internal and external standards for the quantification of libraries

A convenient and easy method based on 1H NMR spectroscopy with both external and internal standards is described for the quantification of members of libraries.     

光源的偏振态对动态光散射颗粒测量结果的影响

研究了在动态光散射纳米颗粒测量中,光源的偏振态对测量结果的影响。采用了粒径为100nm、体积浓度为0.5%的标准颗粒作为样品,使He-Ne激光通过起偏器得到0°～180°方向的偏振光,测量了散射光强、偏振度和粒径测量值的变化,计算了相应的粒径均值偏差和标准差,并将这一结果与无偏振He-Ne激光入射进行了比较。结果表明,当入射光为线偏振光时,偏振方向垂直于散射面时测量效果最好;另一方面,由于颗粒系散射迭加造成的散射光偏振度降低,使线偏振光源与无偏振光源产生的散射光偏振度无明显差别,证明在测量中可以使用无偏振He-Ne激光代替。     

Design and application of robust rf pulses for toroid cavity NMR spectroscopy

We present robust radio frequency (rf) pulses that tolerate a factor of six inhomogeneity in the B? field, significantly enhancing the potential of toroid cavity resonators for NMR spectroscopic applications. Both point-to-point (PP) and unitary rotation (UR) pulses were optimized for excitation, inversion, and refocusing using the gradient ascent pulse engineering (GRAPE) algorithm based on optimal control theory. In addition, the optimized parameterization (OP) algorithm applied to the adiabatic BIR-4 UR pulse scheme enabled ultra-short (50 μs) pulses with acceptable performance compared to standard implementations. OP also discovered a new class of non-adiabatic pulse shapes with improved performance within the BIR-4 framework. However, none of the OP-BIR4 pulses are competitive with the more generally optimized UR pulses. The advantages of the new pulses are demonstrated in simulations and experiments. In particular, the DQF COSY result presented here represents the first implementation of 2D NMR spectroscopy using a toroid probe.     

Solid-state 13C and 1H spin diffusion NMR analyses of the microfibril structure for bacterial cellulose

To obtain further information about the cause for the rather large splitting of the C4 resonance line into the downfield (C4D) and upfield (C4U) lines in CP/MAS ¹³C NMR spectra for native cellulose, ¹³C and ¹H spin diffusion measurements have been conducted by using different types of bacterial cellulose samples. In ¹³C spin diffusion measurements, the C4D resonance line is selectively inverted by the Dante π pulse sequence and the ¹³C spin diffusion is allowed to proceed from the C4D carbons to other carbons including the C4U carbons with use of the ¹³C4-enriched bacterial cellulose sample. The analysis based on the simple spin diffusion theory for the process experimentally observed reveals that the C4U carbons may be located at distances less than about 1 nm from the C4D carbons. In ¹H spin diffusion measurements, poly(vinyl alcohol) (PVA) films in which ribbon assemblies of bacterial cellulose are dispersed are employed and the ¹H spin diffusion process is examined from the water-swollen PVA continuous phase to the dispersed ribbon assemblies by the ¹³C detection through the ¹H–¹³C CP technique. As a result, it is found that the C4D and C4U carbons are almost equally subjected to the ¹H spin diffusion from the PVA phase, indicating that the C4U carbons are not localized in some limited area, e.g. in the surfacial region, but are distributed in the whole area in the microfibrils. These experimental results suggest that the C4U carbons may exist as structural defects probably due to conformational irregularity associated with disordered hydrogen bonding of the CH₂OH groups in the microfibrils.     

光调制技术用于提高光谱法舌诊的测量信噪比

为了解决光谱采集受环境光干扰严重的问题,首次将光调制技术用于提高光谱法舌诊测量的信噪比。系统采用调制盘对参考光信号强度进行调制,运用此装置采集同一被测体在分别叠加绿色、紫色、红色激光以及自然环境光干扰情况下的反射光谱,对采集来的数据运用离散傅里叶变换进行解调,提取最大谐波分量,然后对提取的最大谐波分量进行归一化,绘制解调后的光谱曲线,通过比较发现,不同干扰情况下所测同一被测体经过调制解调后的反射光谱曲线走向基本一致,结果表明光调制技术能够去除舌体反射光谱采集中环境杂散光的干扰,为高信噪比舌诊光谱数据采集提供了一种新途径。