Detection of atomic spin labels in a lipid bilayer using a single-spin nanodiamond probe.
ABSTRACT: Magnetic field fluctuations arising from fundamental spins are ubiquitous in nanoscale biology, and are a rich source of information about the processes that generate them. However, the ability to detect the few spins involved without averaging over large ensembles has remained elusive. Here, we demonstrate the detection of gadolinium spin labels in an artificial cell membrane under ambient conditions using a single-spin nanodiamond sensor. Changes in the spin relaxation time of the sensor located in the lipid bilayer were optically detected and found to be sensitive to near-individual (4 ± 2) proximal gadolinium atomic labels. The detection of such small numbers of spins in a model biological setting, with projected detection times of 1 s [corresponding to a sensitivity of ?5 Gd spins per Hz(1/2)], opens a pathway for in situ nanoscale detection of dynamical processes in biology.
Project description: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.
Project description:The ability to sense the magnetic state of individual magnetic nano-objects is a key capability for powerful applications ranging from readout of ultradense magnetic memory to the measurement of spins in complex structures with nanometer precision. Magnetic nano-objects require extremely sensitive sensors and detection methods. We create an atomic spin sensor consisting of three Fe atoms and show that it can detect nanoscale antiferromagnets through minute, surface-mediated magnetic interaction. Coupling, even to an object with no net spin and having vanishing dipolar stray field, modifies the transition matrix element between two spin states of the Fe atom-based spin sensor that changes the sensor's spin relaxation time. The sensor can detect nanoscale antiferromagnets at up to a 3-nm distance and achieves an energy resolution of 10 ?eV, surpassing the thermal limit of conventional scanning probe spectroscopy. This scheme permits simultaneous sensing of multiple antiferromagnets with a single-spin sensor integrated onto the surface.
Project description:In nanoscale metrology, dissipation of the sensor limits its performance. Strong dissipation has a negative impact on sensitivity, and sensor-target interaction even causes relaxation or dephasing of the latter. The weak dissipation of nitrogen-vacancy (NV) sensors in room temperature diamond enables detection of individual target nuclear spins, yet limits the spectral resolution of nuclear magnetic resonance (NMR) spectroscopy to several hundred Hertz, which typically prevents molecular recognition. Here, we use the NV intrinsic nuclear spin as a nonvolatile classical memory to store NMR information, while suppressing sensor back-action on the target using controlled decoupling of sensor, memory, and target. We demonstrate memory lifetimes up to 4?min and apply measurement and decoupling protocols, which exploit such memories efficiently. Our universal NV-based sensor device records single-spin NMR spectra with 13?Hz resolution at room temperature.Dissipation of the sensor is a limiting factor in metrology. Here, Pfender et al. suppress this effect employing the nuclear spin of an NV centre for robust intermediate storage of classical NMR information, allowing then to record single-spin NMR spectra with 13?Hz resolution at room temperature.
Project description:Central spin decoherence caused by nuclear spin baths is often a critical issue in various quantum computing schemes, and it has also been used for sensing single-nuclear spins. Recent theoretical studies suggest that central spin decoherence can act as a probe of many-body physics in spin baths; however, identification and detection of many-body correlations of nuclear spins in nanoscale systems are highly challenging. Here, taking a phosphorus donor electron spin in a (29)Si nuclear spin bath as our model system, we discover both theoretically and experimentally that many-body correlations in nanoscale nuclear spin baths produce identifiable signatures in decoherence of the central spin under multiple-pulse dynamical decoupling control. We demonstrate that under control by an odd or even number of pulses, the central spin decoherence is principally caused by second- or fourth-order nuclear spin correlations, respectively. This study marks an important step toward studying many-body physics using spin qubits.
Project description: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.
Project description:Nuclear magnetic resonance spectroscopy and magnetic resonance imaging at the ultimate sensitivity limit of single molecules or single nuclear spins requires fundamentally new detection strategies. The strong coupling regime, when interaction between sensor and sample spins dominates all other interactions, is one such strategy. In this regime, classically forbidden detection of completely unpolarized nuclei is allowed, going beyond statistical fluctuations in magnetization. Here we realize strong coupling between an atomic (nitrogen-vacancy) sensor and sample nuclei to perform nuclear magnetic resonance on four (29)Si spins. We exploit the field gradient created by the diamond atomic sensor, in concert with compressed sensing, to realize imaging protocols, enabling individual nuclei to be located with Angstrom precision. The achieved signal-to-noise ratio under ambient conditions allows single nuclear spin sensitivity to be achieved within seconds.
Project description: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.
Project description:Methods and techniques to measure and image beyond the state-of-the-art have always been influential in propelling basic science and technology. Because current technologies are venturing into nanoscopic and molecular-scale fabrication, atomic-scale measurement techniques are inevitable. One such emerging sensing method uses the spins associated with nitrogen-vacancy (NV) defects in diamond. The uniqueness of this NV sensor is its atomic size and ability to perform precision sensing under ambient conditions conveniently using light and microwaves (MW). These advantages have unique applications in nanoscale sensing and imaging of magnetic fields from nuclear spins in single biomolecules. During the last few years, several encouraging results have emerged towards the realization of an NV spin-based molecular structure microscope. Here, we present a projection-reconstruction method that retrieves the three-dimensional structure of a single molecule from the nuclear spin noise signatures. We validate this method using numerical simulations and reconstruct the structure of a molecular phantom β-cyclodextrin, revealing the characteristic toroidal shape.
Project description:Atomic spins for quantum technologies need to be individually addressed and positioned with nanoscale precision. C<sub>60</sub> fullerene cages offer a robust packaging for atomic spins, while allowing in-situ physical positioning at the nanoscale. However, achieving single-spin level readout and control of endofullerenes has so far remained elusive. In this work, we demonstrate electron paramagnetic resonance on an encapsulated nitrogen spin (<sup>14</sup>N@C<sub>60</sub>) within a C<sub>60</sub> matrix using a single near-surface nitrogen vacancy (NV) center in diamond at 4.7 K. Exploiting the strong magnetic dipolar interaction between the NV and endofullerene electronic spins, we demonstrate radio-frequency pulse controlled Rabi oscillations and measure spin-echos on an encapsulated spin. Modeling the results using second-order perturbation theory reveals an enhanced hyperfine interaction and zero-field splitting, possibly caused by surface adsorption on diamond. These results demonstrate the first step towards controlling single endofullerenes, and possibly building large-scale endofullerene quantum machines, which can be scaled using standard positioning or self-assembly methods.
Project description:Single nitrogen-vacancy (NV) defect centers in diamond have been exploited as single photon sources and spin qubits due to their room-temperature robust quantum light emission and long electron spin coherence times. They were coupled to a manifold of structures, such as optical cavities, plasmonic waveguides, and even injected into living cells to study fundamental interactions of various nature at the nanoscale. Of particular interest are applications of NVs as quantum sensors for local nanomagnetometry. Here, we employ a nanomanipulation approach to couple a single NV center in a nanodiamond to a single few-nm superparamagnetic iron oxide nanoparticle in a controlled way. After measuring via relaxometry the magnetic particle spin-noise, we take advantage of the crystal strain m s ?=?±?1 spin level separation to detect the superparamagnetic particle's effect in presence of a driving AC magnetic field. Our experiments provide detailed insight in the behavior of such particles with respect to high frequency fields. The approach can be extended to the investigation of increasingly complex, but controlled nanomagnetic hybrid particle assemblies. Moreover, our results suggest that superparamagnetic nanoparticles can amplify local magnetic interactions in order to improve the sensitivity of diamond nanosensors for specific measurement scenarios.