One-Step Ionic Liquid-Assisted Electrochemical Synthesis of Ionic Liquid-Functionalized Graphene Sheet Directly from Graphite

Graphite, inexpensive and available in large quantities, unfortunately does not readily exfoliate to yield individual graphene sheets. Here a mild, one-step electrochemical approach for the preparation of ionic-liquid-functionalized graphite sheets with the assistance of an ionic liquid and water is presented. These ionic-liquid-treated graphite sheets can be exfoliated into functionalized graphene nanosheets that can not only be individuated and homogeneously distributed into polar aprotic solvents, but also need not be further deoxidized. Different types of ionic liquids and different ratios of the ionic liquid to water can influence the properties of the graphene nanosheets. Graphene nanosheet/polystyrene composites synthesized by a liquid-phase blend route exhibit a percolation threshold of 0.1 vol % for room temperature electrical conductivity, and, at only 4.19 vol %, this composite has a conductivity of 13.84 S m(-1), which is 3-15 times that of polystyrene composites filled with single-walled carbon nanotubes.

New Organic Sensitizer for Stable Dye-Sensitized Solar Cells with Solvent-Free Ionic Liquid Electrolytes

We report a high molar extinction coefficient metal-free sensitizer composed of a triarylamine donor in combination with the 2-(2,2'-bithiophen-5-yl)acrylonitrile conjugation unit and cyanoacrylic acid as an acceptor. In conjugation with a volatile acetonitrile-based electrolyte or a solvent-free ionic liquid electrolyte, we have fabricated efficient dye-sensitized solar cells showing a corresponding 7.5% or 6.1% efficiency measured under the air mass 1.5 global sunlight. The ionic liquid cell exhibits excellent stability during a 1000 h accelerated test under the light-soaking and thermal dual stress. Intensity-modulated photocurrent and photovolatge spectroscopies were employed along with the transient photoelectrical decay measurements to detail the electron transport in the mesoporous titania films filled with these two electrolytes.

Dewetting behavior of polystyrene film filled with (C6H5C2H4NH3)(2)PbI4

The dewetting behavior of thin (about 30 nm) polystyrene (PS) films filled with different amount of (C6H5C2H4NH3)(2)PbI4 (PhE-PbI4) on the silicon substrate with a native oxide layer was investigated. For different additive concentrations, PhE-PbI4 showed different spatial distributions in the PS films, which had a strong influence on the film wettability, dewetting dynamics, and mechanism. With 0.5 wt % additive, PhE-PbI4 formed a noncontinuous diffusion layer, which caused a continuous hole nucleation in the film. With about 1 wt % additive, a continuous gradient distribution layer of PhE-PbI4 formed in the film, which inhibited the dewetting.

A reversibly tunable colloidal photonic crystal via the infiltrated solvent liquid-solid phase transition

A reversibly tunable colloidal photonic crystal between two stop bands was realized by a liquid-solid phase transition of liquid infiltrated into the air voids of silica opals. The difference of the peak wavelengths of the two stop bands was dependent on the diameter of the silica opals and the difference of the refractive index of the filled solvent between the solid and liquid state. The reversibly tunable photonic crystals have good stability and reproducibility.

Studies on charge transfer across the micro-liquid/liquid interface supported at a double-barrel micropipette

In this paper, the charge transfer across the micro-liquid/liquid interface supported at the orifice of a double-barrel micropipette, namely, a theta-pipette, is reported. Simple ion transfer(TMA(+)), facilitated ion transfer (potassium ion transfer facilitated by DB18C6), and electron transfer (ferrocene and ferri/ferrocyanide system) have been investigated by cyclic voltammetry. The experimental results show that a very thin aqueous film, linking both barrels filled with the aqueous solution and the organic solution respectively, can spontaneously be formed on the outer glass surface of such a double-barrel micropipette to construct a micro-liquid/liquid interface, which provides the asymmetry of diffusion field. Such device is demonstrated experimentally which can be employed as one of the simplest electrochemical cells to investigate the charge transfer across the liquid/liquid interface.

Facilitated ion transfer across the micro-liquid /liquid interface supported at the tip of a silanized micropipette

Glass micropipettes with silanized inner walls can be filled with an organic solvent for voltammetric measurements in an aqueous solution. This arrangement was employed to investigate systematically the mechanism of facilitated potassium ion transfer by an ionophore dibenzo-18-crown-6 (DB18C6) across a micro-water/1.2-dichloroethane(W/DCE) interface supported at the tip of a silanized micropipette. Our experimental results verify that this facilitated ion transfer across the liquid/liquid interface did occur by an interfacial complexation-dissociation process (TIC-TID mechanism). The ratio of the diffusion coefficient of DB18C6 to that of its complexed ion in the DCE phase was calculated to be 1.74 +/- 0.07.

The rheological and extrusion behaviour of blends based on phenolphthalein poly(ether-ether-sulfone) and thermotropic liquid crystalline polymer

A novel engineering thermoplastic, phenolphthalein poly (ether-ether-sulfone) (PES-C) was blended with a commercial thermotropic liquid crystalline polymer(TLCP), Vectra A950, up to 30 weight percent of TLCP. A rheometrics dynamic spectrometer (RDS-I) and a CEAST capillary rheometer, a rheoscope 1000 were employed to investigate the melt rheology and extrusion behaviour at both the low and high shearing rates. The morphologies of the blends under different shearing were observed with a scanning electron microscope(SEM) and correlated to the observed rheology. The principal normal stress differences measured with cone-and-plate geometry give a temperature-independent correlation for both blend and PES-C when they are plotted against shear stress. But the extrudate swell of the blends showed a strong temperature dependence at each shear stress. The concentration dependence of extrudate swell shows a contrary behaviour to that of the inorganic filled system. A reasonable hypothesis based on the relaxation and disorientation of TLCP during flowing in the capillary and exiting was given to explain it. The melt fracture was checked after extrusion from capillary and was discussed.

Liquid metal turbulent flow dynamics in a cylindrical container with free surface: experiment and numerical analysis

The liquid metal flow in induction crucible models is known to be unstable, turbulent and difficult to predict in the regime of medium frequencies when the electromagnetic skin-layer is of considerable extent. We present long term turbulent flow measurements by a permanent magnet incorporated potential difference velocity probe in a cylindrical container filled with eutectic melt In-Ga-Sn. The parallel numerical simulation of the long time scale development of the turbulent average flow is presented. The numerical flow model uses an implicit pseudo-spectral code and k-w turbulence model, which was recently developed for the transitional flow modelling. The results compare reasonably to the experiment and demonstrate the time development of the turbulent flow field and the turbulence energy.

Liquid metal turbulent flow dynamics in a cylindrical container with free surface: experiment and numerical analysis

The liquid metal flow in inducation crucible models is known to be higly unstable and turbutlen in the regim e of medium frequecies when the elctronmagnetic skin-layer is of considerable extent. We present long term turbulent flow measurements by a permanent magnet incorporated potential difference veolocity probe in a cylindirical container filled with eutecti mlt In-Ga-SN. The parallel numerical simulation of the long time scale development of the turbulen average flow is presented. The numerical lfow model uses a pseud-spectral code and k-w turbulence model, which was recently developed for the transitional flow modelling. The result compare reasonably to the experiment and demonstrate the time development of the turbulent flow field.

Levitated liquid droplets in AC and DC magnetic field

Electromagnetic levitation of liquid metal droplets can be used to measure the properties of highly reactive liquid materials. Two independent numerical models, the commercial COMSOL and the spectral-collocation based free surface code SPHINX, have been applied to solve the transient electromagnetic, fluid flow and thermodynamic equations, which describe the levitated liquid motion and heating processes. The SPHINX model incorporates free surface deformation to accurately model the oscillations that result from the interaction between the electromagnetic and gravity forces, temperature dependent surface tension, magnetically controlled turbulent momentum transport. The models are adapted to incorporate periodic laser heating at the top of the droplet, which is used to measure the thermal conductivity of the material. Novel effects in the levitated droplet of magnetically damped turbulence and nonlinear growth of velocities in high DC magnetic field are analysed.

Magnetic damping of levitated liquid droplets in AC and DC field

The intense AC magnetic field required to produce levitation in terrestrial conditions, along with the buoyancy and thermo-capillary forces, results in turbulent convective flow within the droplet. The use of a homogenous DC magnetic field allows the convective flow to be damped. However the turbulence properties are affected at the same time, leading to a possibility that the effective turbulent damping is considerably reduced. The MHD modified K-Omega turbulence model allows the investigation of the effect of magnetic field on the turbulence. The model incorporates free surface deformation, the temperature dependent surface tension, turbulent momentum transport, electromagnetic and gravity forces. The model is adapted to incorporate a periodic laser heating at the top of the droplet, which have been used to measure the thermal conductivity of the material by calculating the phase lag between the frequency of the laser heating and the temperature response at the bottom. The numerical simulations show that with the gradual increase of the DC field the fluid flow within the droplet is initially increasing in intensity. Only after a certain threshold magnitude of the field the flow intensity starts to decrease. In order to achieve the flow conditions close to the ‘laminar’ a D.C. magnetic field >4 Tesla is required to measure the thermal conductivity accurately. The reduction in the AC field driven flow in the main body of the drop leads to a noticeable thermo-capillary convection at the edge of the droplet. The uniform vertical DC magnetic field does not stop a translational oscillation of the droplet along the field, which is caused by the variation in total levitation force due to the time-dependent surface deformation.

Electrically switchable nonreciprocal transmission of plasmonic nanorods with liquid crystal

The electro-optic response of a cell consisting of a thin layer of liquid crystal deposited onto gold nanorods embedded in thin film alumina with a transparent top electrode has been investigated. For p-polarized light incident from the liquid crystal side, the extinction peak associated with the nanorod longitudinal plasmon resonance is completely suppressed. The peak could be recovered by applying an external electric field parallel to the long axis of the nanorods. No extinction peak suppression is observed when the light was incident from the nanorod side of the cell. The effect is explained by polarization properties of liquid crystal.

Flow patterns and pressure drop of ionic liquid-water two-phase flows in microchannels

The two-phase flow of a hydrophobic ionic liquid and water was studied in capillaries made of three different materials (two types of Teflon, FEP and Tefzel, and glass) with sizes between 200µm and 270µm. The ionic liquid was 1-butyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}amide, with density and viscosity of 1420kgm and 0.041kgms, respectively. Flow patterns and pressure drop were measured for two inlet configurations (T- and Y-junction), for total flow rates of 0.065-214.9cmh and ionic liquid volume fractions from 0.05 to 0.8. The continuous phase in the glass capillary depended on the fluid that initially filled the channel. When water was introduced first, it became the continuous phase with the ionic liquid forming plugs or a mixture of plugs and drops within it. In the Teflon microchannels, the order that fluids were introduced did not affect the results and the ionic liquid was always the continuous phase. The main patterns observed were annular, plug, and drop flow. Pressure drop in the Teflon microchannels at a constant ionic liquid flow rate, was found to increase as the ionic liquid volume fraction decreased, and was always higher than the single phase ionic liquid value at the same flow rate as in the two-phase mixture. However, in the glass microchannel during plug flow with water as the continuous phase, pressure drop for a constant ionic liquid flow rate was always lower than the single phase ionic liquid value. A modified plug flow pressure drop model using a correlation for film thickness derived for the current fluids pair showed very good agreement with the experimental data. © 2013 Elsevier Ltd.

Translating proteomics into environmental health : biomarkers discovery for tobacco smoke-induced biological damage

Tese de doutoramento, Biologia (Biologia Molecular), Universidade de Lisboa, Faculdade de Ciências, 2015

Novel optical PVC probes for on-site detection/determination of fluoroquinolones in a solid/liquid interface: Application to the determination of Norfloxacin in aquaculture water

A novel optical disposable probe for screening fluoroquinolones in fish farming waters is presented, having Norfloxacin (NFX) as target compound. The colorimetric reaction takes place in the solid/liquid interface consisting of a plasticized PVC layer carrying the colorimetric reagent and the sample solution. NFX solutions dropped on top of this solid-sensory surface provided a colour change from light yellow to dark orange. Several metals were tested as colorimetric reagents and Fe(III) was selected. The main parameters affecting the obtained colour were assessed and optimised in both liquid and solid phases. The corresponding studies were conducted by visible spectrophotometry and digital image acquisition. The three coordinates of the HSL model system of the collected image (Hue, Saturation and Lightness) were obtained by simple image management (enabled in any computer). The analytical response of the optimised solid-state optical probe against concentration was tested for several mathematical transformations of the colour coordinates. Linear behaviour was observed for logarithm NFX concentration against Hue+Lightness. Under this condition, the sensor exhibited a limit of detection below 50 μM (corresponding to about 16 mg/mL). Visual inspection also enabled semi-quantitative information. The selectivity was ensured against drugs from other chemical groups than fluoroquinolones. Finally, similar procedure was used to prepare an array of sensors for NFX, consisting on different metal species. Cu(II), Mn(II) and aluminon were selected for this purpose. The sensor array was used to detect NFX in aquaculture water, without any prior sample manipulation.