Unraveling Eumelanin Radical Formation by Nanodiamond Optical Relaxometry in a Living Cell.

Defect centers in a nanodiamond (ND) allow the detection of tiny magnetic fields in their direct surroundings, rendering them as an emerging tool for nanoscale sensing applications. Eumelanin, an abundant pigment, plays an important role in biology and material science. Here, for the first time, we evaluate the comproportionation reaction in eumelanin by detecting and quantifying semiquinone radicals through the nitrogen-vacancy color center. A thin layer of eumelanin is polymerized on the surface of nanodiamonds (NDs), and depending on the environmental conditions, such as the local pH value, near-infrared, and ultraviolet light irradiation, the radicals form and react in situ. By combining experiments and theoretical simulations, we quantify the local number and kinetics of free radicals in the eumelanin layer. Next, the ND sensor enters the cells via endosomal vesicles. We quantify the number of radicals formed within the eumelanin layer in these acidic compartments by applying optical relaxometry measurements. In the future, we believe that the ND quantum sensor could provide valuable insights into the chemistry of eumelanin, which could contribute to the understanding and treatment of eumelanin- and melanin-related diseases.

Germanium Vacancy in Diamond Quantum Memory Exceeding 20 ms.

Negatively charged group-IV defects in diamond show great potential as quantum network nodes due to their efficient spin-photon interface. However, reaching sufficiently long coherence times remains a challenge. In this work, we demonstrate coherent control of germanium vacancy center (GeV) at millikelvin temperatures and extend its coherence time by several orders of magnitude to more than 20 ms. We model the magnetic and amplitude noise as an Ornstein-Uhlenbeck process, reproducing the experimental results well. The utilized method paves the way to optimized coherence times of group-IV defects in various experimental conditions and their successful applications in quantum technologies.

Protecting Quantum Information via Destructive Interference of Correlated Noise.

Decoherence and imperfect control are crucial challenges for quantum technologies. Common protection strategies rely on noise temporal autocorrelation, which is not optimal if other correlations are present. We develop and demonstrate experimentally a strategy that uses the cross-correlation of two noise sources. Utilizing destructive interference of cross-correlated noise extends the coherence time tenfold, improves control fidelity, and surpasses the state-of-the-art sensitivity for high frequency quantum sensing, significantly expanding the applicability of noise protection strategies.

Transform-Limited Photon Emission from a Lead-Vacancy Center in Diamond above 10 K.

Transform-limited photon emission from quantum emitters is essential for high-fidelity entanglement generation. In this Letter, we report the coherent optical property of a single negatively charged lead-vacancy (PbV) center in diamond. Photoluminescence excitation measurements reveal stable fluorescence with a linewidth of 39 MHz at 6 K, close to the transform limit estimated from the lifetime measurement. We observe 4 orders of magnitude different linewidths of the two zero-phonon lines, and find that the phonon-induced relaxation in the ground state contributes to this huge difference in the linewidth. Because of the suppressed phonon absorption in the PbV center, we observe nearly transform-limited photon emission up to 16 K, demonstrating its high temperature robustness compared to other color centers in diamond.

Revealing the Origin of Fast Delayed Fluorescence in a Donor Functionalized Bisterpyridine.

A new carbazole-substituted bisterpyridine with pronounced delayed fluorescence is presented. While the molecular donor-acceptor-donor design suggests the origin of this to be thermally activated delayed fluorescence (TADF), results from various photophysical characterizations, OLED characteristics, temperature-dependent NMR spectroscopy, and DFT calculations all point against the involvement of triplet states. The molecule exhibits blue emission at about 440 nm with two or more fast decay channels in the lower nanosecond range in both solution and thin films. The delayed emission is proposed to be caused by rotational vibrational modes. We suggest that these results are generally applicable, especially for more complex molecules, and should be considered as alternative or competitive emissive relaxation pathways in the field of organic light emitting materials.

Roadmap on nanoscale magnetic resonance imaging.

The field of nanoscale magnetic resonance imaging (NanoMRI) was started 30 years ago. It was motivated by the desire to image single molecules and molecular assemblies, such as proteins and virus particles, with near-atomic spatial resolution and on a length scale of 100 nm. Over the years, the NanoMRI field has also expanded to include the goal of useful high-resolution nuclear magnetic resonance (NMR) spectroscopy of molecules under ambient conditions, including samples up to the micron-scale. The realization of these goals requires the development of spin detection techniques that are many orders of magnitude more sensitive than conventional NMR and MRI, capable of detecting and controlling nanoscale ensembles of spins. Over the years, a number of different technical approaches to NanoMRI have emerged, each possessing a distinct set of capabilities for basic and applied areas of science. The goal of this roadmap article is to report the current state of the art in NanoMRI technologies, outline the areas where they are poised to have impact, identify the challenges that lie ahead, and propose methods to meet these challenges. This roadmap also shows how developments in NanoMRI techniques can lead to breakthroughs in emerging quantum science and technology applications. .

A Stable Chichibabin Diradicaloid with Near-Infrared Emission.

Conjugated molecules with multiple radical centers such as the iconic Chichibabin diradicaloid hold promise as building blocks in materials for quantum sensing and quantum information processing. However, it is a considerable challenge to design simple analogues of the Chichibabin hydrocarbon that are chemically inert, exhibit high diradical character and emit light at a distinct wavelength that may offer an optical readout of the spin state in functional ensembles. Here we describe the serendipitous discovery of the stable TTM-TTM diradicaloid, which exhibits high diradical character, a striking sky-blue color and near-infrared (NIR) emission (in solution). This combination of properties is unique among related diradicaloids and is due to the presence of hydrogen and chlorine atoms in "just the right positions", allowing a perfectly planar, yet predominantly benzenoid bridge to connect the two sterically stabilized radical centers. In-depth studies of the optical and magnetic properties suggest that this structural motif could become a mainstay building block of organic spin materials.

Parahydrogen-Polarized Fumarate for Preclinical in Vivo Metabolic Magnetic Resonance Imaging.

We present a versatile method for the preparation of hyperpolarized [1-13C]fumarate as a contrast agent for preclinical in vivo MRI, using parahydrogen-induced polarization (PHIP). To benchmark this process, we compared a prototype PHIP polarizer to a state-of-the-art dissolution dynamic nuclear polarization (d-DNP) system. We found comparable polarization, volume, and concentration levels of the prepared solutions, while the preparation effort is significantly lower for the PHIP process, which can provide a preclinical dose every 10 min, opposed to around 90 min for d-DNP systems. With our approach, a 100 mM [1-13C]-fumarate solution of volumes up to 3 mL with 13-20% 13C-hyperpolarization after purification can be produced. The purified solution has a physiological pH, while the catalyst, the reaction side products, and the precursor material concentrations are reduced to nontoxic levels, as confirmed in a panel of cytotoxicity studies. The in vivo usage of the hyperpolarized fumarate as a perfusion agent in healthy mice and the metabolic conversion of fumarate to malate in tumor-bearing mice developing regions with necrotic cell death is demonstrated. Furthermore, we present a one-step synthesis to produce the 13C-labeled precursor for the hydrogenation reaction with high yield, starting from 13CO2 as a cost-effective source for 13C-labeled compounds.

Optimal Sensing Protocol for Statistically Polarized Nano-NMR with NV Centers.

Diffusion noise represents a major constraint to successful liquid state nano-NMR spectroscopy. Using the Fisher information as a faithful measure, we theoretically calculate and experimentally show that phase sensitive protocols are superior in most experimental scenarios, as they maximize information extraction from correlations in the sample. We derive the optimal experimental parameters for quantum heterodyne detection (Qdyne) and present the most accurate statistically polarized nano-NMR Qdyne detection experiments to date, leading the way to resolve chemical shifts and J couplings at the nanoscale.

Observation of discrete time-crystalline order in a disordered dipolar many-body system.

Understanding quantum dynamics away from equilibrium is an outstanding challenge in the modern physical sciences. Out-of-equilibrium systems can display a rich variety of phenomena, including self-organized synchronization and dynamical phase transitions. More recently, advances in the controlled manipulation of isolated many-body systems have enabled detailed studies of non-equilibrium phases in strongly interacting quantum matter; for example, the interplay between periodic driving, disorder and strong interactions has been predicted to result in exotic 'time-crystalline' phases, in which a system exhibits temporal correlations at integer multiples of the fundamental driving period, breaking the discrete time-translational symmetry of the underlying drive. Here we report the experimental observation of such discrete time-crystalline order in a driven, disordered ensemble of about one million dipolar spin impurities in diamond at room temperature. We observe long-lived temporal correlations, experimentally identify the phase boundary and find that the temporal order is protected by strong interactions. This order is remarkably stable to perturbations, even in the presence of slow thermalization. Our work opens the door to exploring dynamical phases of matter and controlling interacting, disordered many-body systems.

Bayesian-Based Hybrid Method for Rapid Optimization of NV Center Sensors.

NV centers are among the most promising platforms in the field of quantum sensing. Magnetometry based on NV centers, especially, has achieved concrete development in areas of biomedicine and medical diagnostics. Improving the sensitivity of NV center sensors under wide inhomogeneous broadening and fieldamplitude drift is a crucial issue of continuous concern that relies on the coherent control of NV centers with high average fidelity. Quantum optimal control (QOC) methods provide access to this target; nevertheless, the high time consumption of current methods due to the large number of needful sample points as well as the complexity of the parameter space has hindered their usability. In this paper, we propose the Bayesian estimation phase-modulated (B-PM) method to tackle this problem. In the case of the state transforming of an NV center ensemble, the B-PM method reduced the time consumption by more than 90% compared with the conventional standard Fourier basis (SFB) method while increasing the average fidelity from 0.894 to 0.905. In the AC magnetometry scenario, the optimized control pulse obtained with the B-PM method achieved an eight-fold extension of coherence time T2 compared with the rectangular π pulse. Similar application can be made in other sensing situations. As a general algorithm, the B-PM method can be further extended to the open- and closed-loop optimization of complex systems based on a variety of quantum platforms.

Silicon-Vacancy Nanodiamonds as High Performance Near-Infrared Emitters for Live-Cell Dual-Color Imaging and Thermometry.

Nanodiamonds (NDs) with color centers are excellent emitters for various bioimaging and quantum biosensing applications. In our work, we explore new applications of NDs with silicon-vacancy centers (SiV) obtained by high-pressure high-temperature (HPHT) synthesis based on metal-catalyst-free growth. They are coated with a polypeptide biopolymer, which is essential for efficient cellular uptake. The unique optical properties of NDs with SiV are their high photostability and narrow emission in the near-infrared region. Our results demonstrate for the first time that NDs with SiV allow live-cell dual-color imaging and intracellular tracking. Also, intracellular thermometry and challenges associated with SiV atomic defects in NDs are investigated and discussed for the first time. NDs with SiV nanoemitters provide new avenues for live-cell bioimaging, diagnostic (SiV as a nanosized thermometer), and theranostic (nanodiamonds as drug carrier) applications.

Detection of Few Hydrogen Peroxide Molecules Using Self-Reporting Fluorescent Nanodiamond Quantum Sensors.

Hydrogen peroxide (H2O2) plays an important role in various signal transduction pathways and regulates important cellular processes. However, monitoring and quantitatively assessing the distribution of H2O2 molecules inside living cells requires a nanoscale sensor with molecular-level sensitivity. Herein, we show the first demonstration of sub-10 nm-sized fluorescent nanodiamonds (NDs) as catalysts for the decomposition of H2O2 and the production of radical intermediates at the nanoscale. Furthermore, the nitrogen-vacancy quantum sensors inside the NDs are employed to quantify the aforementioned radicals. We believe that our method of combining the peroxidase-mimicking activities of the NDs with their intrinsic quantum sensor showcases their application as self-reporting H2O2 sensors with molecular-level sensitivity and nanoscale spatial resolution. Given the robustness and the specificity of the sensor, our results promise a new platform for elucidating the role of H2O2 at the cellular level.

Hyperpolarized Solution-State NMR Spectroscopy with Optically Polarized Crystals.

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.

One decade of quantum optimal control in the chopped random basis.

The chopped random basis (CRAB) ansatz for quantum optimal control has been proven to be a versatile tool to enable quantum technology applications such as quantum computing, quantum simulation, quantum sensing, and quantum communication. Its capability to encompass experimental constraints-while maintaining an access to the usually trap-free control landscape-and to switch from open-loop to closed-loop optimization (including with remote access-or RedCRAB) is contributing to the development of quantum technology on many different physical platforms. In this review article we present the development, the theoretical basis and the toolbox for this optimization algorithm, as well as an overview of the broad range of different theoretical and experimental applications that exploit this powerful technique.

Nanodiamond Theranostic for Light-Controlled Intracellular Heating and Nanoscale Temperature Sensing.

Temperature is an essential parameter in all biological systems, but information about the actual temperature in living cells is limited. Especially, in photothermal therapy, local intracellular temperature changes induce cell death but the local temperature gradients are not known. Highly sensitive nanothermometers would be required to measure and report local temperature changes independent of the intracellular environment, including pH or ions. Fluorescent nanodiamonds (ND) enable temperature sensing at the nanoscale independent of external conditions. Herein, we prepare ND nanothermometers coated with a nanogel shell and the photothermal agent indocyanine green serves as a heat generator and sensor. Upon irradiation, programmed cell death was induced in cancer cells with high spatial control. In parallel, the increase in local temperature was recorded by the ND nanothermometers. This approach represents a great step forward to record local temperature changes in different cellular environments inside cells and correlate these with thermal biology.

Interaction of a heralded single photon with nitrogen-vacancy centers in a diamond.

A simple, room-temperature, cavity- and vacuum-free interface for a photon-matter interaction is implemented. In the experiment, a heralded single photon generated by the process of spontaneous parametric down-conversion is absorbed by an ensemble of nitrogen-vacancy color centers. The broad absorption spectrum associated with the phonon sideband solves the mismatch problem of a narrow absorption bandwidth in a typical atomic medium and broadband spectrum of quantum light. The heralded single photon source is tunable in the spectral range 452 - 575 nm, which overlaps well with the absorption spectrum of nitrogen-vacancy centers.

Determination of the Three-Dimensional Magnetic Field Vector Orientation with Nitrogen Vacany Centers in Diamond.

Absolute knowledge about the magnetic field orientation plays a crucial role in single spin-based quantum magnetometry and the application toward spin-based quantum computation. In this paper, we reconstruct the three-dimensional orientation of an arbitrary static magnetic field with individual nitrogen vacancy (NV) centers in diamond. We determine the polar and the azimuthal angle of the magnetic field orientation relative to the diamond lattice. Therefore, we use information from the photoluminescence anisotropy of the NV, together with a simple pulsed optically detected magnetic resonance experiment. Our nanoscopic magnetic field determination is generally applicable and does not rely on special prerequisites such as strongly coupled nuclear spins or particular controllable fields. Hence, our presented results open up new paths for precise NMR reconstructions and the modulation of the electron-electron spin interaction in EPR measurements by specifically tailored magnetic fields.

dc Magnetometry with Engineered Nitrogen-Vacancy Spin Ensembles in Diamond.

The exquisite optical and spin properties of nitrogen-vacancy (NV) centers in diamond have made them a promising platform for quantum sensing. The prospect of NV-based sensors relies on the controlled production of these atomic-scale defects. Here we report on the fabrication of a preferentially oriented, shallow ensemble of NV centers and their applicability for sensing dc magnetic fields. For the present sample, the residual paramagnetic impurities are the dominant source of environmental noise, limiting the dephasing time (T2*) of the NVs. By controlling the P1 spin-bath, we achieve a 4-fold improvement in the T2* of the NV ensemble. Further, we show that combining spin-bath control and homonuclear decoupling sequence cancels NV-NV interactions and partially protects the sensors from a broader spin environment, thus extending the ensemble T2* up to 10 µs. With this decoupling protocol, we measure an improved dc magnetic field sensitivity of 1.2 nT µm3/2 Hz-1/2. Using engineered NVs and decoupling protocols, we demonstrate the prospects of harnessing the full potential of NV-based ensemble magnetometry.

Limits on Spectral Resolution Measurements by Quantum Probes.

The limits of frequency resolution in nano-NMR experiments have been discussed extensively in recent years. It is believed that there is a crucial difference between the ability to resolve a few frequencies and the precision of estimating a single one. Whereas the efficiency of single frequency estimation gradually increases with the square root of the number of measurements, the ability to resolve two frequencies is limited by the specific timescale of the signal and cannot be compensated for by extra measurements. Here we show theoretically and demonstrate experimentally that the relationship between these quantities is more subtle and both are only limited by the Cramér-Rao bound of a single frequency estimation.