A simple and mild chemical oxidation route to high-purity nano-graphene oxide

Nano-graphene oxide (nGO) is used in a wide range of applications including cellular imaging, drug delivery, desalination and energy storage. Current preparation protocols are similar as for standard graphene oxide (GO) and typically rely on mixtures of sulfuric acid and potassium permanganate. We present a new route to nGO (∼30 nm diameter) using a quite defective arc-discharge carbon source and only 9 M nitric acid as the oxidising agent. The preparation can be scaled up proportionately with current GO protocols with 50 mL of half-concentrated nitric acid able to process one gram of arc-discharge material. The workup is straight forward and involves neutralization with sodium hydroxide which precipitates the sodium salt of nGO from solution. The only by-product of the new procedure is aqueous sodium nitrate which makes this protocol the cleanest route yet to nGO. The presence and quantities of functional groups in our nGO are determined and compared with standard GO. We anticipate that this new route to nGO will foster a range of new applications. The presence of highly reactive carboxylic anhydride groups on our nGO material in particular offers an excellent opportunity for purpose-specific chemical functionalization

Highly efficient heavy-metal extraction from water with carboxylated graphene nanoflakes

Heavy metals such a lead or cadmium have a wide range of detrimental and devastating effects on human health. It is therefore of paramount importance to efficiently remove heavy metals from industrial wastewater streams as well as drinking water. Carbon materials, including graphene and graphene oxide (GO), have recently been advocated as efficient sorption materials for heavy metals. We show that highly carboxylated graphene nanoflakes (cx-GNF) outperform nano-graphene oxide (nGO) as well as traditional GO with respect to extracting Fe 2+ , Cu 2+ , Fe 3+ , Cd 2+ and Pb 2+ cations from water. The sorption capacity for Pb 2+ , for example, is more than six times greater for the cx-GNF compared to GO which is attributed to the efficient formation of lead carboxylates as well as strong cation-π interactions. The large numbers of carboxylic acid groups as well as the intact graphenic regions of the cx-GNF are therefore responsible for the strong binding of the heavy metal cations. Remarkably, the performance of the as-made cx-GNF can easily compete with previously reported carbon materials that have undergone additional chemical-functionalisation procedures for the purpose of heavy-metal extraction. Furthermore, the recyclability of the cx-GNF material with respect to Pb 2+ loading is demonstrated as well as the outstanding performance for Pb 2+ extraction in the presence of excess Ca 2+ or Mg 2+ cations which are often present under environmental conditions. Out of all the graphene materials, the cx-GNF therefore show the greatest potential for future application in heavy-metal extraction processes

The influence of acidic edge groups on the electrochemical performance of graphene nanoflakes

Graphene nanoflakes (GNF) with lateral dimensions of ca. 30 nm and edge-terminated with carboxylic acid functionalities have been characterised and the influence of acidic functionalities on the [Fe(CN)6]3−/4− redox couple studied using cyclic voltammetry and spectroelectrochemical methods. The presence of the COOH-terminated GNF in solution as well as immobilised onto an electrode surface was found to inhibit the redox reaction, supporting the conclusion that GNF promote instability of [Fe(CN)6]3−/4− in solution. The redox reaction was also much less influenced by the presence of GNF in D2O, highlighting the role played by readily available protons in destabilising the [Fe(CN)6]3−/4− redox couple. In the presence of GNF in solution, an additional, very intense cyanide stretch IR band was observed that was attributed to the formation of a new, non-soluble species. When D2O was used as the solvent, the IR spectrum showed no evidence of a new cyano species

Electrochemical characterisation of graphene nanoflakes with functionalised edges

Graphene nanoflakes (GNF) of diameter ca. 30 nm and edge-terminated with carboxylic acid (COOH) or amide functionalities were characterised electrochemically after drop-coating onto a boron-doped diamond (BDD) electrode. In the presence of the outer-sphere redox probe ferrocenemethanol there was no discernible difference in electrochemical response between the clean BDD and GNF-modified electrodes. When ferricyanide or hydroquinone were used as redox probes there was a marked difference in response at the electrode modified with COOH-terminated GNF in comparison to the unmodified BDD and amide-terminated GNF electrode. The response of the COOH-terminated GNF electrode was highly pH dependent, with the most dramatic differences in response noted at pH < 8. This pH range coincides with partial protonation of the carboxylic acid groups as determined by titration. The acid edge groups occupy a range of bonding environments and are observed to undergo deprotonation over a pH range ca. 3.7 to 8.3. The protonation state of the GNF influences the oxidation mechanism of hydroquinone and in particular the number of solution protons involved in the reaction mechanism. The voltammetric response of ferricyanide is very inhibited by the presence of COOH-terminated GNF at pH < 8, especially in low ionic strength solution. While the protonation state of the GNF is clearly a major factor in the observed response, the exact role of the acid group in the redox process has not been firmly established. It may be that the ferricyanide species is unstable in the solution environment surrounding the GNF, where dynamic protonation equilibria are at play, perhaps through disruption to ion pairing

Multi-functionalised graphene nanoflakes as tumour-targeting theranostic drug-delivery vehicles

Graphene nanoflakes (GNFs) consist of a graphene sheet approximately 30 nm in diameter with a pristine aromatic system and an edge terminated with carboxylic acid groups. Their high water solubility and relative ease of functionalisation using carboxylate chemistry means that GNFs are potential scaffolds for the synthesis of theranostic agents. In this work, GNFs were multi-functionalised with derivatives of (i) a peptide-based Glu-NH-C(O)-NH-Lys ligand that binds prostate-specific membrane antigen (PSMA), (ii) a potent anti-mitotic drug (R)-ispinesib, (iii) the chelate desferrioxamine B (DFO), and (iv) an albumin-binding tag reported to extend pharmacokinetic half-life in vivo. Subsequent 68Ga radiochemistry and experiments in vitro and in vivo were used to evaluate the performance of GNFs in theranostic drug design. Efficient 68Ga-radiolabelling was achieved and the particle-loading of (R)-ispinesib and Glu-NH-C(O)-NH-Lys was confirmed using cellular assays. Using dose–response curves and FACS analysis it was shown that GNFs loaded with (R)-ispinesib inhibited the kinesin spindle protein (KSP) and induced G2/M-phase cell cycle arrest. Cellular uptake and blocking experiments demonstrated that GNFs functionalised with the Glu-NH-C(O)-NH-Lys ligand showed specificity toward PSMA expressing cells (LNCaP). The distribution profile and excretion rates of 68Ga-radiolabelled GNFs in athymic nude mice was evaluated using time–activity curves derived from dynamic positron-emission tomography (PET). Image analysis indicated that GNFs have low accumulation and retention in background tissue, with rapid renal clearance. In summary, our study shows that GNFs are suitable candidates for use in theranostic drug design

Surface redox chemistry and mechanochemistry of insulating polystyrene nanospheres

Cyclic voltammetry (CV) of polystyrene nanospheres was carried out after immobilisation onto boron-doped diamond electrodes. Although the polystyrene is insulating, a voltammetric response was obtained. This was attributed to the high surface area of the nanospheres, allowing the redox chemistry of the polystyrene surface to be probed despite the non-conducting nature of the bulk. The polystyrene redox response was found to be strongly dependent on prior mechanical agitation. Centrifuged, sonicated and vortexed polystyrene nanospheres all exhibited significantly higher oxidation currents than the non-agitated polystyrene. Mechanical treatment by sonication and centrifugation was found to bring about changes to surface chemistry of the polystyrene spheres, in particular the introduction of oxygen functionalities. For these samples the CV response is attributed to the presence of surface phenol functionalities. On the non-agitated and vortex treated polystyrene surfaces X-ray photoelectron spectroscopy revealed an absence of oxygen functionalities that could explain the redox response. Repetition of the CV experiment in the presence of a solution spin trap suggests that radical species play a role in the observed response. For the vortexed sample the increased oxidation currents were attributed to significant surface roughening and deformation, as revealed by Transmission Electron Microscopy

Multi-Wavelength Observations of the Blazar 1ES 1011+496 in Spring 2008

The BL Lac object 1ES 1011+496 was discovered at Very High Energy gamma-rays by MAGIC in spring 2007. Before that the source was little studied in different wavelengths. Therefore a multi-wavelength (MWL) campaign was organized in spring 2008. Along MAGIC, the MWL campaign included the Metsahovi radio observatory, Bell and KVA optical telescopes and the Swift and AGILE satellites. MAGIC observations span from March to May, 2008 for a total of 27.9 hours, of which 19.4 hours remained after quality cuts. The light curve showed no significant variability. The differential VHE spectrum could be described with a power-law function. Both results were similar to those obtained during the discovery. Swift XRT observations revealed an X-ray flare, characterized by a harder when brighter trend, as is typical for high synchrotron peak BL Lac objects (HBL). Strong optical variability was found during the campaign, but no conclusion on the connection between the optical and VHE gamma-ray bands could be drawn. The contemporaneous SED shows a synchrotron dominated source, unlike concluded in previous work based on nonsimultaneous data, and is well described by a standard one zone synchrotron self Compton model. We also performed a study on the source classification. While the optical and X-ray data taken during our campaign show typical characteristics of an HBL, we suggest, based on archival data, that 1ES 1011+496 is actually a borderline case between intermediate and high synchrotron peak frequency BL Lac objects.Comment: 13 pages, accepted for publication in MNRA

Teraelectronvolt pulsed emission from the Crab Pulsar detected by MAGIC

Aims. We investigate the extension of the very high-energy spectral tail of the Crab Pulsar at energies above 400 GeV. Methods. We analyzed similar to 320 h of good-quality Crab data obtained with the MAGIC telescope from February 2007 to April 2014. Results. We report the most energetic pulsed emission ever detected from the Crab Pulsar reaching up to 1.5 TeV. The pulse profile shows two narrow peaks synchronized with those measured in the GeV energy range. The spectra of the two peaks follow two different power-law functions from 70GeV up to 1.5 TeV and connect smoothly with the spectra measured above 10GeV by the Large Area Telescope (LAT) on board the Fermi satellite. When making a joint fit of the LAT and MAGIC data above 10 GeV the photon indices of the spectra differ by 0.5 +/- 0.1. Conclusions. Using data from the MAGIC telescopes we measured the most energetic pulsed photons from a pulsar to date. Such TeV pulsed photons require a parent population of electrons with a Lorentz factor of at least 5x10(6). These results strongly suggest IC scattering off low-energy photons as the emission mechanism and a gamma-ray production region in the vicinity of the light cylinder