Electrochemical scanning probe analysis used as a benchmark for carbon forms quality test.

Carbon forms (graphite, pyrolytic graphite, highly oriented pyrolytic graphite (HOPG), glassy carbon, carbon foam, graphene, buckypaper, etc) are a wide class of materials largely used in technology and energy storage. The huge request of carbon compounds with reliable and tunable physical and chemical properties is tackled by contriving new production protocols and/or compound functionalizations. To achieve these goals, new samples must be tested in a trial-and-error strategy with techniques that provide information in terms of both specimen quality and properties. In this work, we prove that electrochemical scanning probe techniques allow testing the performances of carbon compounds when are used as an electrode inside an electrochemical cell. Comparing the results with a reference sample (namely, HOPG) gives an insight on defects in the specimen structure, performances, and possible applications of the new samples. In this study, we concentrate on traditional carbon forms already employed in many fields versus new recently-developed specimens, in view of possible applications to the field of energy storage.

Designing Cascades of Electron Transfer Processes in Multicomponent Graphene Conjugates.

A novel family of nanocarbon-based materials was designed, synthesized, and probed within the context of charge-transfer cascades. We integrated electron-donating ferrocenes with light-harvesting/electron-donating (metallo)porphyrins and electron-accepting graphene nanoplates (GNP) into multicomponent conjugates. To control the rate of charge flow between the individual building blocks, we bridged them via oligo-p-phenyleneethynylenes of variable lengths by ß-linkages and the Prato-Maggini reaction. With steady-state absorption, fluorescence, Raman, and XPS measurements we realized the basic physico-chemical characterization of the photo- and redox-active components and the multicomponent conjugates. Going beyond this, we performed transient absorption measurements and corroborated by single wavelength and target analyses that the selective (metallo)porphyrin photoexcitation triggers a cascade of charge transfer events, that is, charge separation, charge shift, and charge recombination, to enable the directed charge flow. The net result is a few nanosecond-lived charge-separated state featuring a GNP-delocalized electron and a one-electron oxidized ferrocenium.

Modeling and Electrochemical Characterization of Electrodes Based on Epoxy Composite with Functionalized Nanocarbon Fillers at High Concentration.

This paper deals with the electrochemical characterization and the equivalent circuit modeling of screen-printed electrodes, modified by an epoxy composite and loaded with carbon nanotubes (CNTs), pristine and functionalized NH2, and graphene nanoplates (GNPs). The fabrication method is optimized in order to obtain a good dispersion even at high concentration, up to 10%, to increase the range of investigation. Due to the rising presence of filler on the surface, the cyclic voltammetric analysis shows an increasing of (i) electrochemical response and (ii) filler concentration as observed by the scanning electron microscopy (SEM). Epoxy/CNTs-NH2 and epoxy/GNPs, at 10% of concentration, show the best electrochemical behavior. Furthermore, epoxy/CNTs-NH2 show a lower percolation threshold than epoxy/CNT, probably due to the direct bond created by amino groups. Furthermore, the electrochemical impedance spectroscopy (EIS) is used to obtain an electrical equivalent circuit (EEC). The EEC model is a remarkable evolution of previous circuits present in the literature, by inserting an accurate description of the capacitive/inductive/resistive characteristics, thus leading to an enhanced knowledge of phenomena that occur during electrochemical processes.

X-ray Absorption and Magnetic Circular Dichroism in CVD Grown Carbon Nanotubes.

Nowadays, a deep knowledge of procedures of synthesis of nanostructured materials plays an important role in achieving nano-materials with accurate and wanted properties and performances. Carbon-based nanostructured materials continue to attract a huge amount of research efforts, because of their wide-ranging properties. Using X-ray absorption (XAS) and X-ray magnetic circular dichroism (XMCD) spectroscopy in the soft X-ray regime, by the synchrotron radiation, we studied the L3,2 absorption edges of iron (Fe) nanoparticles, when they are embedded in oriented Multi Wall Carbon Nanotube (MWCNTs) layers grown by thermal Chemical Vapor Deposition (CVD) technique catalyzed by this transition metal. This could allow us to understand the valence state and role of catalysts and thus their electronic and magnetic structures. It is important to note that the control of the size of these tethered nanoparticles is of primary importance for the purpose of tailoring the physical and chemical properties of these hierarchical materials. The MWCNTs samples used in XAS and XMCD measurements were synthesized by the CVD technique. The actual measurements were carried out by the group NEXT of the INFN- LNF with the logistic experimental support of the INFM-CNR and the Synchrotron Elettra Trieste.

Electrical Permittivity and Conductivity of a Graphene Nanoplatelet Contact in the Microwave Range.

This paper investigates the electrical properties in the microwave range of a contact made by graphene nanoplatelets. The final goal is that of estimating the range of values for the equivalent electrical complex permittivity of a contact obtained by integrating low-cost graphene in the form of nanoplatelets (GNPs) into a high-frequency electrical circuit. To this end, a microstrip-like circuit is designed and realized, where the graphene nanoplatelets are self-assembled into a gap between two copper electrodes. An experimental characterization is carried out, both to study the structural properties of the nanomaterials and of the realized devices, and to measure the electromagnetic scattering parameters in the microwave range by means of a microstrip technique. A full-wave electromagnetic model is also derived and used to investigate the relationship between the measured quantities and the physical and geometrical parameters. The combined use of the experimental and simulation results allows for retrieving the values of the equivalent complex permittivity. The equivalent electrical conductivity values are found to be well below the values expected for isolated graphene nanoplatelets. The real part of the electrical relative permittivity attains values comparable to those obtained with GNP nanocomposites.

Regulation of angiogenesis through the efficient delivery of microRNAs into endothelial cells using polyamine-coated carbon nanotubes.

MicroRNAs (miRNAs) directly regulate gene expression at a post-transcriptional level and represent an attractive therapeutic target for a wide range of diseases. Here, we report a novel strategy for delivering miRNAs to endothelial cells (ECs) to regulate angiogenesis, using polymer functionalized carbon nanotubes (CNTs). CNTs were coated with two different polymers, polyethyleneimine (PEI) or polyamidoamine dendrimer (PAMAM), followed by conjugation of miR-503 oligonucleotides as recognized regulators of angiogenesis. We demonstrated a reduced toxicity for both polymer-coated CNTs, compared with pristine CNTs or polymers alone. Moreover, polymer-coated CNT stabilized miR-503 oligonucleotides and allowed their efficient delivery to ECs. The functionality of PAMAM-CNT-miR-503 complexes was further demonstrated in ECs through regulation of target genes, cell proliferation and angiogenic sprouting and in a mouse model of angiogenesis. This comprehensive series of experiments demonstrates that the use of polyamine-functionalized CNTs to deliver miRNAs is a novel and effective means to regulate angiogenesis.

Multiwalled carbon nanotube buckypaper induces cell cycle arrest and apoptosis in human leukemia cell lines through modulation of AKT and MAPK signaling pathways.

MWCNT buckypaper (BP) shows physico-chemical and mechanical properties that make it potentially useful as a substrate in nano-bio interface research including in tissue engineering. When used as a scaffold material, BP comes into contact with host cells and surrounding tissues; therefore it is critical to determine its biocompatibility and interaction with living systems. The aim of this study was to investigate BP effects on cell growth, apoptosis and reactive oxygen species (ROS) production in three human leukemia cell lines HL-60, U-937 and K-562. BP was able to induce both the reduction of cell proliferation, associated with an arrest in G0/G1 phase of cell cycle and the increase of apoptosis in leukemic cell lines, thus exerting both cytostatic and cytotoxic effects. The growth inhibitory effect was likely mediated by the decrease of cyclins D, E, A, B1 levels and CDK4 expression; meanwhile, the apoptotic effect, not mediated by ROS production, was presumably due to the combined action of the survival and pro-apoptotic AKT and MAPK signal transduction pathways. These results raised the issue of biocompatibility of MWCNT BP for the creation of carbon nanotubes based scaffolds to utilize as prostheses in tissue engineering.

Growth inhibition, cell-cycle alteration and apoptosis in stimulated human peripheral blood lymphocytes by multiwalled carbon nanotube buckypaper.

AIM: This study was designed to investigate the cytotoxicity of multiwalled carbon nanotube buckypaper (BP) in stimulated human peripheral blood lymphocytes. Materials & methods & results: BP treatment led to a delay in the cell growth, as proven by a minor increase in the cell number over time relative to that seen in untreated cells, assessed by trypan blue, resazurin and neutral red assays. The analysis of cell-cycle profile, by propidium iodide staining, indicated that BP treatment blocked cell-cycle progression by arresting cells at the G0/G1 phase. Moreover, increased apoptosis was also recorded by Annexin V-fluorescein isothiocyanate/propidium iodide staining. CONCLUSION: The results presented here demonstrate an inhibitor effect of BP on cell growth that was likely through cytostatic and cytotoxic events.

Micro-Raman study of the role of sterilization on carbon nanotubes for biomedical applications.

AIM: We investigate the effect of four different types of sterilization procedures on the structural properties and morphological features of single-wall carbon nanotube samples approachable by micro-Raman spectroscopy. Sterilization procedures (treatment in humid heat autoclave or ethylene oxide and irradiation with gamma-rays or UV light) are necessary in view of the use of carbon nanotube sterile samples in in vivo toxicity tests on laboratory rats. Micro-Raman spectroscopy allows us to estimate several details about the morphology of the single-wall carbon nanotube mixture (mainly the presence of disorder and diameter distribution) before and after the sterilization treatment. RESULTS: The best of these treatments, in other words, the one that least affected the morphology and structural properties of carbon nanotubes, was found to be UV irradiation and has thus been selected for future in vivo tests on rats.