Excited-State Lifetime of NV Centers for All-Optical Magnetic Field Sensing.

We investigate the magnetic field-dependent fluorescence lifetime of microdiamond powder containing a high density of nitrogen-vacancy centers. This constitutes a non-intensity quantity for robust, all-optical magnetic field sensing. We propose a fiber-based setup in which the excitation intensity is modulated in a frequency range up to 100MHz. The change in magnitude and phase of the fluorescence relative to B=0 is recorded where the phase shows a maximum in magnetic contrast of 5.8∘ at 13MHz. A lock-in amplifier-based setup utilizing the change in phase at this frequency shows a 100 times higher immunity to fluctuations in the optical path compared to the intensity-based approach. A noise floor of 20µT/Hz and a shot-noise-limited sensitivity of 0.95µT/Hz were determined.

Elucidating the Role of Halides and Iron during Radiolysis-Driven Oxidative Etching of Gold Nanocrystals Using Liquid Cell Transmission Electron Microscopy and Pulse Radiolysis.

Graphene liquid cell transmission electron microscopy (TEM) has enabled the observation of a variety of nanoscale transformations. Yet understanding the chemistry of the liquid cell solution and its impact on the observed transformations remains an important step toward translating insights from liquid cell TEM to benchtop chemistry. Gold nanocrystal etching can be used as a model system to probe the reactivity of the solution. FeCl3 has been widely used to promote gold oxidation in bulk and liquid cell TEM studies, but the roles of the halide and iron species have not been fully elucidated. In this work, we observed the etching trajectories of gold nanocrystals in different iron halide solutions. We observed an increase in gold nanocrystal etch rate going from Cl-- to Br-- to I--containing solutions. This is consistent with a mechanism in which the dominant role of halides is as complexation agents for oxidized gold species. Additionally, the mechanism through which FeCl3 induces etching in liquid cell TEM remains unclear. Ground-state bleaching of the Fe(III) absorption band observed through pulse radiolysis indicates that iron may react with Cl2·- radicals to form an oxidized transient species under irradiation. Complete active space self-consistent field (CASSCF) calculations indicate that the FeCl3 complex is oxidized to an Fe species with an OH radical ligand. Together our data indicate that an oxidized Fe species may be the active oxidant, while halides modulate the etch rate by tuning the reduction potential of gold nanocrystals.

Zn2+ -Ion Sensing by Fluorescent Schiff Base Calix[4]arene Macrocycles.

A macrocyclic ligand (H2 L) containing two o,o'-bis(iminomethyl)phenol and two calix[4]arene head units has been synthesized and its coordination chemistry towards divalent Ni and Zn investigated. The new macrocycle forms complexes of composition [ML] (M=Zn, M=Ni) and [ZnL(py)2 ], which were characterized by elemental analysis; IR, UV/Vis, and NMR spectroscopy; electrospray ionization mass spectrometry (ESI-MS); and X-ray crystallography (for [ZnL(py)2 ] and [NiL]). H2 L allows the sensitive optical detection of Zn2+ among a series of biologically relevant metal ions by a dual fluorescence enhancement/quenching effect in solution. The fluorescence intensity of the macrocycle increases by a factor of ten in the presence of Zn2+ with a detection limit in the lower nanomolar region.

Functionalization of 68Ga-Radiolabeled Nanodiamonds with Octreotide Does Not Improve Tumor-Targeting Capabilities.

Nanodiamonds (NDs) are emerging as a novel nanoparticle class with growing interest in medical applications. The surface coating of NDs can be modified by attaching binding ligands or imaging probes, turning them into multi-modal targeting agents. In this investigation, we assessed the targeting efficacy of octreotide-functionalized 68Ga-radiolabelled NDs for cancer imaging and compared it with the tumor uptake using [68Ga]Ga-DOTA-TOC. In vivo studies in mice bearing AR42J tumors demonstrated the highest accumulation of the radiolabeled functionalized NDs in the liver and spleen, with relatively low tumor uptake compared to [68Ga]Ga-DOTA-TOC. Our findings suggest that, within the scope of this study, functionalization did not enhance the tumor-targeting capabilities of NDs.

Fluorescence Lifetime Control of Nitrogen Vacancy Centers in Nanodiamonds for Long-Term Information Storage.

Today's huge amount of data generation and transfer induced an urgent requirement for long-term data storage. Here, we demonstrate and discuss a concept for long-term storage using NV centers inside nanodiamonds. The approach is based upon the radiation-induced generation of additional vacancies (so-called GR1 states), which quench the initial NV centers, resulting in a reduced overall fluorescence lifetime of the NV center. Using the tailored fluorescence lifetime of the NV center to code the information, we demonstrate a "beyond binary" data storage density per bit. We also demonstrate that this process is reversible by heating the sample or the spot of information. This proof of principle shows that our technique may be a promising alternative data storage technology, especially in terms of long-term storage, due to the high stability of the involved color centers. In addition to the proof-of-principle demonstration using macroscopic samples, we suggest and discuss the usage of focused electron beams to write information in nanodiamond materials, to read it out with focused low-intensity light, and to erase it on the macro-, micro-, or nanoscale.

Facile modification of phosphole-based aggregation-induced emission luminogens with sulfonyl isocyanates.

Phosphole oxides undergo a highly chemoselective reaction with sulfonyl isocyanates forming sulfonylimino phospholes in high yields. This facile modification proved to be a powerful tool for obtaining new phosphole-based aggregation-induced emission (AIE) luminogens with high fluorescence quantum yields in the solid state. Changing the chemical environment of the phosphorus atom of the phosphole framework results in a significant shift of the fluorescence maximum to longer wavelengths.

Synthesis, radiolabeling, and preclinical in vivo evaluation of 68Ga-radiolabelled nanodiamonds.

PURPOSE: Nanodiamonds (NDs) represent a new class of nanoparticles and have gained increasing interest in medical applications. Modifying the surface coating by attaching binding ligands or imaging probes can transform NDs into multi-modal targeting probes. This study evaluated the biokinetics and biodistribution of 68Ga-radiolabelled NDs in a xenograft model. PROCEDURES: NDs were coated with an albumin-derived copolymer modified with desferrioxamine to provide a chelator for radiolabeling. In vivo studies were conducted in AR42J tumor-bearing CD1 mice to evaluate biodistribution and tumor accumulation of the NDs. RESULTS: Coated NDs were successfully radiolabeled using 68Ga at room temperature with radiolabeling efficiencies up to 91.8 ± 3.2 % as assessed by radio-TLC. In vivo studies revealed the highest accumulation in the liver and spleen, whereas tumor radioactivity concentration was low. CONCLUSIONS: Radiolabeling of coated NDs could be achieved. However, the obtained results indicate these coated NDs' limitations in their biodistribution within the conducted studies.

Facet-selective etching trajectories of individual semiconductor nanocrystals.

The size and shape of semiconductor nanocrystals govern their optical and electronic properties. Liquid cell transmission electron microscopy (LCTEM) is an emerging tool that can directly visualize nanoscale chemical transformations and therefore inform the precise synthesis of nanostructures with desired functions. However, it remains difficult to controllably investigate the reactions of semiconductor nanocrystals with LCTEM, because of the highly reactive environment formed by radiolysis of liquid. Here, we harness the radiolysis processes and report the single-particle etching trajectories of prototypical semiconductor nanomaterials with well-defined crystalline facets. Lead selenide nanocubes represent an isotropic structure that retains the cubic shape during etching via a layer-by-layer mechanism. The anisotropic arrow-shaped cadmium selenide nanorods have polar facets terminated by either cadmium or selenium atoms, and the transformation trajectory is driven by etching the selenium-terminated facets. LCTEM trajectories reveal how nanoscale shape transformations of semiconductors are governed by the reactivity of specific facets in liquid environments.

Dinuclear lanthanide complexes supported by a hybrid salicylaldiminato/calix[4]arene-ligand: synthesis, structure, and magnetic and luminescence properties of (HNEt3)[Ln2(HL)(L)] (Ln = SmIII, EuIII, GdIII, TbIII).

The synthesis, structures, and properties of a new calix[4]arene ligand with an appended salicylaldimine unit (H4L = 25-[2-((2-methylphenol)imino)ethoxy]-26,27,28-trihydroxy-calix[4]arene) and four lanthanide complexes (HNEt3)[Ln2(HL)(L)] (Ln = SmIII (4), EuIII (5), GdIII (6), and TbIII (7)) are reported. X-ray crystallographic analysis (for 4 and 6) reveals an isostructural series of dimeric complexes with a triply-bridged NO3Ln(µ-O)2(OHO)LnO3N core and two seven coordinated lanthanide ions. According to UV-vis spectrometric titrations in MeCN and ESI-MS the dimeric nature is maintained in solution. The apparent stability constants range between log K = 5.8 and 6.3. The appended salicylaldimines sensitize EuIII and TbIII emission (λexc 311 nm) in the solid state or immersed in a polycarbonate glass at 77 K (for 5, 7) and at 295 K (for 7).

Controlling the fluorescence properties of nitrogen vacancy centers in nanodiamonds.

Control over the formation and fluorescence properties of nitrogen vacancy (NV) centers in nanodiamonds (NDs) is an important factor for their use in medical and sensor applications. However, reports providing a deep understanding of the potential factors influencing these properties are rare and focus only on a few influencing factors. The current contribution targets this issue and we report a comprehensive study of the fluorescence properties of NVs in nanodiamonds as a function of electron irradiation fluence and surface termination. Here we show that process parameters such as defect center interactions, in particular, different nitrogen defects and radiation induced lattice defects, as well as surface functionalities have a strong influence on the fluorescence intensity, fluorescence lifetime and the charge state ratio of the NV centers. By employing a time-correlated single photon counting approach we also established a method for fast macroscopic monitoring of the fluorescence properties of ND samples. We found that the fluorescence properties of NV centers may be controlled or even tuned depending upon the radiation treatment, annealing, and surface termination.

Photoluminescence properties of tetrahedral zinc(ii) complexes supported by calix[4]arene-based salicylaldiminato ligands.

The synthesis and photophysical properties of four new hybrid salicylaldiminato-calix[4]arene ligands and their corresponding zinc(ii) complexes are described. The Schiff bases were obtained from condensation reactions between cone-25,27-di(aminoethoxy)-26,28-dihydroxy-calix[4]arene and salicylaldehyde (H2L1) or o-vanillin (H2L2) and 1,3-alt-25,27-di(aminoethoxy)-26,28-di(n-propyloxy)-calix[4]arene and 3,5-di-tert-butyl-salicylaldehyde (H2L3) or o-vanillin (H2L4). Complexation reactions were investigated by ESI-MS, IR, NMR, UV-vis absorption and steady-state and time resolved fluorescence spectroscopy, and X-ray crystallography. All ligands support 1 : 1 complexes (ZnL1-ZnL4), with equilibrium constants derived from absorption spectrophotometry in the range log K11 = 5.5-8.2 (MeCN or MeOH/CH2Cl2, I = 0.01 M). The zinc complexes show blue fluorescence, both in solution as well as in the solid state, with λem, Φf, and τ ranging from 472-504 nm, 0.11-0.60, and 2-9 ns, respectively. The nature of the substituents on the salicylaldiminato fragments was found to be the main parameter that influences the photophysical properties of the zinc complexes. Insights into the electronic nature of the UV-vis transitions were obtained with time dependent density functional theory (TD-DFT) calculations.

How fast is the reaction of hydrated electrons with graphene oxide in aqueous dispersions?

Understanding the mechanism of the reduction of graphene oxide (GO) is a key-question in graphene related materials science. Here, we investigate the kinetics of the reaction of radiolytically generated hydrated electrons with GO in water. The electron transfer proceeds on the ns time scale and not on the ps time scale, as recently reported by Gengler et al. (Nat. Commun., 2013, 4, 2560).