ABSTRACT
Dynamic nuclear polarization (DNP) is routinely used as a method for increasing the sensitivity to nuclear magnetic resonance (NMR). Recently, high-field solid-effect DNP in viscous liquids on 1H nuclei was demonstrated using narrow-line polarizing agents. Here we expand the applicability of DNP in viscous media to 13C nuclei. To hyperpolarize 13C nuclei, we combined solid-effect 1H DNP with a subsequent transfer of the 1H polarization to 13C via insensitive nuclei enhanced by polarization transfer (INEPT). We demonstrate this approach using a triarylmethyl radical as a polarizing agent and glycerol-13C3 as an analyte. We achieved 13C enhancement factors of up to 45 at a magnetic field of 9.4 T and room temperature.
ABSTRACT
Dynamic nuclear polarization (DNP) is a hyperpolarization method that is widely used for increasing the sensitivity of nuclear magnetic resonance (NMR) experiments. DNP is efficient in solid-state and liquid-state NMR, but its implementation in the intermediate state, namely, viscous media, is still less explored. Here, we show that a 1H DNP enhancement of over 50 can be obtained in viscous liquids at a magnetic field of 9.4 T and a temperature of 315 K. This was accomplished by using narrow-line polarizing agents in glycerol, both the water-soluble α,γ-bisdiphenylen-ß-phenylallyl (BDPA) and triarylmethyl radicals, and a microwave/RF double-resonance probehead. We observed DNP enhancements with a field profile indicative of the solid effect and investigated the influence of microwave power, temperature, and concentration on the 1H NMR results. To demonstrate potential applications of this new DNP approach for chemistry and biology, we show hyperpolarized 1H NMR spectra of tripeptides, triglycine, and glypromate, in glycerol-d8.
ABSTRACT
Dynamic nuclear polarization (DNP) is a powerful method to enhance NMR sensitivity. Much progress has been achieved recently to optimize DNP performance at high magnetic fields in solid-state samples, mostly by utilizing the solid or the cross effect. In liquids, only the Overhauser mechanism is active, which exhibits a DNP field profile matching the EPR line shape of the radical, distinguishable from other DNP mechanisms. Here, we observe DNP enhancements with a field profile indicative of the solid effect and thermal mixing at â¼320 K and a magnetic field of 9.4 T in the fluid phase of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid bilayers doped with the radical BDPA (1,3-bis(diphenylene)-2-phenylallyl). This interesting observation might open up new perspectives for DNP applications in macromolecular systems at ambient temperatures.
