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

A 50 l CYGNO prototype overground characterization

The nature of dark matter is still unknown and an experimental program to look for dark matter particles in our Galaxy should extend its sensitivity to light particles in the GeV mass range and exploit the directional information of the DM particle motion (Vahsen et al. in CYGNUS: feasibility of a nuclear recoil observatory with directional sensitivity to dark matter and neutrinos, arXiv:2008.12587, 2020). The CYGNO project is studying a gaseous time projection chamber operated at atmospheric pressure with a Gas Electron Multiplier (Sauli in Nucl Instrum Meth A 386:531, https://doi.org/10.1016/S0168-9002(96)01172-2, 1997) amplification and with an optical readout as a promising technology for light dark matter and directional searches. In this paper we describe the operation of a 50 l prototype named LIME (Long Imaging ModulE) in an overground location at Laboratori Nazionali di Frascati (LNF) of INFN. This prototype employs the technology under study for the 1 cubic meter CYGNO demonstrator to be installed at the Laboratori Nazionali del Gran Sasso (LNGS) (Amaro et al. in Instruments 2022, 6(1), https://www.mdpi.com/2410-390X/6/1/6, 2022). We report the characterization of LIME with photon sources in the energy range from few keV to several tens of keV to understand the performance of the energy reconstruction of the emitted electron. We achieved a low energy threshold of few keV and an energy resolution over the whole energy range of 10–20%, while operating the detector for several weeks continuously with very high operational efficiency. The energy spectrum of the reconstructed electrons is then reported and will be the basis to identify radio-contaminants of the LIME materials to be removed for future CYGNO detectors

Explosive Fragmentation of Luminescent Diamond Particles

Development of efficient and cost-effective mass-production techniques for size reduction of high-pressure, high-temperature (HPHT) diamonds with sizes from tens to hundreds of micrometers remains one of the primary goals towards commercial production of fluorescent submicron and nanodiamond (fND). fNDs offer great advantages for many applications, especially in labelling, tracing, and biomedical imaging, owing to their brightness, exceptional photostability, mechanical robustness and intrinsic biocompatibility. This study proposes a novel processing method utilizing explosive fragmentation that can potentially be used for the fabrication of submicron to nanoscale size fluorescent diamond particles. In the proposed method, synthetic HPHT 20 µm and 150 µm microcystalline diamond particles containing color centers are rapidly fragmented in conditions of high explosive detonation. X-ray diffraction and Raman spectroscopy show that the detonation fragmented diamond particles consist of good quality submicron diamonds of ~420-800 nm in size, while fluorescence spectroscopy shows photoluminescence spectra with noticeable changes for large (150 µm) starting microcrystalline diamond particles, and no significant changes in photoluminescence properties for smaller (20 µm) starting microcrystalline diamond particles. The proposed detonation method shows potential as an efficient, cost effective, and industrially scalable alternative to milling for the fragmentation of fluorescent diamond microcrystals into submicron-to-nano-size domain

Quantitative Determination of Ligand Densities on Nanomaterials by X‑ray Photoelectron Spectroscopy

X-ray photoelectron spectroscopy (XPS) is a nearly universal method for quantitative characterization of both organic and inorganic layers on surfaces. When applied to nanoparticles, the analysis is complicated by the strong curvature of the surface and by the fact that the electron attenuation length can be comparable to the diameter of the nanoparticles, making it necessary to explicitly include the shape of the nanoparticle to achieve quantitative analysis. We describe a combined experimental and computational analysis of XPS data for molecular ligands on gold nanoparticles. The analysis includes scattering in both Au core and organic shells and is valid even for nanoparticles having diameters comparable to the electron attenuation length (EAL). To test this model, we show experimentally how varying particle diameter from 1.3 to 6.3 nm leads to a change in the measured <i>A</i>_C/<i>A</i>_Au peak area ratio, changing by a factor of 15. By analyzing the data in a simple computational model, we demonstrate that ligand densities can be obtained, and, moreover, that the actual ligand densities for these nanoparticles are a constant value of 3.9 ± 0.2 molecules nm^–2. This model can be easily extended to a wide range of core–shell nanoparticles, providing a simple pathway to extend XPS quantitative analysis to a broader range of nanomaterials

Natural Organic Matter Concentration Impacts the Interaction of Functionalized Diamond Nanoparticles with Model and Actual Bacterial Membranes

Changes to nanoparticle surface charge, colloidal stability, and hydrodynamic properties induced by interaction with natural organic matter (NOM) warrant consideration in assessing the potential for these materials to adversely impact organisms in the environment. Here, we show that acquisition of a coating, or “corona”, of NOM alters the hydrodynamic and electrokinetic properties of diamond nanoparticles (DNPs) functionalized with the polycation poly­(allylamine HCl) in a manner that depends on the NOM-to-DNP concentration ratio. The NOM-induced changes to DNP properties alter subsequent interactions with model biological membranes and the Gram-negative bacterium <i>Shewanella oneidensis</i> MR-1. Suwannee River NOM induces changes to DNP hydrodynamic diameter and apparent ζ-potential in a concentration-dependent manner. At low NOM-to-DNP ratios, DNPs aggregate to a limited extent but retain a positive ζ-potential apparently due to nonuniform adsorption of NOM molecules leading to attractive electrostatic interactions between oppositely charged regions on adjacent DNP surfaces. Diamond nanoparticles at low NOM-to-DNP ratios attach to model membranes to a larger extent than in the absence of NOM (including those incorporating lipopolysaccharide, a major bacterial outer membrane component) and induce a comparable degree of membrane damage and toxicity to <i>S. oneidensis</i>. At higher NOM-to-DNP ratios, DNP charge is reversed, and DNP aggregates remain stable in suspension. This charge reversal eliminates DNP attachment to model membranes containing the highest LPS contents studied due to electrostatic repulsion and abolishes membrane damage to <i>S. oneidensis</i>. Our results demonstrate that the effects of NOM coronas on nanoparticle properties and interactions with biological surfaces can depend on the relative amounts of NOM and nanoparticles

A Citric Acid-Derived Ligand for Modular Functionalization of Metal Oxide Surfaces via “Click” Chemistry

Citric acid is a widely used surface-modifying ligand for growth and processing of a variety of nanoparticles; however, the inability to easily prepare derivatives of this molecule has restricted the development of versatile chemistries for nanoparticle surface functionalization. Here, we report the design and synthesis of a citric acid derivative bearing an alkyne group and demonstrate that this molecule provides the ability to achieve stable, multidentate carboxylate binding to metal oxide nanoparticles, while also enabling subsequent multistep chemistry via the Cu­(I)-catalyzed azide–alkyne cycloaddition (CuAAC) reaction. The broad utility of this strategy for the modular functionalization of metal oxide surfaces was demonstrated by its application in the CuAAC modification of ZnO, Fe₂O₃, TiO₂, and WO₃ nanoparticles

Quantification of Free Polyelectrolytes Present in Colloidal Suspension, Revealing a Source of Toxic Responses for Polyelectrolyte-Wrapped Gold Nanoparticles

Polyelectrolyte (PE) wrapping of colloidal nanoparticles (NPs) is a standard method to control NP surface chemistry and charge. Because excess polyelectrolytes are usually employed in the surface modification process, it is critical to evaluate different purification strategies to obtain a clean final product and thus avoid ambiguities in the source of effects on biological systems. In this work, 4 nm diameter gold nanoparticles (AuNPs) were wrapped with 15 kDa poly­(allylamine hydrochloride) (PAH), and three purification strategies were applied: (a) diafiltration or either (b) one round or (c) two rounds of centrifugation. The bacterial toxicity of each of these three PAH-AuNP samples was evaluated for the bacterium <i>Shewanella oneidensis</i> MR-1 and is quantitatively correlated with the amount of unbound PAH molecules in the AuNP suspensions, as judged by X-ray photoelectron spectroscopy, nuclear magnetic resonance experiments and quantification using fluorescent assay. Dialysis experiments show that, for a 15 kDa polyelectrolyte, a 50 kDa dialysis membrane is not sufficient to remove all PAH polymers. Together, these data showcase the importance of choosing a proper postsynthesis purification method for polyelectrolyte-wrapped NPs and reveal that apparent toxicity results may be due to unintended free wrapping agents such as polyelectrolytes