In situ temperature jump high-frequency dynamic nuclear polarization experiments: Enhanced sensitivity in liquid-state NMR spectroscopy

We describe an experiment, in situ temperature jump dynamic nuclear polarization (TJ-DNP), that is demonstrated to enhance sensitivity in liquid-state NMR experiments of low-gamma spins - C-13, N-15, etc. The approach consists of polarizing a sample at low temperature using high-frequency (140 GHz) microwaves and a biradical polarizing agent and then melting it rapidly with a pulse of 10.6 Am infrared radiation, followed by observation of the NMR signal in the presence of decoupling. In the absence of polarization losses due to relaxation, the enhancement should be epsilon(dagger) = epsilon(T-obs/T-mu wave), where epsilon(dagger) is the observed enhancement, epsilon is the enhancement obtained at the temperature where the polarization process occurs, and T-mu wave and T-obs are the polarization and observation temperatures, respectively. In a single experimental cycle, we observe room-temperature enhancements, epsilon(dagger), of C-13 signals in the range 120-400 when using a 140 GHz gyrotron microwave source, T-mu wave = 90 K, and T-obs = 300 K. In addition, we demonstrate that the experiment can be recycled to perform signal averaging that is customary in contemporary NMR spectroscopy. Presently, the experiment is applicable to samples that can be repeatedly frozen and thawed. TJ-DNP could also serve as the initial polarization step in experiments designed for rapid acquisition of multidimensional spectra.