In recent decades, nanodiamonds (NDs) have earned increasing interest in a wide variety of research fields, thanks to their excellent mechanical, chemical, and optical properties, together with the possibility of easily tuning their surface chemistry for the desired purpose. According to the application context, it is essential to acquire an extensive understanding of their interaction with water in terms of hydrophilicity, environmental adsorption, stability in solution, and impact on electrical properties. In this paper, we report on a systematic study of the effects of reducing and oxidizing thermal processes on ND surface water adsorption. Both detonation and milled NDs were analyzed by combining different techniques. Temperature-dependent infrared spectroscopy was employed to study ND surface chemistry and water adsorption, while dynamic light scattering allowed the evaluation of their behavior in solution. The influence of water adsorption on their electrical properties was also investigated and correlated with structural and optical information obtained via Raman/photoluminescence spectroscopy. In general, higher oxygen-containing surfaces exhibited higher hydrophilicity, better stability in solution, and higher electrical conduction, although for the latter the surface graphitic contribution was also crucial. Our results provide in-depth information on the hydrophilicity of NDs in relation to their surface chemical and physical properties, by also evaluating the impacts on their aggregation and electrical conductance.
Sensing based on Nitrogen‐Vacancy (NV) centers in nanodiamonds (NDs) represents a potentially groundbreaking technology with broad applications. Nevertheless, the optimization of their quantum‐optical properties is still a challenging issue. The present work aims at enhancing and controlling NV centers optical properties in NDs by combining their surface chemistry tuning and proton beam irradiation. Systematic thermal oxidations are carried out to study the evolution of surface chemical groups (IR spectroscopy), as well as their influence on optical properties (photoluminescence spectroscopy, PL decay measurements). Proton irradiation is performed by exploring a wide range of fluences (1014 – 1017 cm−2) in order to precisely control the amount of NV centers, thus defining the conditions that maximize their creation and emission intensity. In addition, NV centers charge state control is achieved by assessing NV−/NV0 ratio upon different surface termination tuning and NV centers amount. Finally, a novel predictive mathematical model is developed, allowing for the evaluation of the efficiencies of the formation of both NV− and NV0. Although the model is tested in the specific case study with proton irradiated NDs, it offers a broad applicability, thus representing a key landmark in the prediction of the outcome of ion‐beam‐based color centers generation in diamond.
Novel approach for the functionalization of nanodiamonds with Hyaluronic Acid is proposed, utilizing non-covalent anchoring. NDs exhibit improved properties including increased internalization in human adenocarcinoma cells overexpressing CD44 receptor.
Single-photon emitters (SPEs) within wide-bandgap materials represent an appealing platform for the development of single-photon sources operating at room temperatures. Group III-nitrides have previously been shown to host efficient SPEs, which are attributed to deep energy levels within the large bandgap of the material, in a configuration that is similar to extensively investigated color centers in diamond. Anti-bunched emission from defect centers within gallium nitride and aluminum nitride (AlN) have been recently demonstrated. While such emitters are particularly interesting due to the compatibility of III-nitrides with cleanroom processes, the nature of such defects and the optimal conditions for forming them are not fully understood. Here, we investigate Al implantation on a commercial AlN epilayer through subsequent steps of thermal annealing and confocal microscopy measurements. We observe a fluence-dependent increase in the density of the emitters, resulting in the creation of ensembles at the maximum implantation fluence. Annealing at 600 °C results in the optimal yield in SPEs formation at the maximum fluence, while a significant reduction in SPE density is observed at lower fluences. These findings suggest that the mechanism of vacancy formation plays a key role in the creation of the emitters and open enticing perspectives in the defect engineering of SPEs in solid state.
Nanoparticles are being increasingly studied to enhance radiation effects. Among them, nanodiamonds (NDs) are taken into great consideration due to their low toxicity, inertness, chemical stability, and the possibility of surface functionalization. The objective of this study is to explore the influence of the chemical/physical properties of NDs on cellular radiosensitivity to combined treatments with radiation beams of different energies. DAOY, a human radioresistant medulloblastoma cell line was treated with NDs—differing for surface modifications [hydrogenated (H-NDs) and oxidized (OX-NDs)], size, and concentration—and analysed for (i) ND internalization and intracellular localization, (ii) clonogenic survival after combined treatment with different radiation beam energies and (iii) DNA damage and apoptosis, to explore the nature of ND–radiation biological interactions. Results show that chemical/physical characteristics of NDs are crucial in determining cell toxicity, with hydrogenated NDs (H-NDs) decreasing either cellular viability when administered alone, or cell survival when combined with radiation, depending on ND size and concentration, while OX-NDs do not. Also, irradiation at high energy (γ-rays at 1.25 MeV), in combination with H-NDs, is more efficient in eliciting radiosensitisation when compared to irradiation at lower energy (X-rays at 250 kVp). Finally, the molecular mechanisms of ND radiosensitisation was addressed, demonstrating that cell killing is mediated by the induction of Caspase-3-dependent apoptosis that is independent to DNA damage. Identifying the optimal combination of ND characteristics and radiation energy has the potential to offer a promising therapeutic strategy for tackling radioresistant cancers using H-NDs in conjunction with high-energy radiation.