Electrochemical behaviour of Nafion®+cupromeronic phthalocyanine films

The surface of indium tin oxide (ITO) and graphite+polymer composite electrodes can be modified by Nafion^® films containing a little amount of dispersed electroactive substances, such as phthalocyanines. This procedure allows electroanalytical information on the electroactive deposited substance to be obtained. The preparative methods of these type of modified electrodes are discussed from voltammetric results in this work. The proposed equivalent circuit explains the voltammetric differences between these electrodes. The Nafion^® net acts as a permeable membrane to the hydrogen ions. Besides, the presence of methylviologen within the Nafion^® film makes the electron transport throughout this membrane easy.     

Electrochemical behaviour of self-assembly multilayer films based on iron-substituted α-Keggin polyoxotungstates

Ultrathin multilayer films containing metal-substituted polyoxometalates, [PW₁₁Fe^III(H₂O)O₃₉]⁴⁻ (PW₁₁Fe) or [SiW₁₁Fe^III(H₂O)O₃₉]⁵⁻ (SiW₁₁Fe), and poly(ethylenimine) (PEI) were prepared by the electrostatic layer-by-layer self-assembly method on a glassy carbon electrode. The multilayer films were characterized by cyclic voltammetry and scanning electron microscopy and UV-Vis absorption spectroscopy on a quartz slide was used to monitor film growth. Cyclic voltammetry indicates that the electrochemical properties of the polyoxometalates are completely maintained in the multilayer films, and the influence of scan rate on the voltammetric features showed that the first tungsten reduction process for immobilized PW₁₁Fe and SiW₁₁Fe is a surface-confined process. Studies with [Fe(CN₆)]^3−/4− as electrochemical probe showed that their permeability depends on the thickness of the multilayer films, if the outermost layer is negatively charged. Additionally, the (PEI/SiW₁₁Fe)_n multilayer films showed electrocatalytic properties towards nitrite reduction.     

Hydration of Nafion® studied by AFM and X-ray scattering

Nafion® is a commercially available perfluorosulphonate cation exchange membrane commonly used as a perm-selective separator in chlor-alkali electrolysers and as the electrolyte in solid polymer fuel cells. This usage arises because of its high mechanical, thermal and chemical stability coupled with its high conductivity and ionic selectivity, which depend strongly on the water content. The membrane was therefore studied in different states of hydration with two complementary techniques: atomic force microscopy (AFM) and small angle X-ray scattering (SAXS) combined with a maximum entropy (MaxEnt) reconstruction. Tapping mode phase imaging was successfully used to identify the hydrophobic and hydrophilic regions of Nafion. The images support the MaxEnt interpretation of a cluster model of ionic aggregation, with spacings between individual clusters ranging from 3 to 5 nm, aggregating to form cluster agglomerates with sizes from 5 to 30 nm. Both techniques indicate that the number density of ionic clusters changes as a function of water content, and this explains why the bulk volumetric swelling in water is observed to be significantly less than the swelling inferred from scattering measurements.     

Electrochemical deposition of polypyrrole–carbon nanotube films using steroid dispersants

Polypyrrole (PPR)–carbon nanotube (CNT) films were prepared by an electrodeposition method, combining PPR electropolymerization and anaphoresis of CNT. PPR polymerization experiments showed advantages of a dopant from the catechol family for the deposition of PPR films at reduced electrode potentials. The method allowed the formation of adherent films on stainless steel substrates. The amphiphilic molecules with steroid-like structures, such as carbenoxolone disodium salt, glycyrrhizic acid, ammonium salt, and sodium taurodeoxycholate, were used for dispersion and charging of CNT. The new dispersing agents showed outstanding dispersion ability. In addition to dispersing properties, electrodeposition experiments revealed film-forming properties of carbenoxolone and ability to form pure carbenoxolone or carbenoxolone–CNT films. The PPR–CNT films formed using carbenoxolone disodium salt, glycyrrhizic acid ammonium salt, and sodium taurodeoxycholate showed diverse microstructural features. The dispersion and deposition mechanisms were discussed.     

Preparation and characterization of self-assembled organic–inorganic nacre-like nanocomposite thin films

The SiO₂/Poly(DMCB) nanocomposite thin films were prepared by supermolerculer self-assembly method on glass substrate. In the nanocomposite thin films, the surfactant DMCB was used as both structure-directing agents and poly monomers. The structures of the films were characterized using FT-IR, XRD and TEM. The results indicated that the films were composed of organic and inorganic layers with orderly interlaced arrangement and the distance between organic layer and inorganic layer was 3.48 nm before polymerization and 2.84 nm after polymerization, respectively.     

Dynamic electrostatic charge of lactose-salbutamol sulphate powder blends dispersed from a Cyclohaler®

Context: Electrostatic forces have been claimed to be a mechanism for aerosol deposition in the lungs. However, the extent of its influence on aerosol performance is not clear, particularly for carrier-drug formulations.

Objectives: To prepare lactose-salbutamol powder blends, varying in blend ratio, and identify any relationships between salbutamol dose, electrostatic characteristics and in vitro aerosol performance.

Methods: Decanted lactose and micronized salbutamol sulfate was mixed to produce five blends (equivalent to 50, 100, 200, 300 and 400 µg salbutamol per 33?mg of powder). 33?±?1?mg of a blend was loaded into a Cyclohaler? and dispersed into the electrical Next Generation Impactor (eNGI) at an air flow rate of 60?L/min. This was conducted in triplicate for all five lactose-salbutamol blends.

Results: Fine particle fraction increased with salbutamol dose, from 5.89?±?1.42 to 21.35?±?2.91%. Specific charge (charge divided by mass) distributions for each blend were greatest in magnitude for the 50 µg blend and similar in magnitude between all other blends. However, in eNGI Stage 1 (>8.06?µm), specific charge decreased from 100 µg (?170.4?±?45.8 pC/µg) to 400 µg (?10.0?±?9.1 pC/µg).

Conclusions: The improvement in fine particle fraction with increased salbutamol dose was indicative of fine drug binding to high and low energy sites on the lactose carrier surface. This finding was supported by electrostatic charge results, but the aerosol charge itself was not found to influence aerosol performance by electrostatic forces.     

Electrochemical behaviour of iron—chrome alloys in relation to pitting corrosion

The polarization behaviour and pitting corrosion of Fe-Cr alloys of 7, 13, 18, 24 wt% Cr were studied. Potentiodynamic and galvanostatic measurements were performed in the absence and presence of Cl^–. As the Cr content increases the active dissolution current densities decrease while the passive range and transpassive current densities increase. Polarization parameters gave for the passive transition of the alloys a Cr concentration of -13%. An increase of Cl^– concentration causes the progressive destruction of passivity. It interfered with O₂ evolution, and then destroyed the transpassive region. Still higher Cl^– concentrations initiated pitting corrosion as shown by the oscillations in potential of the galvanostatic polarization curves supported by visual observation. Results are discussed on the basis of competitive adsorption between the aggressive and inhibitor anions for the active sites on the alloys' surface.     

Electrical transport behaviour of silver–PMMA nanocomposite films at low temperature

In this study, the silver nanoparticles, capped with oleylamine, were embedded in polymethylmethacrylate (PMMA) using sonication to fabricate Ag–PMMA nanocomposites. The well-dispersed nanocomposite samples are analysed using UV-Vis absorption spectroscopy, atomic force microscopy and small angle X-ray scattering. The interfacial interaction of Ag nanoparticles and PMMA polymer is investigated using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. It is concluded that a ligand-exchange process occurs when capped silver nanoparticles are incorporated in PMMA polymer. Electrical resistivity of nanocomposite samples was measured by a four-probe technique in the 70–300?K range. The nanocomposites showed a transition with onsets at ～230 and ～160?K. They exhibited a semiconductor-like conductivity at higher temperatures, a rapid metallic conductivity at middle range and nearly temperature independent conductivity at lower temperatures.     

Investigation into The Yellowing on Aging of Sabril® Tablet Cores

Abstract

Uncoated Sabril® tablet cores under long term storage become slightly discolored from the initial white to a yellowish off-white color. In order to ensure the aesthetics of the product, Sabril tablet cores are film coated with an opaque white coating. The nature of this yellowing reaction was of interest even though discolored tablets showed no significant loss of potency on assay. Excipient compatibility studies showed that the vigabatrin active in Sabril mixed with Avicel (microcrystalline cellulose) in the presence of moisture also became off-colored when stressed at elevated temperatures.

The nature of the discoloration in aged Sabril core tablets was investigated. Chromatographic and spectroscopic data indicate that the source of this color comes from the Maillard Reaction between vigabatrin and Avicel which results in a multitude of products analogous to “browning reactions” of food products. A gravimetric determination of the leached colored products from 7 year old Sabril core tablets gave a residue of less than 0.1% relative to vigabatrin. Furthermore, based on spectroscopy, most of this residue was found to be povidone, an excipient in the tablets which was isolated along with the colored substances.

Therefore, the colored products identified in the core of Sabril tablets stored for an extended period of time represent only minor impurities. Their formation through aging arises via the Maillard Reaction and would only constitute a matter of aesthetics. The latter problem is avoided by the currently employed film coating process.

Similar reactions could be predicted for other drugs having amine functional groups if they are formulated with microcrystalline cellulose or reducing sugars.     

Intercalation of nitrogenous substances into HUO2PO4·4H2O

The laminar compound HUO₂PO₄·4H₂O (HUP) interacts with piperidine, hydrazine, pyridine, pyrazine and (dimethylamino-methyl)ferrocene to produce intercalation reactions. The intercalate materials exhibit a layered structure derived from the starting solid. The only observed structural modifications were dimensional changes in the crystal c axes.The amount of adsorbate taken up by the HUP is related to the size and geometry of the guest molecule and its basicity. The guest-host reactions are of the acid-base type as shown by i.r. spectra.     

Polymer/surfactant assisted self-assembly of nanoparticles into Langmuir–Blodgett films

We studied the ability of poly(octadecene-co-maleic anhydride) (PMAO) and a Gemini surfactant [C₁₈H₃₇ (CH₃)₂N⁺Br⁻–(CH₂)₂–N⁺Br⁻(CH₃)₂ C₁₈H₃₇] (18-2-18) to assist in the self-assembly process of CdSe quantum dots (QDs) at the air–water interface. Results show that, while QD agglomeration is generally inhibited by the addition of these components to the Langmuir monolayer of QDs, structure of the film transferred onto mica by the Langmuir–Blodgett method is strongly affected by the dewetting process. Nucleation-and-growth of holes and spinodal-like dewetting were respectively observed in the presence of either PMAO or 18-2-18. When PMAO/18-2-18 mixtures were used, both mechanisms were allowed; nevertheless, even in films prepared with mixtures of low polymer contents, characteristic morphology from the polymer dewetting route prevailed.     

Atomic/molecular layer deposition of hybrid inorganic–organic thin films from erbium guanidinate precursor

Luminescent erbium-based inorganic–organic hybrid materials play an important role in many frontier nano-sized applications, such as amplifiers, detectors and OLEDs. Here, we demonstrate the possibility to fabricate high-quality thin films comprising both erbium and an appropriate organic molecule as a luminescence sensitizer utilizing the combined atomic layer deposition and molecular layer deposition (ALD/MLD) technique. We employ tris(N,N′-diisopropyl-2-dimethylamido guanidinato)erbium(III) [Er(DPDMG)₃] together with 3,5-pyridine dicarboxylic acid as precursors. With the appreciably high film deposition rate achieved (6.4 Å cycle^?1), the guanidinate precursor indeed appears as an interesting new addition to the ALD/MLD precursor variety toward novel materials. Our erbium–organic thin films showed highly promising UV absorption properties and a photoluminescence at 1535 nm for a 325-nm excitation, relevant to possible future luminescence applications.     

Block copolymer assisted self-assembly of nanoparticles into Langmuir–Blodgett films: Effect of polymer concentration

We propose to use the self-assembly ability of a block copolymer to obtain CdSe quantum dots (QDs) structures of different morphology. The methodology proposed consist in transferring mixed Langmuir monolayers of QDs and the polymer poly (styrene-co-maleic anhydride) partial 2 buthoxy ethyl ester cumene terminated, PS-MA-BEE onto mica by the Langmuir–Blodgett (LB) methodology. The morphology of the LB films was analyzed by AFM and TEM measurements. Our results show that it is possible to modulate the self-assembly process by modifying the composition of the mixed Langmuir monolayer precursor of the LB film. The different morphologies are interpreted according to two different dewetting mechanisms, growth of holes and spinodal-like dewetting. The growth of holes dewetting process is driven by gravitatory effects and was observed for LB films obtained by transferring Langmuir monolayer of the smallest elasticity values in which the polymer is in brush conformation. The spinodal dewetting mechanism prevailed when the Langmuir monolayer presents the highest elasticity values.     

Dielectric behaviour of thin films of β-PVDF/PZT and β-PVDF/BaTiO3 composites

Thin films of the composites formed between poly(vinylidene fluoride) (PVDF) and lead zirconium titanate (PZT) and also barium titanate with 0–3 connectivity, have been obtained by dispersion of the ceramic powder in a solution of PVDF in dimethylacetamide DMA. Evaporation of the solvent at 65 °C allowed crystallization of PVDF predominantly in the polar phase, regardless of the amount of PZT or BaTiO₃ powder added upto 40 vol %. The relative permittivity and loss index values were determined for the pure components and for the composites with different ceramic contents, in the frequency range of 100 Hz to 13 MHz. An increase in PZT or BaTiO₃ content resulted in an increase in the relative permittivity of the composites, and the experimental results are shown to be in good agreement with those calculated from the theoretical expression of Yamada et al. [1]. The de electrical conductivity of composites with different compositions was also determined.     

Repelled from the wound,or randomly dispersed? Reverse migration behaviour of neutrophils characterized by dynamic modelling

Following neutralization of infectious threats, neutrophils must be removed from inflammatory sites for normal tissue function to be restored. Recently, a new paradigm has emerged, in which viable neutrophils migrate away from inflammatory sites by a process best described as reverse migration. It has generally been assumed that this process is the mirror image of chemotaxis, where neutrophils are drawn into the areas of infection or tissue damage by gradients of chemotactic cues. Indeed, efforts are underway to identify cues that drive neutrophils away by the reverse process, fugetaxis. By using photoconvertible pigments expressed in neutrophils in transparent zebrafish larvae, we were able to image the position of each neutrophil during inflammation resolution in vivo. These neutrophil coordinates were analysed within a dynamic modelling framework, using different forms of the drift–diffusion equation with model selection and parameter estimation based on approximate Bayesian computation. This analysis revealed the experimental data were best fitted by a model incorporating a diffusion term but no drift term—where the presence of drift would indicate fugetaxis. This result, for the first time, provides rigorous data-driven evidence that reverse migration of neutrophils in vivo is not a form of fugetaxis, but rather a stochastic redistribution.     

Electrochemical corrosion behaviour of ion-beam-mixed Fe-Al alloy: A conversion electron Mössbauer spectroscopic study

The electrochemical corrosion behaviour of ion-beam-mixed Fe-Al composites has been studied by using the technique of interface-sensitive conversion electron Mössbauer spectroscopy (CEMS). Polycrystalline aluminium foils deposited with a film 50 Å thick of the ⁵⁷Fe Mössbauer isotope and an overlayer 250 Å thick of natural iron have been bombarded with 100 keV Ar⁺ ions at a dose in the range of about (1–3)×10¹⁶ ions cm^-2 to induce atomic mixing at the interface. A number of as-deposited and ion-beam-mixed composites have been subjected to electrochemical corrosion treatment in a buffer solution by employing the three- sweep potentiokinetic polarization technique. It has been shown that the atomically mixed interface region exhibits corrosion behaviour considerably different from that exhibited by either iron or aluminium foils. The as-deposited as well as the ion-beam-mixed composites have been characterized by ⁵⁷Fe CEMS prior to the corrosive attack and after passivation so as to identify the structural state of the interface and the transformations occuring in the interface as a result of the corrosive reactions. The standard Mössbauer fitting procedure was used in conjunction with a method of obtaining hyperfine field distributions to establish that the corrosive action of the aqueous medium on the ion-beam-mixed Fe-Al composite leads to the elimination of the magnetic spectral components and to the growth of passive non-magnetic phases such as β-γ-FeOOH and FeO.     

Corrosion behaviour of amorphous Ni–Si thin films on AISI 304L stainless steel

Abstract

Nanoscale Ni – Si thin films are widely used in commercial microelectronic devices because of their promising electrical properties as well as their chemical stability. However, their application in corrosive environment has not been frequently addressed in the literature. In this study, amorphous Ni_0.66Si_0.33, Ni_0.40Si_0.60, and Ni_0.20Si_0.80 thin films are prepared on AISI 304L stainless steel by means of ion-beam sputter (IBS) deposition and their corrosion behaviour is studied using potentiodynamic polarisation measurements. The electrochemical measurements were conducted in 0.05M HCl solution at room temperature. By means of optical interferometer, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), the surface morphology and chemical composition of the thin films were examined before and after the electrochemical measurement. The evaluated results showed that the Ni–Si thin films may exhibit improved corrosion resistance over the 304L substrate provided that Si content is high enough to facilitate the formation of a Si-rich passive film.