Spin-lattice relaxation time in water/graphene-oxide dispersion.

We present the results of the calculations of the spin-lattice relaxation time of water in contact with graphene oxide by means of all-atom molecular dynamics simulations. We fully characterized the water-graphene oxide interaction through the calculation of the relaxation properties of bulk water and of the contact angle as a function of graphene oxide oxidation state and comparing them with the available experimental data. We then extended the calculation to investigate how graphene oxide alters the dynamical and relaxation properties of water in different conditions and concentrations. We show that, despite the diamagnetic nature of the graphene oxide, the confining effects of the bilayers strongly affect the longitudinal relaxation properties of interfacial water, which presents a reduced dynamics due to hydrogen bonds with oxygen groups on graphene oxide. This property makes graphene oxide an interesting platform to investigate water dynamics in confined geometries and an alternative contrast-agent for magnetic resonance imaging applications, especially in view of the possibility to functionalize graphene oxide from theranostic perspectives.

Synchrotron radiation photoemission spectroscopy of the oxygen modified CrCl3 surface.

We investigate the experimentally challenging CrCl3 surface by photon energy dependent photoemission (PE). The core and valence electrons after cleavage of a single crystal, either in a ultra-high vacuum (UHV) or in air, are studied by keeping the samples at 150 °C, aiming at confirming the atomic composition with respect to the expected bulk atomic structure. A common spectroscopic denominator revealed by data is the presence of a stable, but only partially ordered Cl-O-Cr surface. The electronic core levels (Cl 2p, Cr 2p and 3p), the latter ones of cumbersome component determination, allowed us to quantify the electron charge transfer to the Cr atom as a net result of this modification and the increased exchange interaction between metal and ligand atoms. In particular, the analysis of multiplet components by the CMT4XPS code evidenced the charge transfer to be favored, and similarly the reduced crystal field due to the established polarization field. Though it is often claimed that a significant amount of Cl and Cr atomic vacancies has to be included, such a possibility can be excluded on the basis of the sign and the importance of the shift in the binding energy of core level electrons. The present methodological approach can be of great impact to quantify the structure of ordered sub-oxide phases occurring in mono or bi-layer Cr trihalides.

Mechanical exfoliation and layer number identification of single crystal monoclinic CrCl3.

After the recent finding that CrI3, displays ferromagnetic order down to its monolayer, extensive studies have followed to pursue new two-dimensional (2D) magnetic materials. In this article, we report on the growth of single crystal CrCl3 in the layered monoclinic phase. The system after mechanical exfoliation exhibits stability in ambient air (the degradation occurs on a time scale at least four orders of magnitude longer than is observed for CrI3). By means of mechanical cleavage and atomic force microscopy (AFM) combined with optical identification, we demonstrate the systematic isolation of single and few layer flakes onto 270 nm and 285 nm SiO2/Si (100) substrates with lateral size larger than graphene flakes isolated with the same method. The layer number identification has been carried with statistically significant data, quantifying the optical contrast as a function of the number of layers for up to six layers. Layer dependent optical contrast data have been fitted within the Fresnel equation formalism determining the real and imaginary part of the wavelength dependent refractive index of the material. A layer dependent (532 nm) micro-Raman study has been carried out down to two layers with no detectable spectral shifts as a function of the layer number and with respect to the bulk.

YAP/TAZ mechano-transduction as the underlying mechanism of neuronal differentiation induced by reduced graphene oxide.

AIM: The aim of this work is the dissection of the molecular pathways underlying the differentiation effect of reduced graphene oxide (GO) materials in the absence of differentiation agents. MATERIALS & METHODS: Reduced GO is obtained either by drop casting method and heat-treated or biological reduction by the interaction between GO and wtPrxI. Cells were grown on both materials and the differentiation process studied by immunological and morphological detection. RESULTS & CONCLUSION: The results obtained indicate that both reduction methods of GO can determine the modulation of pathway involved in mechano-transduction and differentiation, by affecting YAP/TAZ localization outside the nuclei and increasing neuronal differentiation markers. This suggests that the mechano-transduction pathways are responsible for the differentiation process.

Biomimetic graphene for enhanced interaction with the external membrane of astrocytes.

Graphene and graphene substrates display huge potential as material interfaces for devices and biomedical tools targeting the modulation or recovery of brain functionality. However, to be considered reliable neural interfaces, graphene-derived substrates should properly interact with astrocytes, favoring their growth and avoiding adverse gliotic reactions. Indeed, astrocytes are the most abundant cells in the human brain and they have a crucial physiological role to maintain its homeostasis and modulate synaptic transmission. In this work, we describe a new strategy based on the chemical modification of graphene oxide (GO) with a synthetic phospholipid (PL) to improve interaction of GO with brain astroglial cells. The PL moieties were grafted on GO sheets through polymeric brushes obtained by atom-transfer radical-polymerization (ATRP) between acryloyl-modified PL and GO nanosheets modified with a bromide initiator. The adhesion of primary rat cortical astrocytes on GO-PL substrates increased by about three times with respect to that on glass substrates coated with standard adhesion agents (i.e. poly-d-lysine, PDL) as well as with respect to that on non-functionalized GO. Moreover, we show that astrocytes seeded on GO-PL did not display significant gliotic reactivity, indicating that the material interface did not cause a detrimental inflammatory reaction when interacting with astroglial cells. Our results indicate that the reported biomimetic approach could be applied to neural prosthesis to improve cell colonization and avoid glial scar formation in brain implants. Additionally, improved adhesion could be extremely relevant in devices targeting neural cell sensing/modulation of physiological activity.

XPS study of graphene oxide reduction induced by (100) and (111)-oriented Si substrates.

The reduction of graphene oxide (GO) has been extensively studied in literature in order to let GO partially recover the properties of graphene. Most of the techniques proposed to reduce GO are based on high temperature annealing or chemical reduction. A new procedure, based on the direct reduction of GO by etched Si substrate, was recently proposed in literature. In the present work, we accurately investigated the Si-GO interaction with x-ray photoelectron spectroscopy. In order to avoid external substrate oxidation factors we used EtOH as the GO solvent instead of water, and thermal annealing was carried out in UHV. We investigated the effect of Si(100), Si(111) and Au substrates on GO, to probe the role played by both the substrate composition and substrate orientation during the reduction process. A similar degree of GO reduction was observed for all samples but only after thermal annealing, ruling out the direct reduction effect of the substrate.

Few layered MoS2 lithography with an AFM tip: description of the technique and nanospectroscopy investigations.

A novel technique to lithograph the MoS2 surface is described here. Mechanically exfoliated MoS2 flakes have been patterned with an atomic force microscope tip. After the patterning process, the lithographed areas have been removed by selective chemical etching. The electronic properties of the MoS2 flakes have been analyzed with spatially resolved photoelectron spectroscopy, with tunable incident photon energy, provided by a synchrotron light source. Tens of meV core level shifts can be recorded in relation to the flakes edges, coming from both the exfoliation and from the lithography.

Graphene oxide: from fundamentals to applications.

In this review, we discuss the fundamental characterization of graphene oxide (GO) and its future application perspectives. Morphology is discussed through optical microscopy, fluorescence microscopy, scanning electron microscopy, and atomic force microscopy studies. Chemical, structural, and vibrational properties are discussed through x-ray photoemission spectroscopy and Raman spectroscopy studies. Two easy characterization strategies, based on the correlation between x-ray photoemission spectroscopy and contact angle/optical contrast measurements are reported. Sensing and nano-biotechnology applications are discussed with focus on practical gas sensing and optical sensing, on the one hand, and on the toxicity issue of GO, on the other hand. Synthesis and post-synthesis treatments are also discussed, these latter with emphasis on lithography.

Flake size-dependent cyto and genotoxic evaluation of graphene oxide on in vitro A549, CaCo2 and vero cell lines.

This study was carried out by varying both graphene oxide (GO) concentration (10 μg/mL, 50 μg/mL, 100 μg/mL) and flakes sizes of 1320 nm and 130 nm. Characterization by scanning electron microscopy and Raman spectroscopy demonstrate that the area of GO flakes varies of one order of magnitude but their chemical structure remains unmodified. A 24-h cytotoxicity test showed, for A549, a loss in the viability, while the test exhibits overall a positive increase in the viability for CaCo2 and Vero. A 24-h comet assay shows a marked GO genotoxicity: for micrometer-sized GO flakes the genotoxicity is in positive correlation with the concentration, while for nanometer-sized GO flakes there was a high degree of genotoxicity at the lowest concentration tested.

The electronic structure of gas phase croconic acid compared to the condensed phase: more insight into the hydrogen bond interaction.

The electronic structure of croconic acid in the gas phase has been investigated by means of core level and valence band photoemission spectroscopy and compared with hybrid Heyd-Scuseria-Ernzerhof density functional theory calculations. The results have been compared with the corresponding ones of the condensed phase. In the gas phase, due to the absence of hydrogen bond intermolecular interactions, the O 1 s core level spectrum shows a shift of binding energy between the hydroxyl (O-H) and the carbonyl group (C=O) of 2.1 eV, which is larger than the condensed phase value of 1.6 eV. Interestingly, such a shift decreases exponentially with the increase of the O-H distance calculated from theory. The significant differences between the gas and condensed phase valence band spectra highlight the important role played by the hydrogen bonding in shaping the electronic structure of the condensed phase.

Unravelling the role of the central metal ion in the electronic structure of tris(8-hydroxyquinoline) metal chelates: photoemission spectroscopy and hybrid functional calculations.

The electronic structures of tris(8-hydroxyquinolinato)-erbium(III) (ErQ(3)) and tris(8-hydroxyquinolinato)-aluminum(III) (AlQ(3)) have been studied by means of core level and valence band photoemission spectroscopy with the theoretical support of hybrid Heyd-Scuseria-Ernzerhof density functional theory, to investigate the role played by the central metal atom. A lower binding energy (0.2 eV and 0.3 eV, respectively) of the O 1s and N 1s core levels has been observed for ErQ(3) with respect to AlQ(3). Differences in the valence band spectra, mainly related to the first two peaks next to the highest occupied molecular orbital (HOMO), have been ascribed to an energetic shift (to 0.4 eV lower energies for ErQ(3)) of the σ molecular orbital between the oxygen atoms and the central metal atom. A lower (by 0.5 eV) ionization energy has been measured for the ErQ(3). The interpretation of these results is based on a reduced interaction between the central metal atom and the ligands in ErQ(3), with increased electronic charge around the ligands, due to the higher ionic radius and the lower electronegativity of Er with respect to Al.

Large area extreme-UV lithography of graphene oxide via spatially resolved photoreduction.

The ability to pattern graphene over large areas with nanometer resolution is the current request for nanodevice fabrication at the industrial scale. Existing methods do not match high throughput with nanometer resolution. We propose a high-throughput resistless extreme-UV (EUV) photolithographic approach operating with sub-micrometer resolution on large area (~10 mm(2)) graphene oxide (GO) films via spatially resolved photoreduction. The efficiency of EUV photoreduction is tested with 46.9 nm coherent light produced by a table top capillary discharge plasma source. Irradiated samples are studied by X-ray photoemission spectroscopy (XPS) and micro-Raman Spectroscopy (µRS). XPS data show that 200 mJ/cm(2) EUV dose produces, onto pristine GO, a 6% increase of sp(2) carbon bonds and a 20% decrease of C-O bonds. µRS data demonstrate a photoreduction efficiency 2 orders of magnitude higher than the one reported in the literature for UV-assisted photoreduction. GO patterning is obtained modulating the EUV dose with a Lloyd's interferometer. The lithographic features consist of GO stripes with modulated reduction degree. Such modulation is investigated and demonstrated by µRS on patterns with 2 µm periodicity.

High STEAP1 expression is associated with improved outcome of Ewing's sarcoma patients.

BACKGROUND: Ewing's sarcoma (ES) is the second most common bone or soft-tissue sarcoma in childhood and adolescence and features a high propensity to metastasize. The six-transmembrane epithelial antigen of the prostate 1 (STEAP1) is a membrane-bound mesenchymal stem cell marker highly expressed in ES. Here, we investigated the role of STEAP1 as an immunohistological marker for outcome prediction in patients with ES. PATIENTS AND METHODS: Membranous STEAP1 immunoreactivity was analyzed using immunohistochemistry in 114 primary pre-chemotherapy ES of patients diagnosed from 1983 to 2010 and compared with clinical parameters and patient outcome. Median follow-up was 3.85 years (range 0.43-17.51). RESULTS: A total of 62.3% of the ES samples displayed detectable STEAP1 expression with predominant localization of the protein at the plasma membrane. High membranous STEAP1 immunoreactivity was found in 53.5%, which correlated with better overall survival (P=0.021). Accordingly, no or low membranous STEAP1 expression was identified as an independent risk factor in multivariate analysis (hazard ratio 2.65, P=0.036). CONCLUSION: High membranous STEAP1 expression predicts improved outcome and may help to define a specific subgroup of ES patients, who might benefit from adapted therapy regimens.

Fingerprints of the hydrogen bond in the photoemission spectra of croconic acid condensed phase: an x-ray photoelectron spectroscopy and ab-initio study.

The electronic structure of Croconic Acid in the condensed phase has been studied by comparing core level and valence band x-ray photoelectron spectroscopy experiments and first principles density functional theory calculations using the Heyd-Scuseria-Ernzerhof screened hybrid functional and the GW approximation. By exploring the photoemission spectra for different deposition thicknesses, we show how the formation of the hydrogen bond network modifies the O 1s core level lineshape. Moreover, the valence band can be explained only if the intermolecular interactions are taken into account in the theoretical approach.

Rapid identification of graphene flakes: alumina does it better.

We report a systematic investigation of the colour contrast (CC) of graphene (one, two and three layers) on 50, 72 and 80 nm thick Al(2)O(3)/Si(100) and 100 and 300 nm thick SiO(2)/Si(100). The CC is determined by the analysis of optical microscopy images taken under white light illumination. A corresponding assignment of graphene in the single-layer, double-layer and trilayer phases is made using micro-Raman spectroscopy. A quantitative evaluation allows us to conclude that the colour contrast between 72 nm alumina and graphene is significantly larger than that between 300 nm silicon oxide and graphene (by factors of 2.2, 2.0 and 3.3 for the single-layer, double-layer and trilayer graphene flakes respectively). Moreover, data indicate that, to increase visibility, the use of a red or a green light is preferable.

A study of the mechanical vibrations of a table-top extreme ultraviolet interference nanolithography tool.

A prototype low cost table-top extreme ultraviolet (EUV) laser source (1.5 ns pulse duration, lambda=46.9 nm) was successfully employed as a laboratory scale interference nanolithography (INL) tool. Interference patterns were obtained with a simple Lloyd's mirror setup. Periodic structures on Polymethylmethacrylate/Si substrates were produced on large areas (8 mm(2)) with resolutions from 400 to 22.5 nm half pitch (the smallest resolution achieved so far with table-top EUV laser sources). The mechanical vibrations affecting both the laser source and Lloyd's setup were studied to determine if and how they affect the lateral resolution of the lithographic system. The vibration dynamics was described by a statistical model based on the assumption that the instantaneous position of the vibrating mechanical parts follows a normal distribution. An algorithm was developed to simulate the process of sample irradiation under different vibrations. The comparison between simulations and experiments allowed to estimate the characteristic amplitude of vibrations that was deduced to be lower than 50 nm. The same algorithm was used to reproduce the expected pattern profiles in the lambda/4 half pitch physical resolution limit. In that limit, a nonzero pattern modulation amplitude was obtained from the simulations, comparable to the peak-to-valley height (2-3 nm) measured for the 45 nm spaced fringes, indicating that the mechanical vibrations affecting the INL tool do not represent a limit in scaling down the resolution.

Localization of the dopant in Ge:Mn diluted magnetic semiconductors by x-ray absorption at the Mn K edge.

A unitary picture of the structural properties of Mn(x)Ge(1-x) diluted alloys fabricated by either ion implantation or molecular beam epitaxy (MBE), at various growth temperatures (from 80 to about 623 K) and few per cent concentrations, is proposed. Analysis is based on synchrotron radiation x-ray absorption spectroscopy at the Mn K edge. When the growth temperature exceeds 330 K, the MBE samples show a high number of precipitated ferromagnetic nanoparticles, mainly Mn(5)Ge(3), nucleated from the previous occupation of interstitial tetrahedral sites. Efficient substitution is observed in the case of MBE samples made by alternate layers of GeMn alloys grown at T ≤ 433 K and undoped Ge thick layers. Similar good dilution properties are obtained by implanting Mn ions at low temperatures (80 K). Possible precursors to preferential mechanisms in the alloy formation are discussed on the basis of the present comparative study.

Large area interference lithography using a table-top extreme ultraviolet laser: a systematic study of the degree of mutual coherence.

A prototype low cost table-top Ar capillary discharge laser source (1.5 ns pulse duration, lambda = 46.9 nm) was successfully used to produce, by means of interference lithography (with a simple Lloyd mirror setup), large area (0.1 mm(2)) regular patterns from 400 nm down to 22.5 nm (half-pitch) on PMMA/Si (PMMA: polymethylmethacrylate) substrates. The experiments allowed a systematical investigation of the degree of mutual coherence of the source, giving a clear indication that the interference lithography can be pushed down to the ultimate resolution limit of lambda/4.

Structural, electrical, electronic and optical properties of melanin films.

We present thick, uniform and rather flat melanin films obtained using spray deposition. The morphology of the films was investigated using Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). Temperature-dependent electrical resistance of melanin thin films evidenced a semiconductor-like character and a hysteretic behavior linked to an irreversible process of water molecule desorption from the melanin film. X-ray Photoelectron Spectroscopy (XPS) was carried out to analyze the role of the functional groups in the primary and secondary structure of the macromolecule, showing that the contribution of the 5,6-dihydroxyindole-2-carboxylic acid (DHICA) subunit to the molecule is about 35%. Comparison of the optical absorption of the thick (800nm) and thin (80nm) films showed a spectral change when the thickness increases. From in vacuum photoconductivity (PC) measured at controlled temperatures, we suggest that the melanin films exhibit a possible charge transport mechanism by means of delocalized pi states along the stacked planar secondary structure.

Evaluation of magnetic resonance signal modification induced by hyaluronic acid therapy in chondromalacia patellae: a preliminary study.

Hyaluronic Acid (HA) is an alternative method for the treatment of osteoarthritis (OA), which acts on pain through a double action: anti-inflammatory and synovial fluid (SF) visco-supplementation. Magnetic Resonance Imaging (MRI), utilizing specific sequences, is a valid method for studying the initial phase of chondral damage. The analysis of the data, obtained through the intensity of values taken by positioning Region of Interest (ROIs) within the lesion, determining the differences before and after treatment with HA injected into the knee. The results obtained after six months and one year from the injection were statistically different in respect to those taken before, immediately and after three months of treatment. MRI represents a valid tool to evaluate the grade of chondromalacia patellae and also to follow the cartilage modification induced by HA therapy.