Monday, December 30, 2013

Solid-Phase Polarization Matrixes for Dynamic Nuclear Polarization from Homogeneously Distributed Radicals in Mesostructured Hybrid Silica Materials


Gajan, D., et al., Solid-Phase Polarization Matrixes for Dynamic Nuclear Polarization from Homogeneously Distributed Radicals in Mesostructured Hybrid Silica Materials. J. Am. Chem. Soc., 2013. 135(41): p. 15459-15466.


Mesoporous hybrid silica?organic materials containing homogeneously distributed stable mono- or dinitroxide radicals covalently bound to the silica surface were developed as polarization matrixes for solid-state dynamic nuclear polarization (DNP) NMR experiments. For TEMPO-containing materials impregnated with water or 1,1,2,2-tetrachloroethane, enhancement factors of up to 36 were obtained at ?100 K and 9.4 T without the need for a glass-forming additive. We show that the homogeneous radical distribution and the subtle balance between the concentration of radical in the material and the fraction of radicals at a sufficient inter-radical distance to promote the cross-effect are the main determinants for the DNP enhancements we obtain. The material, as well as an analogue containing the poorly soluble biradical bTUrea, is used as a polarizing matrix for DNP NMR experiments of solutions containing alanine and pyruvic acid. The analyte is separated from the polarization matrix by simple filtration.