Dynamic nuclear polarization

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Dynamic nuclear polarization (DNP) results from transferring spin polarization from electrons to nuclei, thereby aligning the nuclear spins to the extent that electron spins are aligned. Note that the alignment of electron spins at a given magnetic field and temperature is described by the Boltzmann distribution under the thermal equilibrium. [1] [2] [3] It is also possible that those electrons are aligned to a higher degree of order by other preparations of electron spin order such as: chemical reactions (leading to chemical-induced DNP, CIDNP), optical pumping and spin injection. DNP is considered one of several techniques for hyperpolarization. DNP can also be induced using unpaired electrons produced by radiation damage in solids. [4] [5]

Contents

When electron spin polarization deviates from its thermal equilibrium value, polarization transfers between electrons and nuclei can occur spontaneously through electron-nuclear cross relaxation or spin-state mixing among electrons and nuclei. For example, the polarization transfer is spontaneous after a homolysis chemical reaction. On the other hand, when the electron spin system is in a thermal equilibrium, the polarization transfer requires continuous microwave irradiation at a frequency close to the corresponding electron paramagnetic resonance (EPR) frequency. In particular, mechanisms for the microwave-driven DNP processes are categorized into the Overhauser effect (OE), the solid-effect (SE), the cross-effect (CE) and thermal-mixing (TM).

The first DNP experiments were performed in the early 1950s at low magnetic fields [6] [7] but until recently the technique was of limited applicability for high-frequency, high-field NMR spectroscopy, because of the lack of microwave (or terahertz) sources operating at the appropriate frequency. Today such sources are available as turn-key instruments, making DNP a valuable and indispensable method especially in the field of structure determination by high-resolution solid-state NMR spectroscopy. [8] [9] [10]

Mechanisms

Overhauser effect

DNP was first realized using the concept of the Overhauser effect, which is the perturbation of nuclear spin level populations observed in metals and free radicals when electron spin transitions are saturated by microwave irradiation. This effect relies on stochastic interactions between an electron and a nucleus. The "dynamic" initially meant to highlight the time-dependent and random interactions in this polarization transfer process.

The DNP phenomenon was theoretically predicted by Albert Overhauser in 1953 [11] and initially drew some criticism from Norman Ramsey, Felix Bloch and other renowned physicists of the time on the grounds of being "thermodynamically improbable". The experimental confirmation by Carver and Slichter [12] as well as an apologetic letter from Ramsey both reached Overhauser in the same year. [13]

The so-called electron-nucleus cross-relaxation, which is responsible for the DNP phenomenon is caused by rotational and translational modulation of the electron-nucleus hyperfine coupling. The theory of this process is based essentially on the second-order time-dependent perturbation theory solution of the von Neumann equation for the spin density matrix.

While the Overhauser effect relies on time-dependent electron-nuclear interactions, the remaining polarizing mechanisms rely on time-independent electron-nuclear and electron-electron interactions.

Solid effect

The simplest spin system exhibiting the SE DNP mechanism is an electron-nucleus spin pair. The Hamiltonian of the system can be written as:

These terms are referring respectively to the electron and nucleus Zeeman interaction with the external magnetic field, and the hyperfine interaction. S and I are the electron and nuclear spin operators in the Zeeman basis (spin 1⁄2 considered for simplicity), ωe and ωn are the electron and nuclear Larmor frequencies, and A and B are the secular and pseudo-secular parts of the hyperfine interaction. For simplicity we will only consider the case of |A|,|B|<<|ωn|. In such a case A has little effect on the evolution of the spin system. During DNP a MW irradiation is applied at a frequency ωMW and intensity ω1, resulting in a rotating frame Hamiltonian given by

where

The MW irradiation can excite the electron single quantum transitions ("allowed transitions") when ωMW is close to ωe, resulting in a loss of the electron polarization. In addition, due to the small state mixing caused by the B term of the hyperfine interaction, it is possible to irradiate on the electron-nucleus zero quantum or double quantum ("forbidden") transitions around ωMW = ωe ± ωn, resulting in polarization transfer between the electrons and the nuclei. The effective MW irradiation on these transitions is approximately given by Bω1/2ωn.

Static sample case

In a simple picture of an electron-nucleus two-spin system, the solid effect occurs when a transition involving an electron-nucleus mutual flip (called zero quantum or double quantum) is excited by a microwave irradiation, in the presence of relaxation. This kind of transition is in general weakly allowed, meaning that the transition moment for the above microwave excitation results from a second-order effect of the electron-nuclear interactions and thus requires stronger microwave power to be significant, and its intensity is decreased by an increase of the external magnetic field B0. As a result, the DNP enhancement from the solid effect scales as B0−2 when all the relaxation parameters are kept constant. Once this transition is excited and the relaxation is acting, the magnetization is spread over the "bulk" nuclei (the major part of the detected nuclei in an NMR experiment) via the nuclear dipole network. This polarizing mechanism is optimal when the exciting microwave frequency shifts up or down by the nuclear Larmor frequency from the electron Larmor frequency in the discussed two-spin system. The direction of frequency shifts corresponds to the sign of DNP enhancements. Solid effect exist in most cases but is more easily observed if the linewidth of the EPR spectrum of involved unpaired electrons is smaller than the nuclear Larmor frequency of the corresponding nuclei.

Magic angle spinning case

In the case of magic angle spinning DNP (MAS-DNP), the mechanism is different but to understand it, a two spins system can still be used. The polarization process of the nucleus still occurs when the microwave irradiation excites the double quantum or zero quantum transition, but due to the fact that the sample is spinning, this condition is only met for a short time at each rotor cycle (which makes it periodical). The DNP process in that case happens step by step and not continuously as in the static case. [14]

Cross effect

Static case

The cross effect requires two unpaired electrons as the source of high polarization. Without special condition, such a three spins system can only generate a solid effect type of polarization. However, when the resonance frequency of each electron is separated by the nuclear Larmor frequency, and when the two electrons are dipolar coupled, another mechanism occurs: the cross-effect. In that case, the DNP process is the result of irradiation of an allowed transition (called single quantum) as a result the strength of microwave irradiation is less demanded than that in the solid effect. In practice, the correct EPR frequency separation is accomplished through random orientation of paramagnetic species with g-anisotropy. Since the "frequency" distance between the two electrons should be equal to the Larmor frequency of the targeted nucleus, cross-effect can only occur if the inhomogeneously broadened EPR lineshape has a linewidth broader than the nuclear Larmor frequency. Therefore, as this linewidth is proportional to external magnetic field B0, the overall DNP efficiency (or the enhancement of nuclear polarization) scales as B0−1. This remains true as long as the relaxation times remain constant. Usually going to higher field leads to longer nuclear relaxation times and this may partially compensate for the line broadening reduction. In practice, in a glassy sample, the probability of having two dipolarly coupled electrons separated by the Larmor frequency is very scarce. Nonetheless, this mechanism is so efficient that it can be experimentally observed alone or in addition to the solid-effect.[ citation needed ]

Magic angle spinning case

As in the static case, the MAS-DNP mechanism of cross effect is deeply modified due to the time dependent energy level. By taking a simple three spin system, it has been demonstrated that the cross-effect mechanism is different in the Static and MAS case. The cross effect is the result of very fast multi-step process involving EPR single quantum transition, electron dipolar anti-crossing and cross effect degeneracy conditions. In the most simple case the MAS-DNP mechanism can be explained by the combination of a single quantum transition followed by the cross-effect degeneracy condition, or by the electron-dipolar anti-crossing followed by the cross-effect degeneracy condition. [14] [15]

This in turn change dramatically the CE dependence over the static magnetic field which does not scale like B0−1 and makes it much more efficient than the solid effect. [15]

Thermal mixing

Thermal mixing is an energy exchange phenomenon between the electron spin ensemble and the nuclear spin, which can be thought of as using multiple electron spins to provide hyper-nuclear polarization. Note that the electron spin ensemble acts as a whole because of stronger inter-electron interactions. The strong interactions lead to a homogeneously broadened EPR lineshape of the involved paramagnetic species. The linewidth is optimized for polarization transfer from electrons to nuclei, when it is close to the nuclear Larmor frequency. The optimization is related to an embedded three-spin (electron-electron-nucleus) process that mutually flips the coupled three spins under the energy conservation (mainly) of the Zeeman interactions. Due to the inhomogeneous component of the associated EPR lineshape, the DNP enhancement by this mechanism also scales as B0−1.

DNP-NMR enhancement curves

H DNP-NMR enhancement curve for cellulose char heated for several hours at 350 degC. PH - 1 is the relative polarization or intensity of the H signal. Dnp350-01.png
H DNP-NMR enhancement curve for cellulose char heated for several hours at 350 °C. PH – 1 is the relative polarization or intensity of the H signal.

Many types of solid materials can exhibit more than one mechanism for DNP. Some examples are carbonaceous materials such bituminous coal and charcoal (wood or cellulose heated at high temperatures above their decomposition point which leaves a residual solid char). To separate out the mechanisms of DNP and to characterize the electron-nuclear interactions occurring in such solids a DNP enhancement curve can be made. A typical enhancement curve is obtained by measuring the maximum intensity of the NMR FID of the 1H nuclei, for example, in the presence of continuous microwave irradiation as a function of the microwave frequency offset.

Carbonaceous materials such as cellulose char contain large numbers of stable free electrons delocalized in large polycyclic aromatic hydrocarbons. Such electrons can give large polarization enhancements to nearby protons via proton-proton spin-diffusion if they are not so close together that the electron-nuclear dipolar interaction does not broaden the proton resonance beyond detection. For small isolated clusters, the free electrons are fixed and give rise to solid-state enhancements (SS). The maximal proton solid-state enhancement is observed at microwave offsets of ω ≈ ωe ± ωH, where ωe and ωH are the electron and nuclear Larmor frequencies, respectively. For larger and more densely concentrated aromatic clusters, the free electrons can undergo rapid electron exchange interactions. These electrons give rise to an Overhauser enhancement centered at a microwave offset of ωe – ωH = 0. The cellulose char also exhibits electrons undergoing thermal mixing effects (TM). While the enhancement curve reveals the types electron-nuclear spin interactions in a material, it is not quantitative and the relative abundance of the different types of nuclei cannot be determined directly from the curve. [16]

DNP-NMR

DNP can be performed to enhance the NMR signals but also to introduce an inherent spatial dependence: the magnetization enhancement takes place in the vicinity of the irradiated electrons and propagates throughout the sample. Spatial selectivity can finally be obtained using magnetic resonance imaging (MRI) techniques, so that signals from similar parts can be separated based on their location in the sample. [17] [18] DNP has triggered enthusiasm in the NMR community because it can enhance sensitivity in solid-state NMR. In DNP, a large electronic spin polarization is transferred onto the nuclear spins of interest using a microwave source. There are two main DNP approaches for solids. If the material does not contain suitable unpaired electrons, exogenous DNP is applied: the material is impregnated by a solution containing a specific radical. When possible, endogenous DNP is performed using the electrons in transition metal ions (metal-ion dynamic nuclear polarization, MIDNP) or conduction electrons. The experiments usually need to be performed at low temperatures with magic angle spinning. It is important to note that DNP was only performed ex situ as it usually requires low temperature to lower electronic relaxation. [18]

Related Research Articles

The nuclear Overhauser effect (NOE) is the transfer of nuclear spin polarization from one population of spin-active nuclei to another via cross-relaxation. A phenomenological definition of the NOE in nuclear magnetic resonance spectroscopy (NMR) is the change in the integrated intensity of one NMR resonance that occurs when another is saturated by irradiation with an RF field. The change in resonance intensity of a nucleus is a consequence of the nucleus being close in space to those directly affected by the RF perturbation.

CIDNP, often pronounced like "kidnip", is a nuclear magnetic resonance (NMR) technique that is used to study chemical reactions that involve radicals. It detects the non-Boltzmann (non-thermal) nuclear spin state distribution produced in these reactions as enhanced absorption or emission signals.

<span class="mw-page-title-main">Electron paramagnetic resonance</span> Technique to study materials that have unpaired electrons

Electron paramagnetic resonance (EPR) or electron spin resonance (ESR) spectroscopy is a method for studying materials that have unpaired electrons. The basic concepts of EPR are analogous to those of nuclear magnetic resonance (NMR), but the spins excited are those of the electrons instead of the atomic nuclei. EPR spectroscopy is particularly useful for studying metal complexes and organic radicals. EPR was first observed in Kazan State University by Soviet physicist Yevgeny Zavoisky in 1944, and was developed independently at the same time by Brebis Bleaney at the University of Oxford.

<span class="mw-page-title-main">Solid-state nuclear magnetic resonance</span>

Solid-state NMR (ssNMR) spectroscopy is a technique for characterizing atomic level structure in solid materials e.g. powders, single crystals and amorphous samples and tissues using nuclear magnetic resonance (NMR) spectroscopy. The anisotropic part of many spin interactions are present in solid-state NMR, unlike in solution-state NMR where rapid tumbling motion averages out many of the spin interactions. As a result, solid-state NMR spectra are characterised by larger linewidths than in solution state NMR, which can be utilized to give quantitative information on the molecular structure, conformation and dynamics of the material. Solid-state NMR is often combined with magic angle spinning to remove anisotropic interactions and improve the resolution as well as the sensitivity of the technique.

<span class="mw-page-title-main">Muon spin spectroscopy</span>

Muon spin spectroscopy, also known as µSR, is an experimental technique based on the implantation of spin-polarized muons in matter and on the detection of the influence of the atomic, molecular or crystalline surroundings on their spin motion. The motion of the muon spin is due to the magnetic field experienced by the particle and may provide information on its local environment in a very similar way to other magnetic resonance techniques, such as electron spin resonance and, more closely, nuclear magnetic resonance (NMR).

In physics, Larmor precession is the precession of the magnetic moment of an object about an external magnetic field. The phenomenon is conceptually similar to the precession of a tilted classical gyroscope in an external torque-exerting gravitational field. Objects with a magnetic moment also have angular momentum and effective internal electric current proportional to their angular momentum; these include electrons, protons, other fermions, many atomic and nuclear systems, as well as classical macroscopic systems. The external magnetic field exerts a torque on the magnetic moment,

Ferromagnetic resonance, or FMR, is coupling between an electromagnetic wave and the magnetization of a medium through which it passes. This coupling induces a significant loss of power of the wave. The power is absorbed by the precessing magnetization of the material and lost as heat. For this coupling to occur, the frequency of the incident wave must be equal to the precession frequency of the magnetization and the polarization of the wave must match the orientation of the magnetization.

In MRI and NMR spectroscopy, an observable nuclear spin polarization (magnetization) is created by a homogeneous magnetic field. This field makes the magnetic dipole moments of the sample precess at the resonance (Larmor) frequency of the nuclei. At thermal equilibrium, nuclear spins precess randomly about the direction of the applied field. They become abruptly phase coherent when they are hit by radiofrequency (RF) pulses at the resonant frequency, created orthogonal to the field. The RF pulses cause the population of spin-states to be perturbed from their thermal equilibrium value. The generated transverse magnetization can then induce a signal in an RF coil that can be detected and amplified by an RF receiver. The return of the longitudinal component of the magnetization to its equilibrium value is termed spin-latticerelaxation while the loss of phase-coherence of the spins is termed spin-spin relaxation, which is manifest as an observed free induction decay (FID).

<span class="mw-page-title-main">Nuclear magnetic resonance quantum computer</span> Proposed spin-based quantum computer implementation

Nuclear magnetic resonance quantum computing (NMRQC) is one of the several proposed approaches for constructing a quantum computer, that uses the spin states of nuclei within molecules as qubits. The quantum states are probed through the nuclear magnetic resonances, allowing the system to be implemented as a variation of nuclear magnetic resonance spectroscopy. NMR differs from other implementations of quantum computers in that it uses an ensemble of systems, in this case molecules, rather than a single pure state.

In nuclear chemistry and nuclear physics, J-couplings are mediated through chemical bonds connecting two spins. It is an indirect interaction between two nuclear spins that arises from hyperfine interactions between the nuclei and local electrons. In NMR spectroscopy, J-coupling contains information about relative bond distances and angles. Most importantly, J-coupling provides information on the connectivity of chemical bonds. It is responsible for the often complex splitting of resonance lines in the NMR spectra of fairly simple molecules.

<span class="mw-page-title-main">Zero field NMR</span> Acquisition of NMR spectra of chemicals

Zero- to ultralow-field (ZULF) NMR is the acquisition of nuclear magnetic resonance (NMR) spectra of chemicals with magnetically active nuclei in an environment carefully screened from magnetic fields. ZULF NMR experiments typically involve the use of passive or active shielding to attenuate Earth’s magnetic field. This is in contrast to the majority of NMR experiments which are performed in high magnetic fields provided by superconducting magnets. In ZULF experiments the dominant interactions are nuclear spin-spin couplings, and the coupling between spins and the external magnetic field is a perturbation to this. There are a number of advantages to operating in this regime: magnetic-susceptibility-induced line broadening is attenuated which reduces inhomogeneous broadening of the spectral lines for samples in heterogeneous environments. Another advantage is that the low frequency signals readily pass through conductive materials such as metals due to the increased skin depth; this is not the case for high-field NMR for which the sample containers are usually made of glass, quartz or ceramic.

Magnetization transfer (MT), in NMR and MRI, refers to the transfer of nuclear spin polarization and/or spin coherence from one population of nuclei to another population of nuclei, and to techniques that make use of these phenomena. There is some ambiguity regarding the precise definition of magnetization transfer, however the general definition given above encompasses all more specific notions. NMR active nuclei, those with non-zero spin, can be energetically coupled to one another under certain conditions. The mechanisms of nuclear-spin energy-coupling have been extensively characterized and are described in the following articles: Angular momentum coupling, Magnetic dipole–dipole interaction, J-coupling, Residual dipolar coupling, Nuclear Overhauser effect, Spin–spin relaxation, and Spin saturation transfer. Alternatively, some nuclei in a chemical system are labile and exchange between non-equivalent environments. A more specific example of this case is presented in the section Chemical Exchange Magnetization transfer.

<span class="mw-page-title-main">Nuclear magnetic resonance</span> Spectroscopic technique based on change of nuclear spin state

Nuclear magnetic resonance (NMR) is a physical phenomenon in which nuclei in a strong constant magnetic field are perturbed by a weak oscillating magnetic field and respond by producing an electromagnetic signal with a frequency characteristic of the magnetic field at the nucleus. This process occurs near resonance, when the oscillation frequency matches the intrinsic frequency of the nuclei, which depends on the strength of the static magnetic field, the chemical environment, and the magnetic properties of the isotope involved; in practical applications with static magnetic fields up to ca. 20 tesla, the frequency is similar to VHF and UHF television broadcasts (60–1000 MHz). NMR results from specific magnetic properties of certain atomic nuclei. Nuclear magnetic resonance spectroscopy is widely used to determine the structure of organic molecules in solution and study molecular physics and crystals as well as non-crystalline materials. NMR is also routinely used in advanced medical imaging techniques, such as in magnetic resonance imaging (MRI). The original application of NMR to condensed matter physics is nowadays mostly devoted to strongly correlated electron systems. It reveals large manybody couplings by fast broadband detection and it should not to be confused with solid state NMR, which aims at removing the effect of the same couplings by Magic Angle Spinning techniques.

Electron nuclear double resonance (ENDOR) is a magnetic resonance technique for elucidating the molecular and electronic structure of paramagnetic species. The technique was first introduced to resolve interactions in electron paramagnetic resonance (EPR) spectra. It is currently practiced in a variety of modalities, mainly in the areas of biophysics and heterogeneous catalysis.

Acoustic paramagnetic resonance (APR) is a phenomenon of resonant absorption of sound by a system of magnetic particles placed in an external magnetic field. It occurs when the energy of the sound wave quantum becomes equal to the splitting of the energy levels of the particles, the splitting being induced by the magnetic field. APR is a variation of electron paramagnetic resonance (EPR) where the acoustic rather than electromagnetic waves are absorbed by the studied sample. APR was theoretically predicted in 1952, independently by Semen Altshuler and Alfred Kastler, and was experimentally observed by W. G. Proctor and W. H. Tanttila in 1955.

<span class="mw-page-title-main">Pulsed electron paramagnetic resonance</span>

Pulsed electron paramagnetic resonance (EPR) is an electron paramagnetic resonance technique that involves the alignment of the net magnetization vector of the electron spins in a constant magnetic field. This alignment is perturbed by applying a short oscillating field, usually a microwave pulse. One can then measure the emitted microwave signal which is created by the sample magnetization. Fourier transformation of the microwave signal yields an EPR spectrum in the frequency domain. With a vast variety of pulse sequences it is possible to gain extensive knowledge on structural and dynamical properties of paramagnetic compounds. Pulsed EPR techniques such as electron spin echo envelope modulation (ESEEM) or pulsed electron nuclear double resonance (ENDOR) can reveal the interactions of the electron spin with its surrounding nuclear spins.

Electric dipole spin resonance (EDSR) is a method to control the magnetic moments inside a material using quantum mechanical effects like the spin–orbit interaction. Mainly, EDSR allows to flip the orientation of the magnetic moments through the use of electromagnetic radiation at resonant frequencies. EDSR was first proposed by Emmanuel Rashba.

The Russell Varian Prize was an international scientific prize awarded for a single, high-impact and innovative contribution in the field of nuclear magnetic resonance (NMR), that laid the foundation for the development of new technologies in the field. It honored the memory of Russell Varian, the pioneer behind the creation of the first commercial NMR spectrometer and the co-founder, in 1948, of Varian Associates, one of the first high-tech companies in Silicon Valley. The prize carried a monetary award of €15,000 and it was awarded annually between the years 2002 and 2015 by a committee of experts in the field. The award ceremony alternated between the European Magnetic Resonance (EUROMAR) Conference and the International Council on Magnetic Resonance in Biological Systems (ICMRBS) Conference. Originally, the prize was sponsored by Varian, Inc. and later by Agilent Technologies, after the latter acquired Varian, Inc. in 2010. The prize was discontinued in 2016 after Agilent Technologies closed its NMR division.

<span class="mw-page-title-main">Cross-polarization</span> Spectroscopy technique

Cross-polarization (CP), originally published as proton-enhanced nuclear induction spectroscopy is a solid-state nuclear magnetic resonance (ssNMR) technique to transfer nuclear magnetization from different types of nuclei via heteronuclear dipolar interactions. The 1H-X cross-polarization dramatically improves the sensitivity of ssNMR experiments of most experiments involving spin-1/2 nuclei, capitalizing on the higher 1H polarisation, and shorter T1(1H) relaxation times. It was developed by Michael Gibby, Alexander Pines and Professor John S. Waugh at the Massachusetts Institute of Technology.

Anne Lesage is a French engineer who is a group leader at the French National Centre for Scientific Research. She is based at the High Field NMR Centre of the Lyon Institute of Analytical Sciences, where she develops novel nuclear magnetic resonance approaches to characterise solid-state materials.

References

  1. ↑ Goldman, Maurice (1970). Spin Temperature and Nuclear Magnetic Resonance in Solids. Oxford University Press. ISBN   978-0-19-851251-6.
  2. ↑ A. Abragam; M. Goldman (1976). "Principles of Dynamic Nuclear Polarization". Reports on Progress in Physics . 41 (3): 395–467. Bibcode:1978RPPh...41..395A. doi:10.1088/0034-4885/41/3/002. S2CID   250855406.
  3. ↑ J. Puebla; E.A. Chekhovich; M. Hopkinson; P. Senellart; A. Lemaitre; M.S. Skolnick; A.I. Tartakovskii (2013). "Dynamic nuclear polarization in InGaAs/GaAs and GaAs/AlGaAs quantum dots under non-resonant ultra-low power optical excitation". Phys. Rev. B . 88 (4): 9. arXiv: 1306.0469 . Bibcode:2013PhRvB..88d5306P. doi:10.1103/PhysRevB.88.045306. S2CID   76658845.
  4. ↑ Solem, J. C.; Rebka Jr., G. A. (1968). "EPR of atoms and radicals in radiation-damaged H2 and HD". Physical Review Letters. 21 (1): 19. Bibcode:1968PhRvL..21...19S. doi:10.1103/PhysRevLett.21.19.
  5. ↑ Solem, J. C. (1974). "Dynamic polarization of protons and deuterons in solid deuterium hydride". Nuclear Instruments and Methods. 117 (2): 477–485. Bibcode:1974NucIM.117..477S. doi:10.1016/0029-554X(74)90294-8.
  6. ↑ T.R. Carver; C.P. Slichter (1953). "Polarization of Nuclear Spins in Metals". Physical Review . 92 (1): 212–213. Bibcode:1953PhRv...92..212C. doi:10.1103/PhysRev.92.212.2.
  7. ↑ T.R. Carver; C.P. Slichter (1956). "Experimental Verification of the Overhauser Nuclear Polarization Effect". Physical Review . 102 (4): 975–980. Bibcode:1956PhRv..102..975C. doi:10.1103/PhysRev.102.975.
  8. ↑ T. Maly; G.T. Debelouchina; V.S. Bajaj; K.-N. Hu; C.G. Joo; M.L. Mak-Jurkauskas; J.R. Sirigiri; P.C.A. van der Wel; J. Herzfeld; R.J. Temkin; R.G. Griffin (2008). "Dynamic Nuclear Polarization at High Magnetic Fields". The Journal of Chemical Physics . 128 (5): 052211–19. Bibcode:2008JChPh.128e2211M. doi:10.1063/1.2833582. PMC   2770872 . PMID   18266416.
  9. ↑ A.B. Barnes; G. De Paëpe; P.C.A. van der Wel; K.-N. Hu; C.G. Joo; V.S. Bajaj; M.L. Mak-Jurkauskas; J.R. Sirigiri; J. Herzfeld; R.J. Temkin; R.G. Griffin (2008). "High-Field Dynamic Nuclear Polarization for Solid and Solution Biological NMR". Applied Magnetic Resonance. 34 (3–4): 237–263. doi:10.1007/s00723-008-0129-1. PMC   2634864 . PMID   19194532.
  10. ↑ Akbey, U.; Linden, A. H. & Oschkinat, H. (May 2012). "High-Temperature Dynamic Nuclear Polarization Enhanced Magic-Angle-Spinning NMR". Appl. Magn. Reson. 43 (1–2): 81–90. doi:10.1007/s00723-012-0357-2. ISSN   0937-9347. S2CID   254087348.
  11. ↑ Overhauser, A.W. (1953). "Polarization of Nuclei in Metals". Phys. Rev. 92 (2): 411–415. Bibcode:1953PhRv...92..411O. doi:10.1103/PhysRev.92.411.
  12. ↑ Carver, T.R.; Slichter, C.P. (1953). "Polarization of Nuclear Spins in Metals". Phys. Rev. 92 (1): 212–213. Bibcode:1953PhRv...92..212C. doi:10.1103/PhysRev.92.212.2.
  13. ↑ Purdue University Obituary of Albert W. Overhauser Archived 2006-01-09 at the Wayback Machine
  14. 1 2 Mentink-Vigier, F.; Akbey, U.; Hovav, Y.; Vega, S.; Oschkinat, H.; Feintuch, A. (2012). "Fast passage dynamic nuclear polarization on rotating solids". J. Mag. Reson. 224: 13–21. Bibcode:2012JMagR.224...13M. doi:10.1016/j.jmr.2012.08.013. PMID   23000976.
  15. 1 2 Thurber, K. R.; Tycko, R. (2012). "Theory for cross effect dynamic nuclear polarization under magic-angle spinning in solid state nuclear magnetic resonance: the importance of level crossings". J. Chem. Phys. 137 (8): 084508. Bibcode:2012JChPh.137h4508T. doi:10.1063/1.4747449. PMC   3443114 . PMID   22938251.
  16. ↑ Wind, R.A.; Li, L.; Maciel, G.E.; Wooten, J.B. (1993). "Characterization of Electron Spin Exchange Interactions in Cellulose Chars by Means of ESR, 1H NMR, and Dynamic Nuclear Polarization". Applied Magnetic Resonance. 5 (2): 161–176. doi:10.1007/BF03162519. ISSN   0937-9347. S2CID   96672106.
  17. ↑ Moroz, Ilia B.; Leskes, Michal (1 July 2022). "Dynamic Nuclear Polarization Solid-State NMR Spectroscopy for Materials Research". Annual Review of Materials Research. 52 (1): 25–55. Bibcode:2022AnRMS..52...25M. doi: 10.1146/annurev-matsci-081720-085634 . ISSN   1531-7331. S2CID   247375660.
  18. 1 2 Bagheri, Khashayar; Deschamps, Michael; Salager, Elodie (1 April 2023). "Nuclear magnetic resonance for interfaces in rechargeable batteries" (PDF). Current Opinion in Colloid & Interface Science. 64: 101675. doi:10.1016/j.cocis.2022.101675. ISSN   1359-0294. S2CID   255364390.

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