RESUMO
Polarization transfer from unpaired electron radicals to nuclear spins at low-temperature is achieved using microwave irradiation by a process broadly termed dynamic nuclear polarization (DNP). The resulting signal enhancement can easily exceed factors of 104 when paired with cryogenic cooling of the sample. Dissolution-DNP couples low temperature polarization methods with a rapid dissolution step, resulting in a highly polarized solution that can be used for metabolically sensitive magnetic resonance imaging (MRI). Hyperpolarized [1-13C]pyruvate is a powerful metabolic imaging agent for investigation of in vitro and in vivo cellular metabolism by means of NMR spectroscopy and MRI. Radicals (trityl OX063 and BDPA) with narrower EPR linewidths typically produce higher nuclear polarizations when carbon-13 is the target nucleus. Increased solid-state polarization is observed when narrow line radicals are doped with lanthanide ions such as Gd3+, Ho3+, Dy3+, and Tb3+. Earlier results have demonstrated an incongruence between DNP experiments with trityl and BDPA, where the optimal concentrations for polarization transfer are disparate despite similar electron spin resonance linewidths. Here, the effects of Ho-DOTA on the solid-state polarization of [1-13C]pyruvic acid were compared for 3.35 T (1.4 K) and 5 T (1.2 K) systems using BDPA as a radical. Multiple concentrations of BDPA were doped with variable concentrations of Ho-DOTA (0, 0.2, 0.5, 1, and 2 mM), and dissolved in 1 : 1 (v/v) of [1-13C] pyruvic acid/sulfolane mixture. Our results reveal that addition of small amounts of Ho-DOTA in the sample preparation increases the solid-state polarization for [1-13C] pyruvic acid, with the optimum Ho-DOTA concentration of 0.2 mM. Without Ho-DOTA doping, the optimum BDPA concentration found for 3.35 T (1.4 K) is 40 mM, and for 5 T (1.2 K) system it is about 60 mM. In both systems, inclusion of Ho-DOTA in the 13C DNP sample leads to a change in the breadth (ΔDNP) of the extrema between the P(+) and P(-) frequencies in microwave spectra. At no combination of BDPA and Ho3+ did polarizations reach those achievable with trityl. Simplified analysis of increased polarization as a function of decreased electron T1e used to explain results in trityl are insufficient to describe DNP with BDPA.
RESUMO
Dissolution dynamic nuclear polarization was introduced in 2003 as a method for producing hyperpolarized 13C solutions suitable for metabolic imaging. The signal to noise ratio for the imaging experiment depends on the maximum polarization achieved in the solid state. Hence, optimization of the DNP conditions is essential. To acquire maximum polarization many parameters related to sample preparation can be modulated. Recently, it was demonstrated that Ho3+, Dy3+, Tb3+, and Gd3+ complexes enhance the polarization at 1.2 K and 3.35 T when using the trityl radical as the primary paramagnetic center. Here, we have investigated the influence of Ho-DOTA on 13C solid state DNP at 1.2 K and 5 T. We have performed 13C DNP on [1-13C] sodium acetate in 1 : 1 (v/v) water/glycerol with 15 mM trityl OX063 radicals in the presence of a series of Ho-DOTA concentrations (0, 0.5, 1, 2, 3, 5 mM). We have found that adding a small amount of Ho-DOTA in the sample preparation not only enhances the 13C polarization but also decreases the buildup time. The optimum Ho-DOTA concentration was 2 mM. In addition, the microwave sweep spectrum changes character in a manner that suggests both the cross effect and thermal mixing are active mechanisms for trityl radical at 5 T and 1.2 K.
RESUMO
We have performed (69)Ga, (71)Ga, and (137)Ba NMR on Ba8Ga16Ge30, a clathrate semiconductor which has been of considerable interest due to its large figure of merit for thermoelectric applications. In measurements from 4 K to 450 K, we used measurements on the two Ga nuclei to separate the magnetic and electric quadrupole hyperfine contributions and thereby gain information about the metallic and phonon behavior. The results show the presence of a pseudogap in the Ga electronic states within the conduction band, superposed upon a large Ba contribution to the conduction band. Meanwhile the phonon contributions to the Ga relaxation rates are large and increase more rapidly with temperature than typical semiconductors. These results provide evidence for enhanced anharmonicity of the propagative phonon modes over a wide range, providing experimental evidence for enhanced phonon-phonon scattering as a mechanism for the reduced thermal conductivity.
RESUMO
We have performed (63)Cu, (65)Cu, and (137)Ba NMR on Ba8Cu5SixGe41-x, a series of intermetallic clathrates known for their potential as thermoelectric materials, in order to investigate the electronic behavior of the samples. The spectra and spin-lattice relaxation times were measured at 77 K and 290 K for the entire composition range 0 ≤ x ≤ 41. Magnetic and quadrupole shifts and relaxation rates of the Cu NMR data were extracted, and thereby carrier-induced metallic contributions identified. The observed shifts change in a nonlinear way with increasing Si substitution: from x = 0 to about 20 the shifts are essentially constant, while approaching x = 41 they increase rapidly. At the same time, Ba NMR data indicate greater Ba-site participation in the conduction band in Ba8Cu5Si41 than in Ba8Cu5Ge41. The results indicate surprisingly little change in electronic features vs. Si content for most of the composition range, while Ba8Cu5Si41 exhibits enhanced hybridization and a more metallic framework than Ba8Cu5Ge41.
