The effect of nature of polyions and treatment after deposition on wetting characteristics of polyelectrolyte multilayers

The sequential adsorption of oppositely charged polyelectrolytes (PE) occurs to be a powerful tool for obtaining various materials of precisely defined properties. The interfacial features of PE multilayer films are governed by the choice of polycation/polyanion pairs and the conditions of film formation. Additionally, the long time exposure to the conditions different than that encountered during formation usually affects polyelectrolyte multilayer structure.The wettability of heterogeneous surfaces produced by ‘layer-by-layer’ (LbL) adsorption of polyelectrolytes was investigated in this work. We focused on the influence of film treatment after deposition on wetting properties of obtained multilayers. The effect of the nature of the first layer was also studied. Apart from simple arrangements: (polyallylamine hydrochloride)/(polysodium 4-styrenesulfonate) (PAH/PSS) and (poly-l-lysine hydrobromide)/(poly-l-glutamic acid sodium salt) (PLL/PGA) more complicated structures were considered having as a first layer two types of polyethylene imines (PEI) of different molecular weight.Wetting properties of such polyelectrolyte films were determined experimentally by contact angle measurements using technique of direct image analysis of the shape of sessile drop.     

Evolution of modulated structure in Fe–Cr–Co alloy during isothermal ageing with different external magnetic field conditions

The evolution of modulated structure in Fe–Cr–Co alloy during isothermal ageing with and without external magnetic field was investigated by using transmission electron microscopy (TEM) and phase-field simulation. The isotropic modulated structure in Fe–Cr–Co alloy formed during isothermal ageing without external magnetic field could be converted to be anisotropy during further isothermal ageing under an 8 kOe external magnetic (thermo-magnetic treatment), and the formation of anisotropy was slower than the direct formation from spinodal decomposition under external magnetic field and is time dependent. The anisotropy characteristic of modulated structure in Fe–Cr–Co alloy subjected to thermo-magnetic treatment for 1 h remained during further isothermal ageing without external magnetic field for up to 20 h. Novel modulated structure could be obtained through specific thermo-magnetic treatment processes, which was confirmed by phase-field simulation.     

The effect of inactive impurities on a surface in NO-CO reaction: A Monte Carlo simulation

The interaction among the reacting species in the NO-CO reaction on a metal catalytic surface that proceeds according to the Langmuir-Hinshelwood thermal mechanism is studied by means of Monte Carlo simulations. The study of this system is essential for the understanding of the influence of impurities on the catalytic oxidation of NO by CO. It is found that this complex system exhibits irreversible phase transitions between active states with sustained reaction and poisoned states without reaction. The same system has also been investigated by non-thermal (Eley-Rideal) mechanism. Both the phase diagrams of the surface coverage and the steady state production of CO₂ and N₂ are evaluated as a function of the partial pressures of the reactants in the gas phase. From this study, it is observed that with the increase of impurities, the production rate reduces and the reaction stops at a certain point. Moreover, the first order transition in the phase diagram converts into second order phase transition that is in accordance with the experimental findings. Therefore, the first order phase transition, which is a characteristic of such catalytic reactions, is eliminated.     

Electron beam lithography designed chemical nanosensors based on localized surface plasmon resonance

Efficient nanochemosensors designed by electron beam lithography and based on localized surface plasmon resonance excited on noble metal nanocylinders are presented. Using localized surface plasmon resonance spectroscopy, we report here a high sensitivity corresponding to a density of about 18 × 10⁻²¹ mol of adsorbate per nanocylinders, we present the results obtained with gold and silver nanoparticles. This detection corresponds to less than one monolayer of molecules adsorbate on the nanoparticle. Additionally a subsequent layers deposition of polyelectrolytes is used to detect very thin polymer films. Although the results presented in this work are far from conclusive, the advantages of these nanochemosensors discussed here open the possibilities of further developments in a wide range of chemical and medical applications.     

Electron stimulated desorption of H3O from 316L stainless steel

Surface ions generated by electron stimulated desorption from mass spectrometer ion source grids are frequently observed, but often misidentified. For example, in the case of mass 19, the source is often assumed to be surface fluorine, but since the metal oxide on grid surfaces has been shown to form water and hydroxides, a more compelling case can be made for the formation of hydronium. Further, fluorine is strongly electronegative, so it is rarely generated as a positive ion. A commonly used metal for ion source grids is 316L stainless steel. Thermal vacuum processing by bakeout or radiation heating from the filament typically alters the surface composition to predominantly Cr₂O₃. X-ray photoelectron spectral shoulders on the O 1s and Cr 2p_3/2 peaks can be attributed to adsorbed water and hydroxides, the intensity of which can be substantially increased by hydrogen dosing. On the other hand, the sub-peak intensities are substantially reduced by heating and/or by electron bombardment. Electron bombardment diode measurements show an initial work function increase corresponding to predominant hydrogen desorption (H₂) and a subsequent work function decrease corresponding to predominant oxygen desorption (CO). The fraction of hydroxide concentration on the surface was determined from X-ray photoelectron spectroscopy and from the deconvolution of temperature desorption spectra. Electron stimulated desorption yields from the surface show unambiguous H₃O⁺ peaks that can be significantly increased by hydrogen dosing. Time of flight secondary ion mass spectrometry sputter yields show small signals of H₃O⁺, as well as its constituents (H⁺, O⁺ and OH⁺) and a small amount of fluorine as F⁻, but no F⁺ or F⁺ complexes (HF⁺, etc.). An electron stimulated desorption cross-section of σ⁺ ∼ 1.4 × 10⁻²⁰ cm² was determined for H₃O⁺ from 316L stainless steel for hydrogen residing in surface chromium hydroxide.     

The second-harmonic generation in parabolic quantum dots in the presence of electric and magnetic fields

The second-harmonic generation (SHG) coefficient for parabolic quantum dots (QDs) subject to applied electric and magnetic fields is theoretically investigated, within the framework of the compact-density-matrix approach and an iterative method. Numerical results are presented for typical GaAs/AlGaAs parabolic QDs. These results show that the radius of QD and the magnitude of electric and magnetic fields have a great influence on the SHG coefficient. And the peak shifts to the aspect of high energy when considering the influence of electric and magnetic fields. Moreover, the SHG coefficient also depends sensitively on the relaxation rate of the spherical QD system.     

Electron-stimulated desorption of lithium ions from lithium halide thin films

Electron-stimulated desorption of positive lithium ions from thin layers of lithium halides deposited onto Si(1 1 1) are investigated by the time-of-flight technique. The determined values of isotope effect of the lithium (⁶Li⁺/⁷Li⁺) are 1.60 ± 0.04, 1.466 ± 0.007, 1.282 ± 0.004, 1.36 ± 0.01 and 1.33 ± 0.01 for LiH, LiF, LiCl, LiBr and LiI, respectively. The observed most probable kinetic energies of ⁷Li⁺ are 1.0, 1.9, 1.1, 0.9 and 0.9 eV for LiH, LiF, LiCl, LiBr and LiI, respectively, and seem to be independent of the halide component mass. The values of lithium ion emission yield, lithium kinetic energy and lithium isotope effect suggest that the lattice relaxation is only important in the lithium ion desorption process from the LiH system. In view of possible mechanisms and processes involved into lithium ion desorption the obtained results indicate that for LiH, LiCl, LiBr and LiI the ions desorb in a rather classical way. However, for LiF, ion desorption has a more quantum character and the modified wave packet squeezing model has to be taken into account.     

A novel biosensing interfacial design based on the assembled multilayers of the oppositely charged polyelectrolytes

A novel biosensing interfacial design strategy has been produced by the alternate adsorption of the oppositely charged polyelectrolytes. A quartz-crystal microbalance (QCM) as a model transducer was modified by use of mercaptoacetic acid (MAA) self-assembled monolayer (SAM) and the adsorption multilayers of the oppositely charged polyelectrolytes. MAA-SAM was first applied to the gold electrode surface of the crystal, and the positively charged chitosan was used as a double-sided linker to attach the negatively charged alginate-HSA antibodies to the negatively charged MAA-SAM layer. The assembly process and conditions were studied using the real-time output device and the surface topologies of the resulting crystals were characterized by atomic force microscopy (AFM) imaging. It is discovered that the optimal pH of immobilizing antibodies was 7.2 and the suited dilution ratio of antibodies was 10:30. The proposed immunosensor in optimal conditions has a linear detection range of 12.3-184.5 μg/mL for HSA detection. Comparing with the direct immobilization method of antibodies, the immunosensor with the proposed immobilization procedure shows some advantages, such as improved sensitivity due to the well-retained antibody activity and the significantly extended detection range. In particular, the regeneration of the developed immunosensor was simple and fast. Analytical results indicate that the developed immobilization procedure is a promising alternative for the immobilization of biorecognition element on the electrode surface.     

TiO2 nanotubes: photocatalyst for cancer cell killing

The present work reports on the use of self‐organized TiO₂ nanotube layers for the photocatalytic killing of cancer cells. TiO₂ nanotube layers with different dimensions (diameter 50 nm and 100 nm, thickness 800 nm and 1.3 μm, respectively) were grown by anodization of Ti. Upon low dose of UV irradiation, the vitality of cancer cells cultured on these nanotube layers was significantly affected – the cells reduced their shape and size and a significant amount of the dead cells was found. These results demonstrate that self‐organized TiO₂ nanotube layers can be used for photo‐induced cancer cell killing. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Hydration Structure and Intermolecular Interaction in Polyelectrolytes

In hydration, the intermolecular interaction is of decisive importance, since the ions modify the properties of the hydration water molecules, and the water molecules in turn have a strong influence on the interaction between the ions. These processes can be studied in detail with the aid of IR spectroscopy, which in addition provides a picture of the hydration structure. IR spectroscopy also shows that the excess protons are in energy bands and allows the detection of the proton dispersion forces acting between tunneling protons. The results of IR studies on polyelectrolytes contribute to our understanding of the many biological processes that depend on the behavior of ions.