High-pressure High-temperature Nanodiamonds Research Articles

Hydrogenation of HPHT nanodiamonds and their nanoscale interaction with chitosan

Hydrogenation of the surface can provide specific and unique properties to nanodiamonds. In this study, a series of high-pressure high-temperature nanodiamonds (HPHT NDs) with varying levels of hydrogenation and sp2 carbon content is prepared and characterized in terms of optical properties, structure, surface chemistry, particle size distribution, and zeta potential. The higher the surface sp2-C content and level of hydrogenation the better dispersibility in acidic to neutral pH and higher isoelectric points are achieved. We further evaluated the interaction of hydrogenated HPHT NDs with chitosan by infrared spectroscopy and atomic force microscopy. We have found that chitosan is electrostatically attracted to the hydrogenated HPHT NDs, it improves the dispersibility of the HPHT NDs with a lower level of hydrogenation, and it provides colloidal stability in the broad pH range 2–11 to all hydrogenated HPHT NDs. Finally, we demonstrate that chitosan coating enables the decoration of hydrogenated HPHT NDs by silver nanoparticles.

Fluorescent HPHT nanodiamonds have disk- and rod-like shapes

Fluorescent nanodiamonds (FNDs) containing nitrogen-vacancy (NV) centers can be used as nanoscale sensors for temperature and electromagnetic fields and find increasing application in many areas of science and technology from biology to quantum metrology. Decreasing the separation between the NV centers and their sensing target often enhances the measurement sensitivity. FND shape strongly affects this distance from NV centers to the particle surface and therefore properties such as brightness and fluorescence spectrum, and can limit sensor applications. Here, we demonstrate that FNDs made from high-pressure high-temperature (HPHT) diamond have predominantly disk-like shapes. Using single-particle atomic force microscopy in combination with ensemble X-ray and light scattering techniques, we show that a typical FND in the 50–150 nm size range has an aspect ratio of three i.e. is three times thinner (e.g. in z) than it is wide (e.g. in the x-y plane). This high aspect ratio of FNDs is important for many quantum sensing measurements as it will enable enhanced sensitivities compared to spherical or other isotropic particle geometries. We investigate FND shape, fluorescence properties, T1 spin relaxation time and T1 fluorescence contrast as functions of particle size and discuss the implications of FND particle shape on quantum sensing applications.

Femtosecond Optical Nonlinearity of Nanodiamond Suspensions

High pressure-high temperature (HP-HT) nanodiamonds and detonation nanodiamonds have unique optical properties and are promising materials for various applications in photonics. In this work, for the first time, comparative studies of the nonlinear optical properties of aqueous suspensions of HP-HT and detonation nanodiamonds under femtosecond laser excitation are performed. Using the z-scan technique, it was found that for the same laser pulse parameters HP-HT nanodiamonds exhibited optical limiting due to two-photon absorption while detonation nanodiamonds exhibited saturable absorption accompanied by short-term optical bleaching, revealing the different electronic-gap structures of the two types of nanodiamonds. The saturable absorption properties of detonation nanodiamonds are characterized by determining the saturable and non-saturable absorption coefficients, the saturation intensity, and the ratio of saturable to non-saturable losses. The nonlinear absorption in HP-HT nanodiamonds is described with the nonlinear absorption coefficient that decreases with decreasing concentration of nanoparticles linearly. The results obtained show the possibility of using aqueous suspensions of nanodiamonds for saturable absorption and optical limiting applications.

Low-Power Laser Graphitization of High Pressure—High Temperature Nanodiamond Films

Laser-induced graphitization of 100 nm monocrystals of diamond particles synthesized by high-pressure high-temperature (HP-HT) methods is not typically observed. The current study demonstrates the graphitization of 150 nm HP-HT nanodiamond particles in ca. 20-μm-thick thin films formed on a glass substrate when the intensity of a focused 633 nm He-Ne laser exceeds a threshold of ~ 33 kW/cm2. Graphitization is accompanied by green luminescence. The structure and morphology of the samples were investigated before and after laser excitation while using X-ray diffraction (XRD), Raman spectroscopy, atomic force (AFM), and scanning electron microscopy (SEM). These observations are explained by photoionization of [Ni-N]- and [N]-centers, leading to the excitation of electrons to the conduction band of the HP-HT nanodiamond films and an increase of the local temperature of the sample, causing the transformation of sp3 HP-HT nanodiamonds to sp2-carbon.

Laser modification of high-pressure high-temperature nanodiamonds

Micro-thin semitransparent films of purified high pressure high temperature nanodiamonds were produced on a glass substrate. A focused 632.8 nm He-Ne laser irradiation is shown to cause an emission of light in the green region of the optical spectrum accompanied with laser-induced blackening of the obtained films. Possible mechanisms of the observed phenomenon are discussed.

Effect of Surface Chemistry on the Fluorescence of Detonation Nanodiamonds.

Detonation nanodiamonds (DNDs) have unique physical and chemical properties that make them invaluable in many applications. However, DNDs are generally assumed to show weak fluorescence, if any, unless chemically modified with organic molecules. We demonstrate that detonation nanodiamonds exhibit significant and excitation-wavelength-dependent fluorescence from the visible to the near-infrared spectral region above 800 nm, even without the engraftment of organic molecules to their surfaces. We show that this fluorescence depends on the surface functionality of the DND particles. The investigated functionalized DNDs, produced from the same purified DND as well as the as-received polyfunctional starting material, are hydrogen, hydroxyl, carboxyl, ethylenediamine, and octadecylamine-terminated. All DNDs are investigated in solution and on a silicon wafer substrate and compared to fluorescent high-pressure high-temperature nanodiamonds. The brightest fluorescence is observed from octadecylamine-functionalized particles and is more than 100 times brighter than the least fluorescent particles, carboxylated DNDs. The majority of photons emitted by all particle types likely originates from non-diamond carbon. However, we locally find bright and photostable fluorescence from nitrogen-vacancy centers in diamond in hydrogenated, hydroxylated, and carboxylated detonation nanodiamonds. Our results contribute to understanding the effects of surface chemistry on the fluorescence of DNDs and enable the exploration of the fluorescent properties of DNDs for applications in theranostics as nontoxic fluorescent labels, sensors, nanoscale tracers, and many others where chemically stable and brightly fluorescent nanoparticles with tailorable surface chemistry are needed.

Uptake and intracellular accumulation of diamond nanoparticles - a metabolic and cytotoxic study.

Diamond nanoparticles, known as nanodiamonds (NDs), possess several medically significant properties. Having a tailorable and easily accessible surface gives them great potential for use in sensing and imaging applications and as a component of cell growth scaffolds. In this work we investigate in vitro interactions of human osteoblast-like SAOS-2 cells with four different groups of NDs, namely high-pressure high-temperature (HPHT) NDs (diameter 18–210 nm, oxygen-terminated), photoluminescent HPHT NDs (diameter 40 nm, oxygen-terminated), detonation NDs (diameter 5 nm, H-terminated), and the same detonation NDs further oxidized by annealing at 450 °C. The influence of the NDs on cell viability and cell count was measured by the mitochondrial metabolic activity test and by counting cells with stained nuclei. The interaction of NDs with cells was monitored by phase contrast live-cell imaging in real time. For both types of oxygen-terminated HPHT NDs, the cell viability and the cell number remained almost the same for concentrations up to 100 µg/mL within the whole range of ND diameters tested. The uptake of hydrogen-terminated detonation NDs caused the viability and the cell number to decrease by 80–85%. The oxidation of the NDs hindered the decrease, but on day 7, a further decrease was observed. While the O-terminated NDs showed mechanical obstruction of cells by agglomerates preventing cell adhesion, migration and division, the H-terminated detonation NDs exhibited rapid penetration into the cells from the beginning of the cultivation period, and also rapid cell congestion and a rapid reduction in viability. These findings are discussed with reference to relevant properties of NDs such as surface chemical bonds, zeta potential and nanoparticle types.

Carboxylated nanodiamonds can be used as negative reference in in vitro nanogenotoxicity studies.

Nanodiamonds (NDs) are promising nanomaterials for biomedical applications. However, a few studies highlighted an in vitro genotoxic activity for detonation NDs, which was not evidenced in one of our previous work quantifying γ-H2Ax after 20 and 100 nm high-pressure high-temperature ND exposures of several cell lines. To confirm these results, in the present work, we investigated the genotoxicity of the same 20 and 100 nm NDs and added intermediate-sized NDs of 50 nm. Conventional in vitro genotoxicity tests were used, i.e., the in vitro micronucleus and comet assays that are recommended by the French National Agency for Medicines and Health Products Safety for the toxicological evaluation of nanomedicines. In vitro micronucleus and in vitro comet assays (standard and hOGG1-modified) were therefore performed in two human cell lines, the bronchial epithelial 16HBE14o- cells and the colon carcinoma T84 cells. Our results did not show any genotoxic activity, whatever the test, the cell line or the size of carboxylated NDs. Even though these in vitro results should be confirmed in vivo, they reinforce the potential interest of carboxylated NDs for biomedical applications or even as a negative reference nanoparticle in nanotoxicology. Copyright © 2017 John Wiley & Sons, Ltd.

Bright and photostable nitrogen-vacancy fluorescence from unprocessed detonation nanodiamond.

Bright and photostable fluorescence from nitrogen-vacancy (NV) centers is demonstrated in unprocessed detonation nanodiamond particle aggregates. The optical properties of these particles is analyzed using confocal fluorescence microscopy and spectroscopy, time resolved fluorescence decay measurements, and optically detected magnetic resonance experiments. Two particle populations with distinct optical properties are identified and compared to high-pressure high-temperature (HPHT) fluorescent nanodiamonds. We find that the brightness of one detonation nanodiamond particle population is on the same order as that of highly processed fluorescent 100 nm HPHT nanodiamonds. Our results may open the path to a simple and up-scalable route for the production of fluorescent NV nanodiamonds for use in bioimaging applications.

Size and Purity Control of HPHT Nanodiamonds down to 1 nm.

High-pressure high-temperature (HPHT) nanodiamonds originate from grinding of diamond microcrystals obtained by HPHT synthesis. Here we report on a simple two-step approach to obtain as small as 1.1 nm HPHT nanodiamonds of excellent purity and crystallinity, which are among the smallest artificially prepared nanodiamonds ever shown and characterized. Moreover we provide experimental evidence of diamond stability down to 1 nm. Controlled annealing at 450 °C in air leads to efficient purification from the nondiamond carbon (shells and dots), as evidenced by X-ray photoelectron spectroscopy, Raman spectroscopy, photoluminescence spectroscopy, and scanning transmission electron microscopy. Annealing at 500 °C promotes, besides of purification, also size reduction of nanodiamonds down to ∼1 nm. Comparably short (1 h) centrifugation of the nanodiamonds aqueous colloidal solution ensures separation of the sub-10 nm fraction. Calculations show that an asymmetry of Raman diamond peak of sub-10 nm HPHT nanodiamonds can be well explained by modified phonon confinement model when the actual particle size distribution is taken into account. In contrast, larger Raman peak asymmetry commonly observed in Raman spectra of detonation nanodiamonds is mainly attributed to defects rather than to the phonon confinement. Thus, the obtained characteristics reflect high material quality including nanoscale effects in sub-10 nm HPHT nanodiamonds prepared by the presented method.

Luminescent Diamond Nanoparticles: Physical, Chemical and Biological Aspects of the Phenomenon.

Biosensors based on nanodiamonds are able to penetrate through the cell membrane in a targeted manner and probe changes in real-time in the inner cellular space. In this work we performed exclusive theoretical and experimental study of nanodiamond particles adjusted for application in optically-traceable intracellular nanodiamond sensors. Theoretical and experimental study of specific optical properties of high-pressure high-temperature nanodiamonds containing NV- and NV0 centres were performed. The results are supported by theoretical modeling. The final result of this study was detection of luminescence ND in living cells and in vivo application od luminiscence NDs in chicken embryo, showing the detectability of luminescence ND using a standard confocal microscope. On the level of in cells selectivity numerous clusters of ND particles were present within the cytoplasm and at the same time no particles were absent in the nucleus-ND particles can be used as imaging or delivery system for specific cell parts targeting. From our study we can say that biosensors based on nanodiamonds (NDs) are able to penetrate through the cell membrane in a targeted manner and probe changes in the inner cellular space.

Magnetical and Optical Properties of Nanodiamonds Can Be Tuned by Particles Surface Chemistry: Theoretical and Experimental Study

In this paper, new steps toward a better understanding and utilization of high-pressure high-temperature nanodiamonds (NDs) containing nitrogen-vacancy (NV) centers have been taken. NV–-related long-term luminescence of oxygenated particles increased in comparison to plasma hydrogenated NDs’ NV– luminescence. The optically detected NV– electron spin resonance process can be also significantly affected by ND termination. For H-terminated ND particles the NV– to NV0 conversion energy is lower than the NV– excitation energy, so that the delocalized triplet electrons can be more easily released from the original positions and drawn to the electron-attracting localities in the material. The final result of this study was application of luminescent NDs in cells, showing the detectability of luminescent NDs in a standard confocal microscope and ND subcellular distribution in the cells by TEM.

Precise estimation of HPHT nanodiamond size distribution based on transmission electron microscopy image analysis

Abstract Fluorescent nanodiamonds (NDs) are extremely promising fluorescent probes and sensors in experimental biology. For these applications, NDs obtained from high-pressure, high-temperature (HPHT) synthesis are used. Commercial HPHT NDs are polydisperse and of irregular shape. In this work, we used image analysis of transmission electron microscopy (TEM) micrographs to determine the actual size distribution of an HPHT ND sample with high precision. We developed novel TEM sample preparation procedure, which includes hydrophilization of a carbon-coated TEM grid by UV/ozone treatment and subsequent charge reversal and charge-controlled adsorption of nanoparticles. This method results in NDs spread evenly on the grid and radically improves the quality of TEM samples. Image analysis of TEM micrographs of commercial NDs revealed an unexpectedly high abundance of sub-10 nm NDs in the sample. This method can also be used for preparing TEM samples of other negatively charged nanoparticles, such as citrate-stabilized gold.

Super-resolving single nitrogen vacancy centers within single nanodiamonds using a localization microscope

In this paper, we show super-resolving single nitrogen vacancy (NV) centers with a sub-20 nanometer resolution in a wide-field localization microscope based on the discovery of photoluminescence blinking in high-pressure high-temperature nanodiamonds (NDs). The photon statistics reveals that NDs containing not only single but also multiple NV centers show photoluminescence blinking. The combination of an atomic force microscope and an optical localization microscope built on the blinking feature enables the optically resolved two NV centers within single NDs for the first time. Our method establishes new avenues for studying nanoscale photon dynamics associated with single NV centers within NDs together with ND-based ultra-sensitive bioimaging devices.

High-speed micro-energy switching

Fluorescent nanodiamonds (NDs) are extremely promising fluorescent probes and sensors in experimental biology. For these applications, NDs obtained from high-pressure, high-temperature (HPHT) synthesis are used. Commercial HPHT NDs are polydisperse and of irregular shape. In this work, we used image analysis of transmission electron microscopy (TEM) micrographs to determine the actual size distribution of an HPHT ND sample with high precision. We developed novel TEM sample preparation procedure, which includes hydrophilization of a carbon-coated TEM grid by UV/ozone treatment and subsequent charge reversal and charge-controlled adsorption of nanoparticles. This method results in NDs spread evenly on the grid and radically improves the quality of TEM samples. Image analysis of TEM micrographs of commercial NDs revealed an unexpectedly high abundance of sub-10 nm NDs in the sample. This method can also be used for preparing TEM samples of other negatively charged nanoparticles, such as citrate-stabilized gold.