On The Potential of Dynamic Nuclear Polarization Enhanced Diamonds in Solid-State and Dissolution (13) C†NMR Spectroscopy.

Dynamic nuclear polarization (DNP) is a versatile option to improve the sensitivity of NMR and MRI. This versatility has elicited interest for overcoming potential limitations of these techniques, including the achievement of solid-state polarization enhancement at ambient conditions, and the maximization of (13) C signal lifetimes for performing in vivo MRI scans. This study explores whether diamond's (13) C behavior in nano- and micro-particles could be used to achieve these ends. The characteristics of diamond's DNP enhancement were analyzed for different magnetic fields, grain sizes, and sample environments ranging from cryogenic to ambient temperatures, in both solution and solid-state experiments. It was found that (13) C NMR signals could be boosted by orders of magnitude in either low- or room-temperature solid-state DNP experiments by utilizing naturally occurring paramagnetic P1 substitutional nitrogen defects. We attribute this behavior to the unusually long electronic/nuclear spin-lattice relaxation times characteristic of diamond, coupled with a time-independent cross-effect-like polarization transfer mechanism facilitated by a matching of the nitrogen-related hyperfine coupling and the (13) C Zeeman splitting. The efficiency of this solid-state polarization process, however, is harder to exploit in dissolution DNP-enhanced MRI contexts. The prospects for utilizing polarized diamond approaching nanoscale dimensions for both solid and solution applications are briefly discussed.

Local and bulk (13)C hyperpolarization in nitrogen-vacancy-centred diamonds at variable fields and orientations.

Polarizing nuclear spins is of fundamental importance in biology, chemistry and physics. Methods for hyperpolarizing (13)C nuclei from free electrons in bulk usually demand operation at cryogenic temperatures. Room temperature approaches targeting diamonds with nitrogen-vacancy centres could alleviate this need; however, hitherto proposed strategies lack generality as they demand stringent conditions on the strength and/or alignment of the magnetic field. We report here an approach for achieving efficient electron-(13)C spin-alignment transfers, compatible with a broad range of magnetic field strengths and field orientations with respect to the diamond crystal. This versatility results from combining coherent microwave- and incoherent laser-induced transitions between selected energy states of the coupled electron-nuclear spin manifold. (13)C-detected nuclear magnetic resonance experiments demonstrate that this hyperpolarization can be transferred via first-shell or via distant (13)Cs throughout the nuclear bulk ensemble. This method opens new perspectives for applications of diamond nitrogen-vacancy centres in nuclear magnetic resonance, and in quantum information processing.

Bulk nuclear polarization enhanced at room temperature by optical pumping.

Bulk (13)C polarization can be strongly enhanced in diamond at room temperature based on the optical pumping of nitrogen-vacancy color centers. This effect was confirmed by irradiating single crystals at a ~50 mT field promoting anticrossings between electronic excited-state levels, followed by shuttling of the sample into an NMR setup and by subsequent (13)C detection. A nuclear polarization of ~0.5%--equivalent to the (13)C polarization achievable by thermal polarization at room temperature at fields of ~2000 T--was measured, and its bulk nature determined based on line shape and relaxation measurements. Positive and negative enhanced polarizations were obtained, with a generally complex but predictable dependence on the magnetic field during optical pumping. Owing to its simplicity, this (13)C room temperature polarizing strategy provides a promising new addition to existing nuclear hyperpolarization techniques.

Controlling spin-spin network dynamics by repeated projective measurements.

We show that coupled-spin network manipulations can be made highly effective by repeated projections of the evolving quantum states onto diagonal density-matrix states (populations). As opposed to the intricately crafted pulse trains that are often used to fine-tune a complex network's evolution, the strategy hereby presented derives from the "quantum Zeno effect" and provides a highly robust route to guide the evolution by destroying all unwanted correlations (coherences). We exploit these effects by showing that a relaxationlike behavior is endowed to polarization transfers occurring within a N-spin coupled network. Experimental implementations yield coupling constant determinations for complex spin-coupling topologies, as demonstrated within the field of liquid-state nuclear magnetic resonance.

Selective rotation pulses calculated with an inverse scattering algorithm.

Selective rotation pulses cause magnetization within a given frequency range (or slice) to undergo a specified rotation, about a specified axis. Magnetization outside this slice remains unaffected if it is initially along the z axis. It has previously been shown that the design of such pulses can be reduced to the design of selective "point-to-point" pulses, which rotate magnetization within the slice from the y axis. By decomposing the point-to-point pulses into two sub-pulses, it is shown that an inverse scattering algorithm for selective pulse design can be used to calculate selective rotation pulses with any desired spinor response, subject to the constraint that the second spinor component have constant phase across the slice. The design of selective refocusing pulses can be treated specially, requiring the calculation, by the same inverse scattering algorithm, of a single sub-pulse.