Phase-Encoded Hyperpolarized Nanodiamond for Magnetic Resonance Imaging.

Surface-functionalized nanomaterials are of interest as theranostic agents that detect disease and track biological processes using hyperpolarized magnetic resonance imaging (MRI). Candidate materials are sparse however, requiring spinful nuclei with long spin-lattice relaxation (T1) and spin-dephasing times (T2), together with a reservoir of electrons to impart hyperpolarization. Here, we demonstrate the versatility of the nanodiamond material system for hyperpolarized 13C MRI, making use of its intrinsic paramagnetic defect centers, hours-long nuclear T1 times, and T2 times suitable for spatially resolving millimeter-scale structures. Combining these properties, we enable a new imaging modality, unique to nanoparticles, that exploits the phase-contrast between spins encoded with a hyperpolarization that is aligned, or anti-aligned with the external magnetic field. The use of phase-encoded hyperpolarization allows nanodiamonds to be tagged and distinguished in an MRI based on their spin-orientation alone, and could permit the action of specific bio-functionalized complexes to be directly compared and imaged.

Nanodiamond-enhanced MRI via in situ hyperpolarization.

Nanodiamonds are of interest as nontoxic substrates for targeted drug delivery and as highly biostable fluorescent markers for cellular tracking. Beyond optical techniques, however, options for noninvasive imaging of nanodiamonds in vivo are severely limited. Here, we demonstrate that the Overhauser effect, a proton-electron polarization transfer technique, can enable high-contrast magnetic resonance imaging (MRI) of nanodiamonds in water at room temperature and ultra-low magnetic field. The technique transfers spin polarization from paramagnetic impurities at nanodiamond surfaces to 1H spins in the surrounding water solution, creating MRI contrast on-demand. We examine the conditions required for maximum enhancement as well as the ultimate sensitivity of the technique. The ability to perform continuous in situ hyperpolarization via the Overhauser mechanism, in combination with the excellent in vivo stability of nanodiamond, raises the possibility of performing noninvasive in vivo tracking of nanodiamond over indefinitely long periods of time.

Hyperpolarized Nanodiamond Surfaces.

The widespread use of nanodiamond as a biomedical platform for drug-delivery, imaging, and subcellular tracking applications stems from its nontoxicity and unique quantum mechanical properties. Here, we extend this functionality to the domain of magnetic resonance, by demonstrating that the intrinsic electron spins on the nanodiamond surface can be used to hyperpolarize adsorbed liquid compounds at low fields and room temperature. By combining relaxation measurements with hyperpolarization, spins on the surface of the nanodiamond can be distinguished from those in the bulk liquid. These results are likely of use in signaling the controlled release of pharmaceutical payloads.

Hyperpolarized nanodiamond with long spin-relaxation times.

The use of hyperpolarized agents in magnetic resonance, such as (13)C-labelled compounds, enables powerful new imaging and detection modalities that stem from a 10,000-fold boost in signal. A major challenge for the future of the hyperpolarization technique is the inherently short spin-relaxation times, typically <60 s for (13)C liquid-state compounds, which limit the time that the signal remains boosted. Here we demonstrate that 1.1% natural abundance (13)C spins in synthetic nanodiamond can be hyperpolarized at cryogenic and room temperature without the use of free radicals, and, owing to their solid-state environment, exhibit relaxation times exceeding 1 h. Combined with the already established applications of nanodiamonds in the life sciences as inexpensive fluorescent markers and non-cytotoxic substrates for gene and drug delivery, these results extend the theranostic capabilities of nanoscale diamonds into the domain of hyperpolarized magnetic resonance.

Emission and nonradiative decay of nanodiamond NV centers in a low refractive index environment.

The nitrogen vacancy (NV) center is the most widely studied single optical defect in diamond with great potential for applications in quantum technologies. Development of practical single-photon devices requires an understanding of the emission under a range of conditions and environments. In this work, we study the properties of a single NV center in nanodiamonds embedded in an air-like silica aerogel environment which provides a new domain for probing the emission behavior of NV centers in nanoscale environments. In this arrangement, the emission rate is governed primarily by the diamond crystal lattice with negligible contribution from the surrounding environment. This is in contrast to the conventional approach of studying nanodiamonds on a glass coverslip. We observe an increase in the mean lifetime due to the absence of a dielectric interface near the emitting dipoles and a distribution arising from the irregularities in the nanodiamond geometry. Our approach results in the estimation of the mean quantum efficiency (~0.7) of the nanodiamond NV emitters.

Effect of the nanodiamond host on a nitrogen-vacancy color-centre emission state.

Control over the quantum states of individual luminescent nitrogen-vacancy (NV) centres in nanodiamonds (NDs) is demonstrated by careful design of the crystal host: its size, surface functional groups, and interfacing substrate. By progressive etching of the ND host, the NV centres are induced to switch from latent, through continuous, to intermittent or "blinking" emission states. The blinking mechanism of the NV centre in NDs is elucidated and a qualitative model proposed to explain this phenomenon in terms of the centre electron(s) tunnelling to acceptor site(s). These measurements suggest that the substrate material and its proximity to the NV are responsible for the fluorescence intermittency.

Prediction and measurement of the size-dependent stability of fluorescence in diamond over the entire nanoscale.

Fluorescent defects in noncytotoxic diamond nanoparticles are candidates for qubits in quantum computing, optical labels in biomedical imaging, and sensors in magnetometry. For each application these defects need to be optically and thermodynamically stable and included in individual particles at suitable concentrations (singly or in large numbers). In this Letter, we combine simulations, theory, and experiment to provide the first comprehensive and generic prediction of the size, temperature, and nitrogen-concentration-dependent stability of optically active N-V defects in nanodiamonds.