Theoretical Aspects of Dynamic Nuclear Polarization in the Solid State: The Influence of High Radical Concentrations on the Solid Effect and Cross Effect Mechanisms

Dynamic nuclear polarization (DNP) is used to enhance signals in NMR and MRI experiments. During these experiments microwave (MW) irradiation mediates transfer of spin polarization from unpaired electrons to their neighboring nuclei. Solid state DNP is typically applied to samples containing high concentrations (i.e. 10–40?mM) of stable radicals that are dissolved in glass forming solvents together with molecules of interest. Three DNP mechanisms can be responsible for enhancing the NMR signals: the solid effect (SE), the cross effect (CE), and thermal mixing (TM). Recently, numerical simulations were performed to describe the SE and CE mechanisms in model systems composed of several nuclei and one or two electrons. It was shown that the presence of core nuclei, close to DNP active electrons, can result in a decrease of the nuclear polarization, due to broadening of the double quantum (DQ) and zero quantum (ZQ) spectra. In this publication we consider samples with high radical concentrations, exhibiting broad inhomogeneous EPR line-shapes and slow electron cross-relaxation rates, where the TM mechanism is not the main source for the signal enhancements. In this case most of the electrons in the sample are not affected by the MW field applied at a discrete frequency. Numerical simulations are performed on spin systems composed of several electrons and nuclei in an effort to examine the role of the DNP inactive electrons. Here we show that these electrons also broaden the DQ and ZQ spectra, but that they hardly cause any loss to the DNP enhanced nuclear polarization due to their spin-lattice relaxation mechanism. Their presence can also prevent some of the polarization losses due to the core nuclei.     

Dynamic Nuclear Polarization in III–V Semiconductors

We report on electron spin resonance, nuclear magnetic resonance and Overhauser shift experiments on two of the most commonly used III–V semiconductors, GaAs and InP. Localized electron centers in these semiconductors have extended wavefunctions and exhibit strong electron–nuclear hyperfine coupling with the nuclei in their vicinity. These interactions not only play a critical role in electron and nuclear spin relaxation mechanisms, but also result in transfer of spin polarization from the electron spin system to the nuclear spin system. This transfer of polarization, known as dynamic nuclear polarization (DNP), may result in an enhancement of the nuclear spin polarization by several orders of magnitude under suitable conditions. We determine the critical range of doping concentration and temperature conducive to DNP effects by studying these semiconductors with varying doping concentration in a wide temperature range. We show that the electron spin system in undoped InP exhibits electric current-induced spin polarization. This is consistent with model predictions in zinc-blende semiconductors with strong spin–orbit effects.     

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.     

Selective homonuclear Hartmann–Hahn for 13C→13C polarization transfer in solution state NMR

Polarization transfer has become a commonplace technique for the enhancement of a variety of nuclei in high field nuclear magnetic resonance (NMR). In this paper the homonuclear Hartmann-Hahn method for polarization transfer is revisited and it is shown that a 90% transfer of polarization can be achieved experimentally between a pair of scalar coupled ¹³C nuclei in a sample of isotopically enriched glycine. This may show particular utility in the field of dynamic nuclear polarization (DNP) and could be used as an addendum to already established DNP techniques allowing the favourable enhancement to be ‘stored’ on long-lived nuclei and subsequently transferred to shorter-lived nuclei prior to observation.     

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.     

Electrical readout of the local nuclear polarization in the quantum Hall effect: a hyperfine battery

It is demonstrated that the now well-established "flip-flop" mechanism of spin exchange between electrons and nuclei in the quantum Hall effect can be reversed. We use a sample geometry which utilizes separately contacted edge states to establish a local nuclear spin polarization--close to the maximum value achievable--by driving a current between electron states of different spin orientation. When the externally applied current is switched off, the sample exhibits an output voltage of up to a few tenths of a mV, which decays with a time constant typical for the nuclear spin relaxation. The surprising fact that a sample with a local nuclear spin polarization can act as a source of energy and that this energy is well above the nuclear Zeeman splitting is explained by a simple model which takes into account the effect of a local Overhauser shift on the edge state reconstruction.     

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.     

Spin-labeled gel for the production of radical-free dynamic nuclear polarization enhanced molecules for NMR spectroscopy and imaging

Dynamic nuclear polarization (DNP) has recently received much attention as a viable approach to enhance the sensitivity of nuclear magnetic resonance (NMR) spectroscopy and the contrast of magnetic resonance imaging (MRI), where the significantly higher electron spin polarization of stable radicals is transferred to nuclear spins. In order to apply DNP-enhanced NMR and MRI signal to biological and in vivo systems, it is crucial to obtain highly polarized solution samples at ambient temperatures. As stable radicals are employed as the source for the DNP polarization transfer, it is also crucial that the highly polarized sample lacks residual radical concentration because the polarized molecules will be introduced to a biological system that will be sensitive to the presence of radicals. We developed an agarose-based porous media that is covalently spin-labeled with stable radicals. The loading of solvent accessible radical is sufficiently high and their mobility approximates that in solution, which ensures high efficiency for Overhauser mechanism induced DNP without physically releasing any measurable radical into the solution. Under ambient conditions at 0.35 T magnetic field, we measure the DNP enhancement efficiency of (1)H signal of stagnant and continuously flowing water utilizing immobilized stable nitroxide radicals that contain two or three ESR hyperfine splitting lines and compare them to the performance of freely dissolved radicals.     

Optical polarization of nuclei and ODNMR in GaAs/AlGaAs quantum wells

Optical orientation of electrons was used to polarize the crystal lattice nuclei in quantum-size heterostructures and to study the effect of the conduction band spin splitting on the spin states of quasi-two-dimensional (2D) electrons drifting in an external electric field. High (～1%) nuclear polarization was registered using polarized luminescence and ODNMR in single GaAs/AlGaAs quantum wells. Measurement was made of the hyperfine interaction fields created by polarized nuclei on electrons and by electrons on nuclei. The spin-lattice relaxation of nuclei on the non-degenerate 2D electron gas was calculated. A comparison of the theoretical and experimental longitudinal relaxation times permitted the conclusion that the localized charge carriers are responsible for nuclear polarization in quantum wells in the temperature range of 2–77 K. A new effect has been studied, i.e. induction of an effective magnetic field acting on 2D electron spins when electrons drift in an external electric field in the quantum well plane. This effective field B_eff is due to the spin splitting of the conduction band of 2D electrons. The paper discusses possible registration of an ODNMR signal when the field B_eff is modulated by an electric current during optical orientation.     

Electron paramagnetic resonance study of the nuclear spin dynamics in an AlAs quantum well

The nuclear spin dynamics in an asymmetrically doped 16-nm AlAs quantum well grown along the [001] direction has been studied experimentally using the time decay of the Overhauser shift of paramagnetic resonance of conduction electrons. The nonzero spin polarization of nuclei causing the initial observed Overhauser shift is due the relaxation of the nonequilibrium spin polarization of electrons into the nuclear subsystem near electron paramagnetic resonance owing to the hyperfine interaction. The measured relaxation time of nuclear spins near the unity filling factor is (530 ± 30) min at the temperature T = 0.5 K. This value exceeds the characteristic spin relaxation times of nuclei in GaAs/AlGaAs heterostructures by more than an order of magnitude. This fact indicates the decrease in the strength of the hyperfine interaction in the AlAs quantum well in comparison with GaAs/AlGaAs heterostructures.     

Spin transfer from an optically pumped alkali vapor to a solid

We report enhancement of the spin polarization of 133Cs nuclei in CsH salt by spin transfer from an optically pumped cesium vapor. The nuclear polarization was 4.0 times the equilibrium polarization at 9.4 T and 137 degrees C, with larger enhancements at lower fields. This work is the first demonstration of spin transfer from a polarized alkali vapor to the nuclei of a solid, opening up new possibilities for research in hyperpolarized materials.     

Dynamic nuclear polarization in silicon microparticles

We report record high 29Si spin polarization obtained using dynamic nuclear polarization in microcrystalline silicon powder. Unpaired electrons in this silicon powder are due to dangling bonds in the amorphous region of this intrinsically heterogeneous sample. 29Si nuclei in the amorphous region become polarized by forced electron-nuclear spin flips driven by off-resonant microwave radiation while nuclei in the crystalline region are polarized by spin diffusion across crystalline boundaries. Hyperpolarized silicon microparticles have long T1 relaxation times and could be used as tracers for magnetic resonance imaging.     

High-field DNP and ENDOR with a novel multiple-frequency resonance structure.

We describe a new triply tuned (e(-), (1)H, and (13)C) resonance structure operating at an electron Larmor frequency of 139.5 GHz for dynamic nuclear polarization (DNP) and electron nuclear double-resonance (ENDOR) experiments. In contrast to conventional double-resonance structures, the body of the microwave cavity simultaneously acts as a NMR coil, allowing for increased efficiency of radiofrequency irradiation while maintaining a high quality factor for microwave irradiation. The resonator design is ideal for low-gamma-nuclei ENDOR, where sensitivity is limited by the fact that electron spin relaxation times are on the order of the RF pulse lengths. The performance is demonstrated with (2)H ENDOR on a standard perdeuterated bis-diphenylene-phenyl-allyl stable radical. In DNP experiments, we show that the use of this resonator, combined with a low microwave power setup (17 mW), leads to significantly higher (1)H signal enhancement (epsilon approximately 400 +/- 50) than previously achieved at 5-T fields. The results emphasize the importance of optimizing the microwave B(1) field by improving either the quality factor of the microwave resonator or the microwave power level.     

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%。     

The theory of nuclear orientation via electron spin locking (NOVEL)

Nuclear orientation via electron spin locking (NOVEL) is a technique to orient nuclear spins embedded in a solid. Like other methods of dynamic nuclear polarization (DNP) it employs a small amount of unpaired electron spins and uses a microwave field to transfer the polarization of these unpaired electron spins to the nuclear spins. Traditional DNP uses CW microwave fields, but NOVEL uses pulsed electron spin resonance (ESR) techniques: a 90 degree pulse–90 degree phase shift–locking pulse sequence is applied and during the locking pulse the polarization transfer is assured by satisfying the Hartmann–Hahn condition. The transfer is coherent and similar to coherence transfer between nuclear spins. However, NOVEL requires an extension of the existing theory to many, inequivalent nuclear spins and to arbitrary, i.e. high electron and nuclear spin polarization. In this paper both extensions are presented. The theory is applied to the system naphthalene doped with pentacene, where the proton spins are polarized using the photo-excited triplet states of the pentacene molecules and found to show excellent agreement with the experimentally observed evolution of the polarization transfer during the locking pulse.     

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.     

High-frequency dynamic nuclear polarization in the nuclear rotating frame

A proton dynamic nuclear polarization (DNP) NMR signal enhancement (epsilon) close to thermal equilibrium, epsilon = 0.89, has been obtained at high field (B(0) = 5 T, nu(epr) = 139.5 GHz) using 15 mM trityl radical in a 40:60 water/glycerol frozen solution at 11 K. The electron-nuclear polarization transfer is performed in the nuclear rotating frame with microwave irradiation during a nuclear spin-lock pulse. The growth of the signal enhancement is governed by the rotating frame nuclear spin-lattice relaxation time (T(1rho)), which is four orders of magnitude shorter than the nuclear spin-lattice relaxation time (T(1n)). Due to the rapid polarization transfer in the nuclear rotating frame the experiment can be recycled at a rate of 1/T(1rho) and is not limited by the much slower lab frame nuclear spin-lattice relaxation rate (1/T(1n)). The increased repetition rate allowed in the nuclear rotating frame provides an effective enhancement per unit time(1/2) of epsilon(t) = 197. The nuclear rotating frame-DNP experiment does not require high microwave power; significant signal enhancements were obtained with a low-power (20 mW) Gunn diode microwave source and no microwave resonant structure. The symmetric trityl radical used as the polarization source is water-soluble and has a narrow EPR linewidth of 10 G at 139.5 GHz making it an ideal polarization source for high-field DNP/NMR studies of biological systems.     

Direct observation of the electron spin relaxation induced by nuclei in quantum dots

We have studied the electron spin relaxation in semiconductor InAs/GaAs quantum dots by time-resolved optical spectroscopy. The average spin polarization of the electrons in an ensemble of p-doped quantum dots decays down to 1/3 of its initial value with a characteristic time T(Delta) approximately 500 ps, which is attributed to the hyperfine interaction with randomly oriented nuclear spins. We show that this efficient electron spin relaxation mechanism can be suppressed by an external magnetic field as small as 100 mT.