National Institute Of Materials Physics - Romania

A dual strategy for the electrochemical detection for 20S proteasome (20S) is proposed, based on the oriented immobilization of a capture monoclonal antibody (Ab beta) on a self-assembled monolayer of 4-mercaptophenylboronic acid (4-MPBA) on gold electrodes, which led to the Au/4-MPBA/Ab beta immunosensor. The methodology comprises the correlation of 20S concentration with (i) its proteolytic activity toward the Z-LLE-AMC substrate, using the Au/4-MPBA/Ab beta/20S, and (ii) the enzymatic activity of an alkaline phosphatase (AlkP) from the AlkP-labeled secondary antibody (Ab(core)-AlkP), which involves the conversion of aminophenylphosphate to the electroactive aminophenol using Au/4-MPBA/Ab beta/20S/Ab(core)-AlkP. The step-by-step construction of the immunosensor and the interactions at its surface were evaluated by surface plasmon resonance and gravimetric analysis with quartz crystal microbalance, showing a high affinity between both antibodies and 20S. Morphological analysis by scanning electron microscopy demonstrated a pattern of parallel lines upon immobilization of Ab beta on 4-MPBA and morphological changes to a well-organized granular structure upon binding of 20S. A voltametric and impedimetric characterization was performed after each step in the immunosensor construction. The two detection strategies were evaluated. It was shown that the immunosensor responds linearly with 20S concentration in the range between 5 and 100 mu g mL(-1), which corresponds to proteasome levels in serum in the case of diverse pathological situations, and LoD values of 1.4 and 0.2 mu g mL(-1) were calculated for the detection strategies. The immunosensor was applied to the detection of 20S in serum samples with recovery values ranging from 101 to 103%.

We present hybrid nanomaterial architectures, consisting of carbon nanowalls (CNW) templates decorated with tungsten oxide nanoparticles, synthesized using a mechanism based on tungsten oxide sublimation, vapor transport, followed by vapor condensation, in the absence or presence of plasma. The key steps in the decoration mechanism are the sublimation of tungsten oxides, when are exposed in vacuum at high temperature (800 degrees C), and their redeposition on colder surfaces (400-600 degrees C). The morphology and chemical composition of the hybrid architectures, as obtained from Scanning Electron Microscopy and X-ray Photoelectron Spectroscopy, are discussed with respect to substrate nature and the physical conditions of synthesis. We pointed out that the decoration process is strongly dependent on the temperature of the CNW templates and plasma presence. Thus, the decoration process performed with plasma was effective for a wider range of template temperatures, in contrast with the decoration process performed without plasma. The results are useful for applications using the sensing and photochemical properties of tungsten oxides, and have also relevance for fusion technology, tungsten walls erosion and material redeposition being widely observed in fusion machines.

In this study, the cerium-doped hydroxyapatite (Ca10-xCex(PO4)(6)(OH)(2) with x(Ce) = 0.1, 10Ce-HAp) coatings obtained by the spin coating method were presented for the first time. The stability of the 10Ce-HAp suspension particles used in the preparation of coatings was evaluated by ultrasonic studies, transmission electron microscopy (TEM), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The surface morphology of the 10Ce-HAp coating was studied by SEM and atomic force microscopy (AFM) techniques. The obtained 10Ce-HAp coatings were uniform and without cracks or unevenness. Glow discharge optical emission spectroscopy (GDOES) and X-ray photoelectron spectroscopy (XPS) were used for the investigation of fine chemical depth profiling. The antifungal properties of the HAp and 10Ce-HAp suspensions and coatings were assessed using Candida albicans ATCC 10231 (C. albicans) fungal strain. The quantitative antifungal assays demonstrated that both 10Ce-HAp suspensions and coatings exhibited strong antifungal properties and that they successfully inhibited the development and adherence of C. albicans fungal cells for all the tested time intervals. The scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM) visualization of the C. albicans fungal cells adherence to the 10Ce-HAp surface also demonstrated their strong inhibitory effects. In addition, the qualitative assays also suggested that the 10Ce-HAp coatings successfully stopped the biofilm formation.

The azathioprine (AZA) electrochemical adsorption onto the screen-printed carbon electrodes (SPCE) modified with the reduced graphene oxide (RGO) sheets in the absence and in the presence of polyaniline-emeraldine salt (PANI-ES) is reported in this work. Using cyclic voltammetry(CV), in the case of the SPCE modified with the RGO sheets non-functionalized and functionalized with PANI-ES, respectively, an irreversible process at the electrode/electrolyte interface is highlighted to take place. In the case of the SPCE modified with the non-functionalized RGO sheets(SPCE-RGO), the oxidation-reduction processes induce an up-shift of the AZA Raman lines from 856 and 1011 cm(-1) to 863 and 1020 cm(-1), respectively. These variations indicate an AZA adsorption onto the surface of the SPCE modified with the RGO sheets that takes place throughtthe imidazole and pyrimidine cycles of mercaptopurine, when the generation of the pi-pi(*) bonds between the mercaptopurine structure and hexagonal carbon cycles of RGO occurs. The electrochemical functionalization of the RGO sheets with PANI-ES is proved bythe appearance of the Raman lines at 1165, 1332-1371, 1496 and 1585 and 1616 cm(-1). The oxidation-reduction processes induced at the interface of the SPCE modified with PANI-ES functionalized RGO sheets and the electrolyte consisting into a phosphate buffer (PB) and AZA lead to thegeneration of new positive charges onto the PANI macromolecular chain and the adsorption of the drug on the working electrode surface that takes place via the pi-pi(*) bonds established between the benzene/quinoide rings of PANI and the imidazole/ purine cyclesof AZA. These results indicate that the SPCE modified with the PANI-ES functionalized RGO sheets shows potential applications in the field of sensors for AZA detection.

Looking for multifunctional materials, an assessment of the performances both as fire retardant and generator of electrically conductive surfaces for a three component mixture of graphene oxide, phosphoric acid and melamine applied on wood chipboard was performed. A simple approach was used to investigate the intumescent char formation and quantify the loss mass during vertical burning tests, in which the prepared samples were exposed for a certain time interval to a flame generated by an ethanol lamp in ambient conditions. Moreover, mass loss evolution and structural changes that occur during the burning process were more comprehensive investigated by differential thermal and thermogravimetric (DTA/TGA) techniques. By comparing the performances between the wood chipboard samples without any coverage and those covered with one or multiple component mixture, an increase of protection against the fire action was noticed when the three component mixture was used. Also, an improvement of the electrical properties was observed, after flame exposure of the samples covered with multiple layers (i.e., two and three), when the three component mixture was used. Morphological and structural investigations by microscopy (optical and electronic-SEMEDX), X-ray diffraction (XRD) and spectral (Raman, FTIR) methods are described. An assessment of market potential is also discussed.

Chemical polymerization of o-phenylenediamine (OPD) in the presence of poly(ethylene oxide), double-wall carbon nanotubes (DWNTs) and ferric chloride is carried out in order to obtain composites based on the poly(o-phenylenediamine)-poly(ethylene oxide) (POPD-PEO) fibres covered and interconnected with DWNTs. Vibrational and photoluminescence properties of these composite materials as well as their morphologies are shown by infrared (IR) spectroscopy, Raman scattering, photoluminescence (PL) and scanning electron microscopy (SEM). An adsorption of DWNTs onto the POPD rods surface in the absence and in the presence of. PEO is highlighted by SEM. The vibrational changes reported by Raman scattering and IR spectroscopy prove a covalent functionalization of DWNTs with the macromolecular compound POPD which is doped with FeCl4- T ions. New hydrogen bonds are generated between POPD covalently functionalized DWNTs and hydroxyl groups of PEO according to IR spectroscopic studies. The two macromolecular compounds, POPD and POPD-PEO, show a complex emission band with maxima at 572 and 566 nm, having a shoulder at 667 nm. A significant change in the profile of the PL bands of POPD and POPD-PEO is induced in the DWNTs presence. We show that DWNTs induce (i) a diminution in the POPD PL band intensity peaked between 525-600 nm simultaneous with the increase in the intensity of the PL band situated in the 600-800 nm spectral range and (ii) an enhancement process of the emission band localized in the 475-800 nm spectral range in the case of POPD-PEO.

In this work, the electrochemical polymerization of pyrrole in the presence of H3PMo12O40 onto the screen-printed carbon electrodes (SPCE) modified with double-walled carbon nanotubes (DWNTs) is reported. The influence of the pyrrole and H3PMo12O40 concentration as well as a scan rate used to recording of cyclic voltammograms that describe the electrochemical synthesis of polypyrrole (PPY) onto the DWNTs surface is assessed. Using scanning electron microscopy (SEM) we demonstrate that the electrosynthesis of PPY doped with H3PMo12O40 heteropolyanions (PPY-PMo12) results in the generation of a globular morphology. Considering the variations induced of DWNTs in the IR and Raman spectra of PPY doped with H3PMo12O40 heteropolyanions, a functionalization process of carbon nanotubes with macromolecular compound is invoked. According to SEM investigations, DWNTs allow the realization of connections between the globular structures of the macromolecular compound. The changes induced of folic acid (FA) during the oxidation-reduction processes at the interface of the DWNTs functionalized with PPY doped with H3PMo12O40 heteropolyanions (SPCE-DWNT/PPY-PMo12) with electrolyte solution are reported.

Cu-Fe-Sn-S films were obtained on indium tin oxide / glass substrates by a low-cost electrodeposition using an aqueous solution of CuSO4, FeSO4, SnSO4, and Na2S2O3 at room temperature followed by high-temperature sulfurization (500 degrees C) in argon flow. A range of cathodic potentials have been used for electrodeposition, those being chosen after a preliminary cyclic voltammetry study. The coatings were characterized using X-ray diffraction, Raman spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, X-ray Photoelectron Spectroscopy and conventional spectroscopy (diffuse reflectance and specular transmission). The results are discussed with respect to the used applied potential.

The influence of the partial substitution of Fe by Si and thermal treatments on the structural, magnetic and magnetostrictive properties of the Fe67.5Pd30.5Si2 rapidly solidified ribbons has been investigated. A remarkable decrease in the martensite transformation temperature, with similar to 65 K lower than that of the Fe-Pd archetype alloy, is observed in the as-prepared ribbons. The thermal treatments shift the martensite transformation temperatures upward, with approximately 13 K for the higher thermal treatment. Also, these induce an improvement in the crystallinity in these ribbons with high texture and an increase in the crystallite size as a result of reducing the internal defects and stress. The thermodynamic considerations discussed in the frame of the Clapeyron-Clausius relation by using the calorimetric and thermomagnetic measurements (up to 7 T) reveal a weak influence of the magnetic fields on the martensitic transformation temperatures (similar to 0.5 K/T). The magnetostriction decrease with temperature under small magnetic fields was discussed, beside an unusual behaviour in the technically saturated domain. This behaviour is based on the coexistence of the ordinary and forced magnetostrictions, the last one increasing faster with the temperature decreasing.

A composite material with applications in optoelectronics has been investigated. Pulsed laser deposition CdSe-doped glass film was prepared by the combinatorial deposition from two targets, namely pure CdSe and glass belonging to the 20Li(2)O-10Al(2)O(3)-7BaO-2La(2)O(3)-2ZnO-59P(2)O(5)system. Exciton peaks in the Vis domain, related to electron-hole pairs transitions from the valence band to the conduction band, were revealed in the optical absorption spectra of the CdSe-doped film. CdSe quantum dots (QDs) band gap energy depends on the CdSe quantum confinement effect. CdSe-doped film photoluminescence exhibits peaks in the red domain assigned to CdSe transitions from the excited state to the ground state. The size of CdSe nanoclusters, determined from x-ray diffraction is correlated with scanning electron microscopy-energy dispersive x-ray spectroscopy and atomic force microscopy results. Vibration modes specific both to CdSe QDs and to the vitreous network have been evidenced by Fourier transform infrared and Raman spectroscopy.