The reversible piezochromic luminescence behavior of carbon dots under a cycle of loading/unloading pressure.

Carbon dots (CDs) have gained intensive interest owing to their small size, unique structure, excellent photoluminescence (PL) properties and broad applications. In particular, pressure-triggered irreversible piezochromic behavior of fluorescent CDs was previously reported and attributed to the sp2-sp3 transition in the carbon core or aggregation-induced emission under high pressure. Here, we report the reversible piezochromic behavior of microwave-heating synthesized CDs (named M-CDs) using ethylenediamine and aspartic acid as precursors. Under a loading/unloading cycle, the PL intensity of M-CDs decreased continuously with the pressure increasing from 101 kPa up to 20 GPa, and the maximum emission of M-CDs at 101 kPa (λmax = 550 nm) was slightly blue-shifted to 541 nm at 20 GPa, but when the pressure was released from 20 GPa to normal environmental conditions, both the emission wavelength and the PL intensity of M-CDs returned to their initial states at 101 kPa. The control sample was also synthesized using the same precursors but through a hydrothermal method and thus named H-CDs. Both H-CDs and M-CDs have similar particle sizes, morphology and excitation-dependent PL behavior under 101 kPa; however, H-CDs showed a typical piezochromic behavior with the emission blue-shifted from 518 to 491 nm when the pressure was increased from 101 kPa to 0.97 GPa, and then red-shifted from 491 to 530 nm when the pressure was increased up to 10.53 GPa. This irreversible behavior of H-CDs was accompanied by a 2-fold enhancement of their PL intensity after releasing the pressure. The remarkable different behaviors of M-CDs and H-CDs under a loading/unloading cycle are caused by different interior structures of M-CDs and H-CDs due to different synthetic processes, which is worthy of further research.

Isolated Spin-7/2 Species of Gadolinium (III) Chelate Complexes on the Surface of 5-nm Diamond Particles.

The magnetic characteristics of a system of triply charged gadolinium ions Gd3+ chelated with carboxyls on the surface of detonation nanodiamond (DND) particles have been studied. Gd3+ ions demonstrate almost perfect spin (S = 7/2) paramagnetism with negligible antiferromagnetic interaction between spins (Weiss temperature about -0.35 K) for a wide range of concentrations up to ~18 ions per 5 nm particle. The study of the concentration dependence of the electron paramagnetic resonance signal for DND intrinsic defects with spin ½ (g = 2.0027) shows that Gd3+ ions are located on average at a distance of no more than 1.4 nm from shallow subsurface defects with spin 1/2. At the same time, they are located (according to density functional theory calculations) at a distance of about or at least 0.28 nm from the particle surface. Magnetic studies also confirm the isolated nature of the gadolinium chelate complexes on the surface of DND particles. DND particles turn out to be an optimal carrier for high-spin 4f- ions (gadolinium) in a highly concentrated isolated state. This property makes DND-Gd particles a candidate for the role of a contrast agent for magnetic resonance imaging.

A comprehensive model of nitrogen-free ordered carbon quantum dots.

We propose and demonstrate a novel range of models to accurately determine the optical properties of nitrogen-free carbon quantum dots (CQDs) with ordered graphene layered structures. We confirm the results of our models against the full range of experimental results for CQDs available from an extensive review of the literature. The models can be equally applied to CQDs with varied sizes and with different oxygen contents in the basal planes of the constituent graphenic sheets. We demonstrate that the experimentally observed blue fluorescent emission of nitrogen-free CQDs can be associated with either small oxidised areas on the periphery of the graphenic sheets, or with sub-nanometre non-functionalised islands of sp2-hybridised carbon with high symmetry confined in the centres of oxidised graphene sheets. Larger and/or less symmetric non-functionalised regions in the centre of functionalised graphene sheet are found to be sources of green and even red fluorescent emission from nitrogen-free CQDs. We also demonstrate an approach to simplify the modelling of the discussed sp2-islands by substitution with equivalent strained polycyclic aromatic hydrocarbons. Additionally, we show that the bandgaps (and photoluminescence) of CQDs are not dependent on either out-of-plane corrugation of the graphene sheet or the spacing between sp2-islands. Advantageously, our proposed models show that there is no need to involve light-emitting polycyclic aromatic molecules (nanographenes) with arbitrary structures grafted to the particle periphery to explain the plethora of optical phenomena observed for CQDs across the full range of experimental works.

Rational Synthesis of Solid-State Ultraviolet B Emitting Carbon Dots via Acetic Acid-Promoted Fractions of sp3 Bonding Strategy.

Carbon dots (CDs) have received tremendous attention for their excellent photoluminescence (PL) properties. However, it remains a great challenge to obtain CDs with ultraviolet (UV, 200-400 nm) emission in solid state, which requires strict control of the CDs structure and overcoming the aggregation-caused quenching (ACQ). Herein, a new sp3 compartmentalization strategy is developed to meet these requirements, by employing acetic acid to promote fractions of sp3 bonding during the synthesis of CDs. It markedly decreases the size of sp2 conjugating units in the CDs, and shifts PL emission to the ultraviolet B (UVB) region (λmax  = 308 nm). Moreover, sp2 domains are well spatially compartmentalized by sp3 domains and the ACQ effect is minimized, enabling the high quantum yield in solid state (20.2%, λex  = 265 nm) with a narrow bandwidth of 24 nm and environmental robustness. The solid-state UVB emissive CDs are highly desired for application in photonic devices. Hence, a demo of UVB light-emitting diodes is fabricated for plant lighting, leading to a 29% increase of ascorbic acid content in the basil. Overall, a rational and efficient way to construct solid UVB-CDs phosphors for wide applications is provided.

High-Quality Green-Emitting Nanodiamonds Fabricated by HPHT Sintering of Polycrystalline Shockwave Diamonds.

We demonstrate a high-pressure, high-temperature sintering technique to form nitrogen-vacancy-nitrogen centres in nanodiamonds. Polycrystalline diamond nanoparticle precursors, with mean size of 25 nm, are produced by the shock wave from an explosion. These nanoparticles are sintered in the presence of ethanol, at a pressure of 7 GPa and temperature of 1300 °C, to produce substantially larger (3-4 times) diamond crystallites. The recorded spectral properties demonstrate the improved crystalline quality. The types of defects present are also observed to change; the characteristic spectral features of nitrogen-vacancy and silicon-vacancy centres present for the precursor material disappear. Two new characteristic features appear: (1) paramagnetic substitutional nitrogen (P1 centres with spin ½) with an electron paramagnetic resonance characteristic triplet hyperfine structure due to the I = 1 magnetic moment of the nitrogen nuclear spin and (2) the green spectral photoluminescence signature of the nitrogen-vacancy-nitrogen centres. This production method is a strong alternative to conventional high-energy particle beam irradiation. It can be used to easily produce purely green fluorescing nanodiamonds with advantageous properties for optical biolabelling applications.

Photoluminescence from NV- Centres in 5 nm Detonation Nanodiamonds: Identification and High Sensitivity to Magnetic Field.

The content of nitrogen-vacancy (NV-) colour centres in the nanodiamonds (DNDs) produced during the detonation of nitrogen-containing explosives was found to be 1.1 ± 0.3 ppm. This value is impressive for nanodiamonds of size < 10 nm with intentionally created NV- centres. The concentration was estimated from the electron paramagnetic resonance as determined from the integrated intensity of the g = 4.27 line. This line is related with "forbidden" ∆ms = 2 transitions between the Zeeman levels of a NV- centre's ground triplet state. Confocal fluorescence microscopy enables detection of the red photoluminescence (PL) of the NV- colour centres in nanoscale DND aggregates formed from the 5-nm nanoparticles. Subwavelength emitters consisting of NV- with sizes a few times smaller than the diffraction-limited spot are clearly distinguished. We have further observed an abrupt drop in the PL intensity when mixing and anti-crossing of the ground and excited states spin levels in NV- occurs under an applied external magnetic field. This effect is a unique quantum feature of NV- centres, which cannot be observed for other visible domain light-emitting colour centres in a diamond lattice.

Comment on "Angstrom-scale probing of paramagnetic center location in nanodiamonds by 3He NMR at low temperatures" by V. Kuzmin, K. Safiullin, G. Dolgorukov, A. Stanislavovas, E. Alakshin, T. Safin, B. Yavkin, S. Orlinskii, A. Kiiamov, M. Presnyakov, A. Klochkov and M. Tagirov, Phys. Chem. Chem. Phys., 2018, 20, 1476.

Kuzmin et al. reported on the application of the 3He NMR relaxometry technique to localization of intrinsic paramagnetic defects in detonation nanodiamond (DND) particles. We found some inconsistencies in the DND characterization, the model of paramagnetic defects' allocation used in that work as well as the estimation of distances between 3He NMR probes and paramagnetic defects, which question the results obtained.