The spin-lattice relaxation time (T1) of a DNP molecular probe is a key parameter in acquiring NMR signals in dissolution-DNP (d-DNP) experiments. Using molecular probes with long T1, NMR spin signals can survive for a duration sufficient for the study of metabolism (1-3 min). Deuteration of directly bonded 13C protonated positions has been useful in prolonging the visibility of hyperpolarized labeled 13C sites that are otherwise protonated. Here, we sought to investigate whether proton irradiation could affect the T1 of such 13C nuclei when such positions are in their naturally abundant form, i.e. directly bonded to protons.