Fluorescent nanodiamond for nanotheranostic applications.

The interest in application of nanodiamonds as nanotheranostics is increasing rapidly over recent years. The combination of properties, such as high refractive index, low toxicity, inertness, high carrier capacity and rich surface functionalities, as well as unique magneto-optical properties of the nitrogen-vacancy centre, renders fluorescent nanodiamonds superior to other nanomaterials as nanotheranostics. In this review, the current state of research on the applications of nanodiamonds as theranostics where they have been utilised in combination with both diagnostics/imaging and therapy simultaneously is discussed. Firstly, a brief introduction to the current knowledge about the synthesis and properties of nitrogen-vacancy centre in nanodiamonds is given. Then, the underlying principles that are responsible for the magneto-optical properties of nitrogen-vacancy centre are explained. The majority of theranostic applications of nanodiamonds rely on the judicious engineering of their surface with bioactive molecules. In the following section, methods of engineering the surface of nanodiamonds while preserving their colloidal stability and their implication on in vitro and in vivo biocompatibility are described. Subsequently, the recent developments and applications of nanodiamond conjugates as photo-theranostics and non-targeted and targeted theranostics are critically discussed. Co-delivery of specifically tailored nanodiamonds with both diagnostic/imaging and therapeutic features can considerably contribute towards nanotheranostics-based personalized medicine.

Structural insights into metal-metalloid glasses from mass spectrometry.

Despite being studied for nearly 50 years, smallest chemically stable moieties in the metallic glass (MG) could not be found experimentally. Herein, we demonstrate a novel experimental approach based on electrochemical etching of amorphous alloys in inert solvent (acetonitrile) in the presence of a high voltage (1 kV) followed by detection of the ions using electrolytic spray ionization mass spectrometry (ESI MS). The experiment shows stable signals corresponding to Pd, PdSi and PdSi2 ions, which emerges due to the electrochemical etching of the Pd80Si20 metallic glass electrode. These fragments are observed from the controlled dissolution of the Pd80Si20 melt-spun ribbon (MSR) electrode. Annealed electrode releases different fragments in the same experimental condition. These specific species are expected to be the smallest and most stable chemical units from the metallic glass which survived the chemical dissolution and complexation (with acetonitrile) process. Theoretically, these units can be produced from the cluster based models for the MG. Similar treatment on Pd40Ni40P20 MSR resulted several complex peaks consisting of Pd, Ni and P in various combinations suggesting this can be adopted for any metal-metalloid glass.

Iron assisted formation of CO2 over condensed CO and its relevance to interstellar chemistry.

Catalytic conversion of CO to CO2 has been investigated in ultrahigh vacuum (UHV) under cryogenic conditions (10 K). This cryogenic oxidation is assisted by iron upon its co-deposition with CO, on a substrate. The study shows that the interaction of Fe and CO results in a Fe-CO complex that reacts in the presence of excess CO at cryogenic conditions leading to CO2. Here, the presence of CO on the surface is a prerequisite for the reaction to occur. Different control experiments confirm that the reaction takes place in the condensed phase and not in the gas phase. Surface sensitive reflection absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), and Cs+ based low energy ion scattering are utilized for this study. The iron assisted formation of CO2 may be proposed as another pathway relevant in interstellar ices, containing CO. This direct oxidation process, which occurs at extremely low temperatures and pressures, in the presence of a reactive metal species like iron (the most abundant metal in the interstellar medium) may have astrochemical importance. It does not require any external energy in the form of photo-irradiation or thermal processing. Such reactions are highly relevant in cold dense molecular clouds where interactions between neutral species are more favoured.

Nonenzymatic Glucose Sensing Using Ni60Nb40 Nanoglass.

Despite being researched for nearly five decades, chemical application of metallic glass is scarcely explored. Here we show electrochemical nonenzymatic glucose-sensing ability of nickel-niobium (Ni60Nb40) amorphous alloys in alkaline medium. Three different Ni60Nb40 systems with the same elemental composition, but varying microstructures are created following different synthetic routes and tested for their glucose-sensing performance. Among melt-spun ribbon, nanoglass, and amorphous-crystalline nanocomposite materials, nanoglass showed the best performance in terms of high anodic current density, sensitivity (20 mA cm-2 mM-1), limit of detection (100 nM glucose), stability, reproducibility (above 5000 cycles), and sensing accuracy among nonenzymatic glucose sensors involving amorphous alloys. When annealed under vacuum, only the heat-treated nanoglass retained a similar electrochemical-sensing property, while the other materials failed to yield desired results. In nanoglass, a network of glassy interfaces, compared to melt-spun ribbon, is plausibly responsible for the enhanced sensitivity.

Combination of pulsed laser ablation and inert gas condensation for the synthesis of nanostructured nanocrystalline, amorphous and composite materials.

A new instrument combining pulsed laser ablation and inert gas condensation for the production of nanopowders is presented. It is shown that various nanostructured materials, such as regular metallic, semiconducting, insulating materials, complex high entropy alloys, amorphous alloys, composites and oxides can be synthesized. The unique variability of the experimental set-up is possible due to the reproducible control of laser power (pulse energy and repetition rate), laser ablation pattern on the target, and experimental conditions during the inert gas condensation, all of which can be controlled and optimized independently. Microstructure analysis of the as-prepared composite and amorphous Ni60Nb40 nanopowders establishes the instrument's ability for the synthesis of materials with unique compositions and atomic structure. It is further shown that small variations of the synthesis parameters can influence materials properties of the final product, in terms of particle size, composition and properties. As an example, the laser power has been used to control the magnetic properties of amorphous Ni60Nb40 nanopowders. A few selected examples of the manifold possibilities of the new synthesis apparatus are presented in this report together with detailed structural characterization of the produced nanopowders.

Extraction of Silver by Glucose.

Unprecedented silver ion leaching, in the range of 0.7 ppm was seen when metallic silver was heated in water at 70 °C in presence of simple carbohydrates, such as glucose, making it a green method of silver extraction. Extraction was facilitated by the presence of anions, such as carbonate and phosphate. Studies confirm a two-step mechanism of silver release, first forming silver ions at the metal surface and later complexation of ionic silver with glucose; such complexes have been detected by mass spectrometry. Extraction leads to microscopic roughening of the surface making it Raman active with an enhancement factor of 5×10(8) .

Zero Volt Paper Spray Ionization and Its Mechanism.

The analytical performance and a suggested mechanism for zero volt paper spray using chromatography paper are presented. A spray is generated by the action of the pneumatic force of the mass spectrometer (MS) vacuum at the inlet. Positive and negative ion signals are observed, and comparisons are made with standard kV paper spray (PS) ionization and nanoelectrospray ionization (nESI). While the range of analytes to which zero volt PS is applicable is very similar to kV PS and nESI, differences in the mass spectra of mixtures are interpreted in terms of the more significant effects of analyte surface activity in the gentler zero volt experiment than in the other methods due to the significantly lower charge. The signal intensity of zero volt PS is also lower than in the other methods. A Monte Carlo simulation based on statistical fluctuation of positive and negative ions in solution has been implemented to explain the production of ions from initially uncharged droplets. Uncharged droplets first break up due to aerodynamics forces until they are in the 2-4 µm size range and then undergo Coulombic fission. A model involving statistical charge fluctuations in both phases predicts detection limits similar to those observed experimentally and explains the effects of binary mixture components on relative ionization efficiencies. The proposed mechanism may also play a role in ionization by other voltage-free methods.

Biogenic aldehyde determination by reactive paper spray ionization mass spectrometry.

Ionization of aliphatic and aromatic aldehydes is improved by performing simultaneous chemical derivatization using 4-aminophenol to produce charged iminium ions during paper spray ionization. Accelerated reactions occur in the microdroplets generated during the paper spray ionization event for the tested aldehydes (formaldehyde, n-pentanaldehyde, n-nonanaldehyde, n-decanaldehyde, n-dodecanaldehyde, benzaldehyde, m-anisaldehyde, and p-hydroxybenzaldehyde). Tandem mass spectrometric analysis of the iminium ions using collision-induced dissociation demonstrated that straight chain aldehydes give a characteristic fragment at m/z 122 (shown to correspond to protonated 4-(methyleneamino)phenol), while the aromatic aldehyde iminium ions fragment to give a characteristic product ion at m/z 120. These features allow straightforward identification of linear and aromatic aldehydes. Quantitative analysis of n-nonaldehyde using a benchtop mass spectrometer demonstrated a linear response over 3 orders of magnitude from 2.5 ng to 5 µg of aldehyde loaded on the filter paper emitter. The limit of detection was determined to be 2.2 ng for this aldehyde. The method had a precision of 22%, relative standard deviation. The experiment was also implemented using a portable ion trap mass spectrometer.

Using ambient ion beams to write nanostructured patterns for surface enhanced Raman spectroscopy.

Electrolytic spray deposition was used to pattern surfaces with 2D metallic nanostructures. Spots that contain silver nanoparticles (AgNP) were created by landing solvated silver ions at desired locations using electrically floated masks to focus the metal ions to an area as little as 20 µm in diameter. The AgNPs formed are unprotected and their aggregates can be used for surface-enhanced Raman spectroscopy (SERS). The morphology and SERS activity of the NP structures were controlled by the surface coverage of landed silver ions. The NP structures created could be used as substrates onto which SERS samples were deposited or prepared directly on top of predeposited samples of interest. The evenly distributed hot spots in the micron-sized aggregates had an average SERS enhancement factor of 10(8) . The surfaces showed SERS activity when using lasers of different wavelengths (532, 633, and 785 nm) and were stable in air.

Development of ultralow energy (1-10 eV) ion scattering spectrometry coupled with reflection absorption infrared spectroscopy and temperature programmed desorption for the investigation of molecular solids.

Extremely surface specific information, limited to the first atomic layer of molecular surfaces, is essential to understand the chemistry and physics in upper atmospheric and interstellar environments. Ultra low energy ion scattering in the 1-10 eV window with mass selected ions can reveal extremely surface specific information which when coupled with reflection absorption infrared (RAIR) and temperature programmed desorption (TPD) spectroscopies, diverse chemical and physical properties of molecular species at surfaces could be derived. These experiments have to be performed at cryogenic temperatures and at ultra high vacuum conditions without the possibility of collisions of neutrals and background deposition in view of the poor ion intensities and consequent need for longer exposure times. Here we combine a highly optimized low energy ion optical system designed for such studies coupled with RAIR and TPD and its initial characterization. Despite the ultralow collision energies and long ion path lengths employed, the ion intensities at 1 eV have been significant to collect a scattered ion spectrum of 1000 counts/s for mass selected CH2(+).

Probing molecular solids with low-energy ions.

Ion/surface collisions in the ultralow- to low-energy (1-100-eV) window represent an excellent technique for investigation of the properties of condensed molecular solids at low temperatures. For example, this technique has revealed the unique physical and chemical processes that occur on the surface of ice, versus the liquid and vapor phases of water. Such instrument-dependent research, which is usually performed with spectroscopy and mass spectrometry, has led to new directions in studies of molecular materials. In this review, we discuss some interesting results and highlight recent developments in the area. We hope that access to the study of molecular solids with extreme surface specificity, as described here, will encourage investigators to explore new areas of research, some of which are outlined in this review.