Fast, broad-band magnetic resonance spectroscopy with diamond widefield relaxometry

We present an alternative to conventional Electron Paramagnetic Resonance spectroscopy equipment. Avoiding the use of bulky magnets and magnetron equipment, we use the photoluminescence of an ensemble of Nitrogen-Vacancy centers at the surface of a diamond. Monitoring their relaxation time (or T1), we detected their cross-relaxation with the compound of interest. In addition, the EPR spectra is encoded through a localized magnetic field gradient. While 12 minutes was necessary to record each data point of the spectrum with previous individual NV center's technics, we are able to reconstruct a full spectrum at once in 3 seconds, over a range from 3 to 11 gauss. In term of sensitivity, only 0.5 microliter of a hexaaquacopper (II) ion solution with 1 micromole per liter concentration was necessary.Comment: Main text (15 pages, 6 Figures) + Supplementary (6 Pages, 7 Figures

Investigation of Surface Magnetic Noise by Shallow Spins in Diamond

We present measurements of spin relaxation times (T1, T1ρ, T2) on very shallow (≲5  nm) nitrogen-vacancy centers in high-purity diamond single crystals. We find a reduction of spin relaxation times up to 30 times compared to bulk values, indicating the presence of ubiquitous magnetic impurities associated with the surface. Our measurements yield a density of 0.01–0.1μB/nm2 and a characteristic correlation time of 0.28(3) ns of surface states, with little variation between samples and chemical surface terminations. A low temperature measurement further confirms that fluctuations are thermally activated. The data support the atomistic picture where impurities are associated with the top carbon layers, and not with terminating surface atoms or adsorbate molecules. The low spin density implies that the presence of A single surface impurity is sufficient to cause spin relaxation of a shallow nitrogen-vacancy center

The Response of HeLa Cells to Fluorescent NanoDiamond Uptake

Fluorescent nanodiamonds are promising probes for nanoscale magnetic resonance measurements. Their physical properties predict them to have particularly useful applications in intracellular analysis. Before using them in intracellular experiments however, it should be clear whether diamond particles influence cell biology. While cytotoxicity has already been ruled out in previous studies, we consider the non-fatal influence of fluorescent nanodiamonds on the formation of reactive oxygen species (an important stress indicator and potential target for intracellular sensing) for the first time. We investigated the influence of different sizes, shapes and concentrations of nanodiamonds on the genetic and protein level involved in oxidative stress-related pathways of the HeLa cell, an important model cell line in research. The changes in viability of the cells and the difference in intracellular levels of free radicals, after diamond uptake, are surprisingly small. At lower diamond concentrations, the cellular metabolism cannot be distinguished from that of untreated cells. This research supports the claims of non-toxicity and includes less obvious non-fatal responses. Finally, we give a handhold concerning the diamond concentration and size to use for non-toxic, intracellular measurements in favour of (cancer) research in HeLa cells

Diamond Color Centers in Diamonds for Chemical and Biochemical Analysis and Visualization

Beyond the sparkle, other properties of diamond havegained increasing attention in the past few decades amongchemists and physicists. Color centers-impurities formed byone or a few foreign atoms or vacancies in the diamondlattice-are one reason for this. While pure diamond istransparent, the presence of color centers causes changes incoloration. Color centers introduce additional electronic statesin the wide band gap of diamond, giving rise to transitions thatabsorb and emit light in the visible spectrum

Quantum monitoring of cellular metabolic activities in single mitochondria

Free radicals play a vital role in all kinds of biological processes including immune responses. However, free radicals have short lifetimes and are highly reactive, making them difficult to measure using current methods. Here, we demonstrate that relaxometry measurement, or T1, inherited from the field of diamond magnetometry can be used to detect free radicals in living cells with subcellular resolution. This quantum sensing technique is based on defects in diamond, which convert a magnetic signal into an optical signal, allowing nanoscale magnetic resonance measurements. We functionalized fluorescent nanodiamonds (FNDs) to target single mitochondria within macrophage cells to detect the metabolic activity. In addition, we performed measurements on single isolated mitochondria. We were able to detect free radicals generated by individual mitochondria in either living cells or isolated mitochondria after stimulation or inhibition

High Temperature Treatment of Diamond Particles Toward Enhancement of Their Quantum Properties

Fluorescence of the negatively charged nitrogen-vacancy (NV-) center of diamond is sensitive to external electromagnetic fields, lattice strain, and temperature due to the unique triplet configuration of its spin states. Their use in particulate diamond allows for the possibility of localized sensing and magnetic-contrast-based differential imaging in complex environments with high fluorescent background. However, current methods of NV(-)production in diamond particles are accompanied by the formation of a large number of parasitic defects and lattice distortions resulting in deterioration of the NV(-)performance. Therefore, there are significant efforts to improve the quantum properties of diamond particles to advance the field. Recently it was shown that rapid thermal annealing (RTA) at temperatures much exceeding the standard temperatures used for NV(-)production can efficiently eliminate parasitic paramagnetic impurities and, as a result, by an order of magnitude improve the degree of hyperpolarization of(13)C via polarization transfer from optically polarized NV(-)centers in micron-sized particles. Here, we demonstrate that RTA also improves the maximum achievable magnetic modulation of NV(-)fluorescence in micron-sized diamond by about 4x over conventionally produced diamond particles endowed with NV-. This advancement can continue to bridge the pathway toward developing nano-sized diamond with improved qualities for quantum sensing and imaging

The interaction of fluorescent nanodiamond probes with cellular media

Fluorescent nanodiamonds (FNDs) are promising tools to image cells, bioanalytes and physical quantities such as temperature, pressure, and electric or magnetic fields with nanometer resolution. To exploit their potential for intracellular applications, the FNDs have to be brought into contact with cell culture media. The interactions between the medium and the diamonds crucially influence sensitivity as well as the ability to enter cells. The authors demonstrate that certain proteins and salts spontaneously adhere to the FNDs and may cause aggregation. This is a first investigation on the fundamental questions on how (a) FNDs interact with the medium, and (b) which proteins and salts are being attracted. A differentiation between strongly binding and weakly binding proteins is made. Not all proteins participate in the formation of FND aggregates. Surprisingly, some main components in the medium seem to play no role in aggregation. Simple strategies to prevent aggregation are discussed. These include adding the proteins, which are naturally present in the cell culture to the diamonds first and then inserting them in the full medium. Graphical abstractSchematic of the interaction of nanodiamonds with cell culture medium. Certain proteins and salts adhere to the diamond surface and lead to aggregation or to formation of a protein corona

Investigation of Surface Magnetic Noise by Shallow Spins in Diamond

We present measurements of spin relaxation times (T1, T1ρ, T2) on very shallow (≲5  nm) nitrogen-vacancy centers in high-purity diamond single crystals. We find a reduction of spin relaxation times up to 30 times compared to bulk values, indicating the presence of ubiquitous magnetic impurities associated with the surface. Our measurements yield a density of 0.01–0.1μB/nm2 and a characteristic correlation time of 0.28(3) ns of surface states, with little variation between samples and chemical surface terminations. A low temperature measurement further confirms that fluctuations are thermally activated. The data support the atomistic picture where impurities are associated with the top carbon layers, and not with terminating surface atoms or adsorbate molecules. The low spin density implies that the presence of A single surface impurity is sufficient to cause spin relaxation of a shallow nitrogen-vacancy center