Correlation of Ac-impedance and in situ X-ray spectra of LiCoO2

In-situ X-ray and AC-impedance spectra have been obtained simultaneously during the deintercalation of lithium from LiCoO2 using a specially designed electrochemical cell. The AC-dispersions have been correlated with the cell parameters obtained from the X-ray spectra. The correlation confirms previous hypothesis on the interpretation of the AC-dispersions in terms of an equivalent circuit comprising an element that relates the change of the intrinsic electronic conductivity, occurring at the early stages of deintercalation, to the semiconductor to metal transition caused by the change of the cell parameters

Local structure of liquid and solid silver halides probed by XAFS.

Investigation of the local structure of the high-temperature liquid and solid phases in the 300-725 K range of AgBr has been performed using the x-ray absorption spectroscopy (XAS). Structural results are compared with existing diffraction studies and computer simulations demonstrating the reliability of the XAS technique in determining the short-range structure. Present results on solid AgBr are in agreement with known thermal expansion data. The short-range g(r) of liquid AgBr is reconstructed showing the unique insight provided by the XAS technique in measuring short-range atom-atom correlations in liquids

Band Gap Implications on Nano-TiO2 Surface Modification with Ascorbic Acid for Visible Light-Active Polypropylene Coated Photocatalyst

The effect of surface modification using ascorbic acid as a surface modifier of nano-TiO2 heterogeneous photocatalyst was studied. The preparation of supported photocatalyst was made by a specific paste containing ascorbic acid modified TiO2 nanoparticles used to cover Polypropylene as a support material. The obtained heterogeneous photocatalyst was thoroughly characterized (scanning electron microscope (SEM), RAMAN, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), and Diffuse Reflectance Spectra (DRS) and successfully applied in the visible light photodegradation of Alizarin Red S in water solutions. In particular, this new supported TiO2 photocatalyst showed a change in the adsorption mechanism of dye with respect to that of only TiO2 due to the surface properties. In addition, an improvement of photocatalytic performances in the visible light photodegration was obtained, showing a strict correlation between efficiency and energy band gap values, evidencing the favorable surface modification of TiO2 nanoparticles

Thermodynamic assessment and microscale Raman spectroscopy of binary CO2/CH4 hydrates produced during replacement applications in natural reservoirs

The present research deals with the micro – scale characterization of sI hydrates containing a binary mixture of methane and carbon dioxide. The application of replacement strategies in natural hydrate reservoirs, always leads to the formation of “mixed” hydrates, whose mechanical and chemical properties are different from those of pure CH4 and CO2 hydrates. As a function of the technique used for the process and due to the variability of the systems, a wide range of different compositions and morphologies can be obtained and the current literature must be expanded, in order to achieve a wide and accurate experimental database of CO2/CH4 hydrate properties. In this work, binary CO2/CH4 hydrates binary CO2/CH4 hydrates were produced in a small – scale reactor and then supercooled, in order to favour their extraction from the reactor and their stability at environmental conditions for a certain period of time. The gas hydrates, prepared with CO2 hydrates of pure water and with CH4 and CO2 mixtures, also in the presence of specific sands, were ex situ analysed by the use Raman-spectroscopy that confirmed the gas uptake in the hydrate structures by identification of the fingerprint of CH4 and CO2 occupancy in the hydrates. The characteristic of water inside the gas hydrates and the interaction between the host molecules and the lattice of water molecules was clarified. The different gas hydrates, analysed by Field Emission Scanning Electron Microscopy instrument equipped with “Coolstage head” under high vacuum condition, differed in morphology and surface features. The analysis of water Raman spectra of the different GHs permitted to describe the relation between symmetric and asymmetric OHs bands, but also provided information about the characteristics of water inside the different GHs, showing that the least ordered water structure was that of GHs containing sand, while the most ordered one was present on binary CO2/CH4 hydrates

From TiO2 and Graphite to Graphene doped TiO2 for visible light photocatalytic degradation of refractory dye.

Graphene production is an ongoing challenge for large-scale applications. Many processes are used to produce graphene 1. Top-down method such as the exfoliation of graphite powder in liquid phase by sonication is a promising route to create high quality graphene in great quantity due to its simplicity, its versatility and its low-cost 2. Graphene with the thickness of a single carbon atom owns unique physical and chemical properties like large surface area, highly flexible structure, high electrical and thermal conductivity and high chemical stability 3. With these properties, graphene is an attractive material in applications that require a fast electron transfer, such as photocatalysis. In fact, graphene based semiconductor nanocomposites are considered as good photocatalyst for pollutant degradation 4. Graphene is an ideal nanomaterial for doping TiO2 because the formation of Ti-O-C bonds extend the visible light absorption of TiO2. Furthermore, electrons are easily transported from TiO2 to graphene nano-sheets and the electron-hole recombination is reduced; this is enhances the oxidative reactivity 5. In this work, graphene doped TiO2 nanocomposite was used as photocatalytic materials for the Alizarin Red S degradation in water solutions. Graphene dispersions were prepared by liquid-phase exfoliation of graphite in the presence of a non-ionic surfactant, Triton X-100. The obtained graphene dispersion was characterized by X-Ray Diffraction, Dynamic Light Scattering and UV-Visible spectroscopy and was subsequently used for the preparation of graphene doped-TiO2 photocatalyst. Graphene doped-TiO2 nanocomposites showed higher adsorption of Alizarin Red S on the catalyst surface and higher photocatalytic activity for its degradation under visible light irradiation, respect to those obtained with pure TiO2 6. References: 1) Dimiev, A. M.; Tour, J. M. ACS Nano, 2014, 8, 3060 - 3068. 2) Samorì, P. et al. Chemical Society Reviews, 2014, 43, 381 - 398. 3) Geim, A.K.; Novoselov, K. S. Nature Materials, 2007, 6, 183 - 191. 4) Khalid, N. R.; Hong, Z. et al. Current Applied Physics, 2013, 13, 659 - 663. 5) Li, F.; Cheng, H. M. et al. Advanced Functional Materials, 2011, 21, 1717 - 1722. 6) Giovannetti, R.; D’ Amato, C. A. et al. Scientific Reports, 2015, 5, 17801

May sediments affect the inhibiting properties of NaCl on CH4 and CO2 hydrates formation? an experimental report.

The equilibria of methane and carbon dioxide clathrate hydrates were measured in presence of a pure-quartz porous sand, with and without NaCl. Two different salt concentrations were tested: 0.030 and 0.037 wt%. Results were compared with phase equilibrium data already present in literature for these species. Despite salt, the porous medium was found to promote the process, mainly for the increased surface/volume ratio and for the improved heat transfer. In presence of salt, sand affected the process differently as a function of temperature: at values higher than 3 – 5 °C, it promoted the process, while for values lower than this range, but still greater than the ice-point, it acted as an inhibitor. However, these results can be considered true only for temperatures above the ice point. Due to similarity of ice water with clathrate hydrates, Raman microscale measurements were performed to gather information about the influence of sediments, salt, and temperature on OH-stretching vibrations of water. The obtained results allowed to clarify how the addition of NaCl, and or sediments to liquid water, under different temperature conditions (15 °C and −15 °C), influenced the water hydrogen bonds. Specifically, the changes of OH-stretching vibrations, when correlated with the NaCl concentrations, demonstrated that the presence of sediments partially inhibited the salt effects in the ice water probably due to hydrophilic interactions with the silanol groups of sediments. SEM measurements showed morphological information on sediments and on ice in different experimental conditions

Development of a New Hyaluronic Acid Based Redox-Responsive Nanohydrogel for the Encapsulation of Oncolytic Viruses for Cancer Immunotherapy

Oncolytic viruses (OVs) are emerging as promising and potential anti-cancer therapeutic agents, not only able to kill cancer cells directly by selective intracellular viral replication, but also to promote an immune response against tumor. Unfortunately, the bioavailability under systemic administration of OVs is limited because of undesired inactivation caused by host immune system and neutralizing antibodies in the bloodstream. To address this issue, a novel hyaluronic acid based redox responsive nanohydrogel was developed in this study as delivery system for OVs, with the aim to protect the OVs following systemic administration. The nanohydrogel was formulated by water in oil (W/O) nanoemulsion method and cross-linked by disulfide bonds derived from the thiol groups of synthesized thiolated hyaluronic acid. One DNA OV Ad[I/PPT-E1A] and one RNA OV Rigvir® ECHO-7 were encapsulated into the developed nanohydrogel, respectively, in view of their potential of immunovirotherapy to treat cancers. The nanohydrogels showed particle size of approximately 300–400 nm and negative zeta potential of around −13 mV by dynamic light scattering (DLS). A uniform spherical shape of the nanohydrogel was observed under the scanning electron microscope (SEM) and transmission electron microscope (TEM), especially, the successfully loading of OV into nanohydrogel was revealed by TEM. The crosslinking between the hyaluronic acid chains was confirmed by the appearance of new peak assigned to disulfide bond in Raman spectrum. Furthermore, the redox responsive ability of the nanohydrogel was determined by incubating the nanohydrogel into phosphate buffered saline (PBS) pH 7.4 with 10 μM or 10 mM glutathione at 37 °C which stimulate the normal physiological environment (extracellular) or reductive environment (intracellular or tumoral). The relative turbidity of the sample was real time monitored by DLS which indicated that the nanohydrogel could rapidly degrade within 10 h in the reductive environment due to the cleavage of disulfide bonds, while maintaining the stability in the normal physiological environment after 5 days. Additionally, in vitro cytotoxicity assays demonstrated a good oncolytic activity of OVs-loaded nanohydrogel against the specific cancer cell lines. Overall, the results indicated that the developed nanohydrogel is a delivery system appropriate for viral drugs, due to its hydrophilic and porous nature, and also thanks to its capacity to maintain the stability and activity of encapsulated viruses. Thus, nanohydrogel can be considered as a promising candidate carrier for systemic administration of oncolytic immunovirotherap