Fast and Sensitive Detection of Paramagnetic Species Using Coupled Charge and Spin Dynamics in Strongly Fluorescent Nanodiamonds.

Sensing of a few unpaired electron spins, such as in metal ions and radicals, is a useful but difficult task in nanoscale physics, biology, and chemistry. Single negatively charged nitrogen-vacancy (NV-) centers in diamond offer high sensitivity and spatial resolution in the optical detection of weak magnetic fields produced by a spin bath but often require long acquisition times on the order of seconds. Here, we present an approach based on coupled spin and charge dynamics in dense NV ensembles in strongly fluorescent nanodiamonds (NDs) to sense external magnetic dipoles. We apply this approach to various paramagnetic species, including gadolinium complexes, magnetite nanoparticles, and hemoglobin in whole blood. Taking advantage of the high NV density, we demonstrate a dramatic reduction in acquisition time (down to tens of milliseconds) while maintaining high sensitivity to paramagnetic centers. Strong luminescence, high sensitivity, and short acquisition time make dense NV- ensembles in NDs a potentially promising tool for biosensing and bioimaging applications.

Co oxide nanostructures for electrocatalytic water-oxidation: effects of dimensionality and related properties.

A facile hydrothermal synthesis route was explored to obtain various nanostructures of Co oxide for applications in electrocatalytic water-splitting. The effect of reaction time and metal precursor ions on the morphology of synthesized nanostructures was studied in detail with the aid of a scanning electron microscope. By systematic optimization of the synthesis parameters, Co oxide nanostructures with single dimensionality were obtained in the form of 0D nanoparticles (NPs), 1D nanowires (NWs), 2D nanosheets (NSs) and 3D nanocrystals (NCs). The effectiveness of the developed nanostructures towards oxygen evolution reaction (OER) was studied and a promising OER activity was recorded for all the samples. Amongst all the developed catalysts, Co(OH)2 NPs showed the lowest overpotential of 339 mV to achieve a current density of 10 mA cm-2, which is even lower than that of noble-metal oxides such as the commercial RuO2 catalyst (370 mV). The specific effect of different parameters such as BET surface area, phase, crystallographic orientation of surface lattice planes, electroactive surface area and surface active species on the OER performance was studied. It was found that the Co3O4 phase is more active for the OER, compared to the Co(OH)2 phase. However, Co(OH)2 NPs showed the best OER performance owing to their higher BET surface area, thereby underlining the significance of the catalyst surface area. The effect of the number of active surface atoms was demonstrated by estimating the electroactive surface area of all Co3O4 nanostructures. It was also shown that the formation of CoO2 species (Co(IV)) on the surface is more beneficial for the OER as compared to the formation of CoOOH species (Co(III)). Finally, the robustness of the developed Co3O4 nanostructures was established by performing a recycling test for the OER (1000 cycles) and the observed change in the catalytic activity was correlated with morphological variation.

An all-optical single-step process for production of nanometric-sized fluorescent diamonds.

Nanodiamonds (NDs) containing negatively charged Nitrogen-Vacancy (NV) centers are promising materials for applications in photonics, quantum computing, and sensing of environmental parameters like temperature, strain and magnetic fields. However, the production of fluorescent NDs remains a technological challenge, requiring a complex multi-step process involving controlled introduction of substitutional nitrogen into the diamond lattice, annealing and fragmentation from macrocrystals to nanocrystals. Here, we report on a single-step, all-optical process for the production of nanometric-sized fluorescent diamonds based on laser ablation of a carbon substrate at low temperature (100 °C) under a nitrogen atmosphere. We demonstrate that this synthesis route yields fluorescent NDs with a concentration of native NV centers controlled by adjusting the experimental ablation conditions. Spin-polarization dependent optical-transitions are observed by optically detected magnetic resonance spectroscopy, thus providing strong evidence of the presence of negatively charged NV centers in the as-grown NDs. Finally, we propose a thermodynamic model able to describe the nucleation of NDs and the formation of NV centers in the present single-step optical process.

Simulation of phase explosion in the nanosecond laser ablation of aluminum.

HYPOTHESIS: Vaporization, spallation and phase explosion are considered to be the main mechanisms contributing to the nanosecond laser ablation of metals. The theory of homogeneous nucleation, together with the dynamics of target heating, allows a space-time resolved simulation of the phase explosion mechanism. METHODS: The thermal phenomena occurring at the target surface are studied within the framework of a thermodynamic continuum approach. A 20ns laser pulse of variable fluence and Gaussian time dependence was assumed. The temperature profile in the target external layers is studied through the heat diffusion equation. The vaporization from the surface is modeled assuming unsteady adiabatic expansion (UAE) of the vapor and a Monte Carlo (MC) method is used to describe the formation of liquid nanodroplets through phase explosion. RESULTS: Liquid nanodroplets in the ablated material are studied at different laser fluences. The size distribution of the nanodroplets formed in the phase explosion process is here reported and connections with experiments are discussed.

On the thermodynamic path enabling a room-temperature, laser-assisted graphite to nanodiamond transformation.

Nanodiamonds are the subject of active research for their potential applications in nano-magnetometry, quantum optics, bioimaging and water cleaning processes. Here, we present a novel thermodynamic model that describes a graphite-liquid-diamond route for the synthesis of nanodiamonds. Its robustness is proved via the production of nanodiamonds powders at room-temperature and standard atmospheric pressure by pulsed laser ablation of pyrolytic graphite in water. The aqueous environment provides a confinement mechanism that promotes diamond nucleation and growth, and a biologically compatible medium for suspension of nanodiamonds. Moreover, we introduce a facile physico-chemical method that does not require harsh chemical or temperature conditions to remove the graphitic byproducts of the laser ablation process. A full characterization of the nanodiamonds by electron and Raman spectroscopies is reported. Our model is also corroborated by comparison with experimental data from the literature.

Comprehensive studies on the interaction of copper nanoparticles with bovine serum albumin using various spectroscopies.

Copper nanoparticles (NPs) of average size of ~7.5nm were synthesized by chemical reduction method. Fluorescence spectroscopy in synchronous and polarization modes were used to examine the nature of interaction between Cu NPs and bovine serum albumin (BSA) at different temperatures. Fluorescence quenching results suggest that Cu NPs interact with BSA molecule through static mechanism, as inferred from the quenching of BSA fluorophore. The calculated thermodynamic parameters (ΔG°, ΔH°, and ΔS°) hint that the binding process occurs spontaneously by involving hydrophobic forces. Synchronous fluorescence spectra reveal that the interaction of Cu NPs with BSA mostly changes the microenvironment of tryptophan and not of tyrosine residues. The formation of BSA-Cu NPs ground state complex was also confirmed from the resonant light scattering and fluorescence polarization spectra. Circular dichroism and Raman spectra indicate that α-helicity of the BSA decreases due to the interaction with Cu NPs. It was also found that Cu NPs are located in the close proximity of BSA molecule, which transfer energy efficiently from the excited state of BSA fluorophore to the Cu NPs.

Systematic investigation on the interaction of bovine serum albumin with ZnO nanoparticles using fluorescence spectroscopy.

Zinc oxide (ZnO) nanoparticles with average size of ~7.5nm were synthesized to investigate their interaction with bovine serum albumin (BSA) at different temperatures. Fluorescence quenching, synchronous and polarization spectroscopy along with UV-vis absorption, circular dichroism and resonance light scattering spectroscopy techniques were used to establish the interaction mechanism between ZnO and BSA. The obtained results confirmed that the ZnO nanoparticles (NPs) quench the fluorophore of BSA by forming ground state complex in the solution. The fluorescence quenching data was also used to determine binding sites and binding constants at different temperatures. The calculated thermodynamic parameters (ΔG°, ΔH°, and ΔS°) suggest that the binding process occurs spontaneously by involving hydrogen bond and van der Waals interactions. The synchronous fluorescence spectra reveal that the microenvironment close to both the tyrosine and tryptophan residues of BSA is perturbed and that the hydrophobicity of both the residues is increased in the presence of ZnO NPs. Resonance light scattering, circular dichroism, and fluorescence polarization spectra suggest the formation of BSA-ZnO complex and conformational changes in BSA. The calculated distance between the BSA and ZnO NPs suggests that the energy transfer from excited state of BSA to ZnO NPs occurs with high efficiency.

New insights on the mechanism of palladium-catalyzed hydrolysis of sodium borohydride from 11B NMR measurements.

To gain insight on the mechanistic aspects of the palladium-catalyzed hydrolysis of NaBH(4) in alkaline media, the kinetics of the reaction has been investigated by (11)B NMR (nuclear magnetic resonance) measurements taken at different times during the reaction course. Working with BH(4)(-) concentration in the range 0.05-0.1 M and with a [substrate]/[catalyst] molar ratio of 0.03-0.11, hydrolysis has been found to follow a first-order kinetic dependence from concentration of both the substrate and the catalyst (Pd/C 10 wt %). We followed the reaction of NaBH(4) and its perdeuterated analogue NaBD(4) in H(2)O, in D(2)O and H(2)O/D(2)O mixtures. When the process was carried out in D(2)O, deuterium incorporation in BH(4)(-) afforded BH(4)(-)(n)D(n)(-) (n = 1, 2, 3, 4) species, and a competition between hydrolysis and hydrogen/deuterium exchange processes was observed. By fitting the kinetics NMR data by nonlinear least-squares regression techniques, the rate constants of the elementary steps involved in the palladium-catalyzed borohydride hydrolysis have been evaluated. Such a regression analysis was performed on a reaction scheme wherein the starting reactant BH(4)(-) is allowed both to reversibly exchange hydrogen with deuterium atoms of D(2)O and to irreversibly hydrolyze into borohydroxy species B(OD)(4)(-). In contrast to acid-catalyzed hydrolysis of sodium borohydride, our results indicate that in the palladium-catalyzed process the rate constants of the exchange processes are higher than those of the corresponding hydrolysis reactions.

Contribution of vaporization and boiling to thermal-spike sputtering by ions or laser pulses.

Here we consider what, in our terminology, we designate as normal vaporization, normal boiling, and phase explosion. In the case of vaporization, one is dealing with the emission of particles (atoms or molecules) from the extreme outer surface of either a solid or liquid for any temperature exceeding 0 K. In the case of boiling, one is (at least ideally) dealing with heterogeneously nucleated bubbles which diffuse to the outer surface of a liquid or solid and then escape, the latter being possible for temperatures equal to or exceeding the boiling temperature (T(b)). In the case of phase explosion one is dealing with the consequences of what happens when a liquid approaches the thermodynamic critical temperature (T(tc) or T(c)), and massive homogeneous nucleation takes place. Although these three mechanisms have been reviewed in reasonable detail in recent work, we will here present evidence, apparently not previously considered, that boiling, whether the distance scale is atomically small (5-15 nm, as for laser-pulse impact on a metal in the absence of thermal diffusion) or much larger, has a prohibitive kinetic obstacle because it requires bubble diffusion if the bubbles are formed other than at the outer surface. That is to say, boiling will never be a significant process whether with ion or laser-pulse impact. This leaves vaporization and phase explosion as the only possible thermal-spike processes capable of expelling material from an ion- or laser-pulse bombarded surface in a significant quantity. But even with vaporization it can be shown that a kinetic obstacle, although not as severe as for boiling, will enter. The final result is that only phase explosion will normally be relevant for sufficiently short time scales.