Динамическая поляризация ядер: принципы и современные применения.

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. 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. 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 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.

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.

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.

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.

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. 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.

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. 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.

Dynamic Nuclear Polarization: New Experimental and Methodology Approaches and Applications in Physics, Chemistry, Biology and Medicine, Appl. Magn. Reson., 2008. 34(3–4)
High field dynamic nuclear polarization – the renaissance, Phys. Chem. Chem. Phys., 2010. 12(22)