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We report on a change in the properties of monomolecular films of polyelectrolyte molecules, induced by illuminating the silicon substrate on which they adsorb. It was found that under illumination the thickness of the adsorbed layer decreases by at least 27% and at the same time the roughness is significantly reduced in comparison to a layer adsorbed without irradiation. Furthermore, the homogeneity of the film topography and the surface potential is shown to be improved by illumination. The effect is explained by a change in surface charge density under irradiation of n- and p-type silicon wafers. The altered charge density in turn induces conformational changes of the adsorbing polyelectrolyte molecules. Their photocontrolled adsorption opens new possibilities for selective manipulation of adsorbed films. This possibility is of potential importance for many applications such as the production of well-defined coatings in biosensors or microelectronics.
We report on a photo-assisted adsorption of gold nanoparticles on a silicon substrate studied using atomic-force microscopy and secondary ion mass-spectrometry. Depending on a silicon conductivity type (n-Si or p-Si), the amount of photo-assisted adsorbed gold nanoparticles either increases (n-Si) or decreases (p-Si) on irradiation. In addition, the impacts of a cationic polyelectrolyte monolayer and adsorption time were also revealed. The polyelectrolyte layer enhances the adsorption of the gold nanoparticles but decreases the influence of light. The results of the photo-assisted adsorption on two types of silicon wafer were explained by electron processes at the substrate/solution interface.
This work was supported by the German-Russian Interdisciplinary Science Center (G-RISC) funded by the German Federal Foreign Office via the German Academic Exchange Service (DAAD), Project No. P-2014b-1, and Russian foundation for basic research, Project No. 16-08-00524_a.
The photosensitive azobenzene-containing surfactant C-4-Azo-OC(6)TMAB is a promising agent for reversible DNA packaging in a solution. The simulation of the trans-isomer surfactant organization into associates in a solution with and without salt as well as its binding to DNA at different NaCl concentrations was carried out by molecular dynamics. Experimental data obtained by spectral and hydrodynamic methods were used to verify the results of simulation. It was shown that head-to-tail aggregates with close to antiparallel orientation of surfactant molecules were formed at certain NaCl and surfactant concentrations (below critical micelle concentration). Such aggregates have two positively charged ends, and therefore, they can be attracted to negatively charged DNA phosphates far located along the chain, as well as those that belong to different molecules. This contributes to the formation of intermolecular DNA-DNA contacts, and this way, the experimentally observed precipitation of DNA can be explained.
The DNA interaction with cis-isomers of photosensitive azobenzene-containing surfactants was studied by both experimental methods and computer simulation. It was shown that before the organization of micelles, such surfactants in the cis-conformation form associates of only a single type with a disordered orientation of molecules. In contrast, for trans-isomers, there exist two types of associates with head-to-head or head-to-tail orientations of molecules in dependence on salt concentration in a solution. The comparison of cis- and trans-isomer binding to DNA and the influence of salt concentration on the formation of their complexes with DNA were studied. It was shown that cis-isomers interact with phosphate groups of DNA and that their molecules were also located along the minor groove of DNA.
We show that Scattering Infrared Near-field Microscopy (SNIM) allows chemical mapping of polymer monolayers that can serve as designed nanostructured surfaces with specific surface chemistry properties on a nm scale. Using s- SNIM a minimum volume of 100 nm x 100 nm x 15 nm is sufficient for a recording of a "chemical'' IR signature which corresponds to an enhancement of at least four orders of magnitudes compared to conventional FT-IR microscopy. We could prove that even in cases where it is essentially difficult to distinguish between distinct polymer compositions based solely on topography, nanophase separated polymers can be clearly distinguished according to their characteristic near-field IR response.
In this paper the study of the tunneling current-voltage (I-V) characteristics of silicon surfaces with n- and p-type conductivity as a function of roughness in the presence of an adsorbed insulating layer of polyethylenimine (PEI) is presented. A new approach is proposed for analysis of the tunnel current-voltage characteristics of a metal-insulator-semiconductor structure based on the combination of two models (Simmons and Schottky). Such joint analysis demonstrates the effect of surface states and evaluates changes in the band bending and electron affinity after the deposition of the polyelectrolyte layer on the semiconductor surface. As a result, we are able to differentiate between the equilibrium tunnel barrier (q phi (0)) and the barrier height (q phi (B)). It is shown that the deposition of the polymer leads to an increase of the equilibrium tunnel barrier by more than 250 meV, irrespective of the roughness and the conductivity type of the silicon substrate. The PEI deposition also leads to changes in the barrier height (less than 25 meV) that are smaller than the equilibrium tunnel barrier changes, indicating pinning of the Fermi level by the electron surface states that are energetically close to it. These surface states can trap charge carriers, a process leading to the formation of a depletion region and band bending on the semiconductor surface. Moreover, the change in the barrier height q Delta phi (B) depends on the conductivity type of the semiconductor, being positive for n-type and negative for p-type, in contrast to q Delta phi (0), which is positive for all substrates. The change is explained by capture of electrons preferably from the semiconductor space-charge region in the presence of a cationic polyelectrolyte, e.g., PEI.
Using scattering scanning nearfield infrared microscopy (s-SNIM), we have imaged the nanoscale phase separation of mixed polystyrene-poly(methyl methacrylate) (PS-PMMA) brushes and investigated changes in the top layer as a function of solvent exposure. We deduce that the top-layer of the mixed brushes is composed primarily of PMMA after exposure to acetone, while after exposure to toluene this changes to PS. Access to simultaneously measured topographic and chemical information allows direct correlation of the chemical morphology of the sample with topographic information. Our results demonstrate the potential of s-SNIM for chemical mapping based on distinct infrared absorption properties of polymers with a high spatial resolution of 80 nm x 80 nm.
The surface tension and dilational surface visco-elasticity of the individual solutions of the biopolymer DNA and the azobenzene-containing cationic surfactant AzoTAB, as well as their mixtures were measured using the drop profile analysis tensiometry. The negatively charged DNA molecules form complexes with the cationic surfactant AzoTAB. Mixed DNA + AzoTAB solutions exhibit high surface activity and surface layer elasticity. Extremes in the dependence of these characteristics on the AzoTAB concentration exist within the concentration range of 3 x 10(-6)-5 x 10(-5) M. The surface tension of the mixture shows a minimum with a subsequent maximum. In the same concentration range the elasticity shows first a maximum and then a subsequent minimum. A recently developed thermodynamic model was modified to account for the dependence of the adsorption equilibrium constant of the adsorbed complex on the cationic surfactant concentration. This modified theory shows good agreement with the experimental data both for the surface tension and the elasticity values over the entire range of studied AzoTAB concentrations. (C) 2016 Elsevier B.V. All rights reserved.