Hyperpolarized substrates prepared via dissolution dynamic nuclear polarization have been proposed as magnetic resonance imaging (MRI) agents for cancer or cardiac failure diagnosis and therapy monitoring through the detection of metabolic impairments in vivo. The use of potentially toxic persistent radicals to hyperpolarize substrates was hitherto required. We demonstrate that by shining UV light for an hour on a frozen pure endogenous substance, namely the glucose metabolic product pyruvic acid, it is possible to generate a concentration of photo-induced radicals that is large enough to highly enhance the 13 C polarization of the substance via dynamic nuclear polarization. These radicals recombine upon dissolution and a solution composed of purely endogenous products is obtained for performing in vivo metabolic hyperpolarized 13 C MRI with high spatial resolution. Our method opens the way to safe and straightforward preclinical and clinical applications of hyperpolarized MRI because the filtering procedure mandatory for clinical applications and the associated pharmacological tests necessary to prevent contamination are eliminated, concurrently allowing a decrease in the delay between preparation and injection of the imaging agents for improved in vivo sensitivity.is a very powerful imaging modality in terms of temporal and spatial resolution of anatomical structures. The modality is widespread, well established in clinical environments, and paramagnetic agents are used extensively for enhanced contrast or perfusion examination. MR is also a unique technique to obtain in vivo metabolic maps using the spectroscopic information that can be extracted from the time-domain acquisitions. In particular, it is possible to monitor the biochemical transformations of specific substrates that are delivered to subjects. Because it gives access to the kinetics of the conversion of substrates into metabolites, MR spectroscopy (MRS) of the carbon nuclei ( 13 C) is one of the most powerful techniques to investigate intermediary metabolism (1).The well-known weakness of MR as a spectroscopic technique is its relatively low sensitivity. It can be offset by so-called hyperpolarization methods, in particular the one based on dynamic nuclear polarization (DNP) (2), which is now commonly referred to as dissolution DNP and was first proposed about a decade ago (3). The hyperpolarized substrates obtained following dissolution DNP are biomolecules in aqueous solution with a largely out-ofequilibrium nuclear spin polarization corresponding to an enhancement of several orders of magnitude compared with the thermal equilibrium polarization attainable in MRI scanners. A basic requirement for DNP is the presence of unpaired electron spins in the sample to be hyperpolarized. These polarizing agents are usually incorporated in the form of persistent radicals. An inherent limit of any hyperpolarization method is that the intrinsic longitudinal nuclear spin relaxation will annihilate the polarization enhancement in the course of time to reach t...

Hyperpolarization via dissolution dynamic nuclear polarization (DNP) is a versatile method to dramatically enhance the liquid-state NMR signal of X-nuclei and can be used for performing metabolic and molecular imaging. It was recently demonstrated that instead of incorporating persistent radicals as source of unpaired electron spins, required for DNP, nonpersistent radicals can be photoinduced in frozen beads of neat pyruvic acid (PA), the most common substrate for metabolic imaging. In the present work, it is shown that the same radicals can be created in frozen solutions containing a fraction of PA in addition to 13 C-or 6 Li-labeled salts or 129 Xe nuclei. The use of these nonpersistent radicals prevents the loss of a substantial part of the polarization during the transfer of hyperpolarized solutions into iron-shielded high-field MRI scanners. It is also demonstrated that UV-irradiated d 4 -PA yields nonpersistent radicals exhibiting similarities with the most efficient and widely used persistent trityl radicals.

Nuclear spin hyperpolarization provides a promising route to overcome the challenges imposed by the limited sensitivity of nuclear magnetic resonance. Here we demonstrate that dissolution of spin-polarized pentacene-doped naphthalene crystals enables transfer of polarization to target molecules via intermolecular cross-relaxation at room temperature and moderate magnetic fields (1.45 T). This makes it possible to exploit the high spin polarization of optically polarized crystals, while mitigating the challenges of its transfer to external nuclei. With this method, we inject the highly polarized mixture into a benchtop NMR spectrometer and observe the polarization dynamics for target 1H nuclei. Although the spectra are radiation damped due to the high naphthalene magnetization, we describe a procedure to process the data to obtain more conventional NMR spectra and extract the target nuclei polarization. With the entire process occurring on a time scale of 1 min, we observe NMR signals enhanced by factors between −200 and −1730 at 1.45 T for a range of small molecules.

Spin ensembles of nitrogen vacancy (NV) centers in diamond are emerging as powerful spin-based sensors for magnetic, electric and thermal field imaging with high spatial and temporal resolution. Here we characterize the formation of depth-confined NV center ensembles, activated by electron irradiation in diamond layers grown by plasma enhanced chemical vapor deposition with nitrogen codoping. To do so, we exploit the high magnetic sensitivity of ensembles of NV centers to probe their spin environment as a function of growth and irradiation parameters. We engineer an NV ensemble whose magnetic sensitivity is within a factor of two of the static NV-NV dipolar interaction limit, thus demonstrating a powerful platform for quantum sensing.

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