Interplay between structural changes, surface states and quantum confinement effects in semiconducting Mg2Si and Ca2Si thin films.

Ab initio techniques have been used to investigate structural changes in semiconducting Mg2Si and Ca2Si thin films (from 17 nm down to 0.2 nm corresponding to the 2D structure) along with band-gap variations due to quantum confinement. Cubic Mg2Si(111) thin films being dynamically stable at thicknesses (d) larger than 0.3 nm displayed an indirect band gap, the reduction of which with increasing d could be reasonably well described by the simple effective mass approximation. Only 2D Mg2Si has a unique structure because of the orthorhombic distortion and the direct band gap. Since the surface energy of cubic Ca2Si(111) films was lower with respect to any surface of the orthorhombic phase, which is the ground state for the Ca2Si bulk, the metastable in-bulk cubic phase in the form of thin films turned out to be preferable in total energy than any orthorhombic Ca2Si thin film for d < 3 nm. Sizable structural distortion and the appearance of surface states in the gap region of Ca2Si thin films with d < 3 nm could be the reason for an odd dependence of the band-gap variation on d.

Morphology, electrokinetic characteristics and the effect on biofilm formation of carrageenan:chitosan polyelectrolyte complexes.

Carrageenan:chitosan (CG:CH) polyelectrolyte complexes (PEC) were obtained and the effect of the initial components ratio on formation was studied by dynamic light scattering, atomic force microscopy (AFM) and electrokinetic measurements. Positively charged PEC particles (average ζ-potential 40.2 mV) were formed, provided that the polycation was present in excess in the complex and was stabilized by chitosan amino groups. According to the AFM data, chitosan was located on the surface of the carrageenan fibers. In PEC where carrageenan prevailed, the number of unbound sulfate groups decreased when the chitosan content increased, this resulted in a decrease in the PEC negative surface charge (from -92.4 to -55.6 mV). In this case, AFM showed that chitosan was incorporated into the network structure of carrageenan and breaks it at a CG:CH ratio of 1:0.5 w/w. Complexes with a high content of kappa-CG inhibited biofilm formation by Gram negative and Gram positive microorganisms.

An approach to growth of Fe-Si multilayers with controlled composition profile-a way to exchange coupled thin films.

The growth, composition and structure of sandwich structures (Fe-rich layer/Si-rich layer/Fe-rich silicide layer) grown on a Si(111) surface were studied by a few complementary microscopic and spectroscopic techniques with high spatial resolution. Intermixing at the Fe/Si and Si/Fe interfaces is demonstrated. Fe-rich layers grown directly on the Si(111) surface are crystalline and have abrupt but rough interfaces at both sides. The succeeding layers are disordered and their interfaces are fuzzy. The distributions of Fe and Si within the layers are laterally non-uniform. The reproducible fabrication of thin non-magnetic silicide spacers of predetermined thickness is demonstrated. Sandwich structures with such spacers exhibit exchange coupling between ferromagnetic Fe-rich layers.

Enhancement of the Si p-n diode NIR photoresponse by embedding ß-FeSi2 nanocrystallites.

By using solid phase epitaxy of thin Fe films and molecular beam epitaxy of Si, a p(+)-Si/p-Si/ß-FeSi2 nanocrystallites/n-Si(111) diode structure was fabricated. Transmission electron microscopy data confirmed a well-defined multilayered structure with embedded nanocrystallites of two typical sizes: 3-4 and 15-20 nm, and almost coherent epitaxy of the nanocrystallites with the Si matrix. The diode at zero bias conditions exhibited a current responsivity of 1.7 mA/W, an external quantum efficiency of about 0.2%, and a specific detectivity of 1.2 × 10(9) cm × Hz(1/2)/W at a wavelength of 1300 nm at room temperature. In the avalanche mode, the responsivity reached up to 20 mA/W (2% in terms of efficiency) with a value of avalanche gain equal to 5. The data obtained indicate that embedding of ß-FeSi2 nanocrystallites into the depletion region of the Si p-n junction results in expansion of the spectral sensitivity up to 1600 nm and an increase of the photoresponse by more than two orders of magnitude in comparison with a conventional Si p-n junction. Thereby, fabricated structure combines advantage of the silicon photodiode functionality and simplicity with near infrared light detection capability of ß-FeSi2.

The supramolecular structure of LPS-chitosan complexes of varied composition in relation to their biological activity.

The complexes of chitosan (Ch) with lipopolysaccharides (LPSs) from Escherichia coli O55:B5 (E-LPS) and Yersinia pseudotuberculosis 1B 598 (Y-LPS) of various weight compositions were investigated using quasi-elastic light scattering, ζ-potential distribution assay and atomic force microscopy. The alteration of ζ-potential of E-LPS-Ch complexes from negative to positive values depending on Ch content was detected. The Y-LPS-Ch complexes had similar positive ζ-potentials regardless of Ch content. The transformation of the supramolecular structure of E-LPS after binding with to Ch was revealed. Screening of E-LPS and Y-LPS particles by Ch in the complexes with high polycation was detected. The ability of LPS-Ch complex to induce biosynthesis of TNF-α and reactive oxygen species in stimulated human mononuclear cells was studied. A significant decrease in activity complexes compared to that of the initial LPS was observed only for E-LPS-Ch complexes.

Soluble chitosan-carrageenan polyelectrolyte complexes and their gastroprotective activity.

The soluble polyelectrolyte complexes (PEC) κ-carrageenan (κ-CG):chitosan was obtained. Binding constant value (2.11 × 10(7)mol(-1)) showed high affinity of κ-CG to chitosan. The complex formation of κ-CG:chitosan 1:10 and 10:1 w/w was shown by centrifugation in a Percoll gradient. Using atomic force microscopy we showed that the supramolecular structure of the complexes is different from each other and from the macromolecular structure of the initial polysaccharides. The gastroprotective and anti-ulcerogenic effect of κ-CG, chitosan and their complexes was investigated on the model of stomach ulcers induced by indometacin in rats. PEC κ-CG:chitosan have gastroprotective properties which depend on their composition. Complex κ-CG:chitosan 1:10 w/w possesses higher gastroprotective activity than the complex 10:1 w/w. These results suggest that the gastroprotective effect of complexes can be associated with their protective layer on the surface of the mucous membrane of a stomach, which avoids a direct contact with the ulcerogenic agent.

Atomic force microscopy imaging of carrageenans from red algae of Gigartinaceae and Tichocarpaceae families.

In the present article, the atomic force microscopy was applied to investigate macromolecular structures of various carrageenan types including hybrid polysaccharides (κ-, κ/ß-, κ/ι-, λ-, and X-carrageenans) depending on polysaccharide concentration. The structures dependence on a polysaccharide concentration also was focused. κ-Carrageenan forms both single and two stranded structures at a low concentration. At high concentrations κ-, κ/ß-, and κ/ι-carrageenans form fibrous network-like structures by a side-by-side association type at the same time for κ/ι-carrageenan end-to-end association type also was found. Comparably to κ-carrageenan, κ/ß-carrageenan network was more open with coarser fibers while κ/ι-carrageenan structure is characterized with a more flexible network. Honeycombed structures due to end-to-end and side-by-side association types were observed for X-carrageenan, while λ-carrageenan formed honeycombed structures only at high concentrations. In order to investigate topographical parameters of the carrageenans macromolecular structure a new method of the autocorrelation function analysis was used for the first time.

An investigation of the electrical and optical properties of thin iron layers grown on the epitaxial Si(111)-(2 × 2)-Fe phase and on an Si(111)7 × 7 surface.

Electrical and optical properties of thin iron layers grown at room temperature on the epitaxial silicide Si(111)-(2 × 2)-Fe phase and on an Si(111)7 × 7 surface were investigated using in situ Hall effect registration, atomic force microscopy, and optical spectroscopy. It was established that Si(111)-(2 × 2)-Fe phase has semiconducting properties with a 0.99 eV effective band gap and acts as a diffusion barrier for the deposited iron atoms, preventing intermixing with the substrate at room temperature. Peculiarities in the optical spectra of a sample with a 2 nm iron film grown on the Si(111)-(2 × 2)-Fe phase typical for both metal and semiconducting natures prove a conservation of the phase under the iron layer. The process of iron growth on the Si(111)-(2 × 2)-Fe phase is accompanied by the development of high stress in the subsurface area resulting in band dispersion changes. Apparently the tension reaches a maximum at an iron layer thickness of 1.35 nm, and a high effective hole mobility equal to 820  cm(2) V(-1) s(-1) was registered.

Investigation of multilayer silicon structures with buried iron silicide nanocrystallites: growth, structure, and properties.

The growth of nanosize islands of iron silicides on Si(100) substrates and epitaxial silicon overgrowth atop them have been studied by low energy electron diffraction and reflectance high energy electron diffraction methods. The near optimal formation conditions of iron silicide islands with high density and minimal sizes have been determined by using of atomic force microscopy. Multilayer (8-10) monolithic structures with buried iron silicide nanocrystallites have been grown after the definition of monocrystalline burying conditions of iron silicides nanocrystallites in silicon lattice. The structure of buried nanocrystallites has been studied in multilayer monolithic heterostructures by high resolution transmission electron microscopy. It was established that in multilayer samples the majority of nanocrystallites have beta-FeSi2 structure, but some of them have gamma-FeSi2 structure. It was observed an influence of additional annealing at 850 degrees C on the morphology and structure of nanocrystallites. By means of deep level transient spectroscopy data one and two trap levels have been observed in multilayer structures (without and with additional annealing, respectively). Photoluminescence spectra have been studied at 4.2 K and the causes of its absence from buried beta-FeSi, NC have been analyzed.

Anisotropic nonadditive ab initio force field for noncovalent interactions of H2.

A quantum mechanical polarizable force field (QMPFF) has been applied to the noncovalent interactions of molecular hydrogen as well as closed-shell monoatomic species (CSMS): rare gases, alkali cations, and halide anions. The importance of all the main energy components is demonstrated: electrostatics (including penetration effect), exchange repulsion, dispersion, and induction. As the MP2 level of quantum mechanics, which is used to parametrize QMPFF, significantly underestimates the H2-H2 dimer binding energy, the force field was refined using state-of-the-art CCSD(T) data. The approach demonstrates excellent transferability, which is confirmed by accurate reproduction of mixed H2-CSMS dimers and the second virial coefficient of hydrogen vapor.

Spin-dependent transport caused by the local magnetic moments inserted in the Aharonov-Bohm rings.

We analyse the conductance of an Aharonov-Bohm (AB) ring with a quantum point contact (QPC) that is inserted in one of its arms and which contains a single electron. The conductance of the device is calculated as a function of the one-dimensional (1D) carrier concentration and the value of the magnetic field perpendicular to the plane of the AB ring. The exchange interaction between the electron localized inside QPC and freely propagating electrons is shown to modify the conductance pattern at small carrier concentration significantly, giving rise to the effects related to the formation of the '0.7 feature' in the quantum conductance staircase.

Water properties from first principles: simulations by a general-purpose quantum mechanical polarizable force field.

We have recently introduced a quantum mechanical polarizable force field (QMPFF) fitted solely to high-level quantum mechanical data for simulations of biomolecular systems. Here, we present an improved form of the force field, QMPFF2, and apply it to simulations of liquid water. The results of the simulations show excellent agreement with a variety of experimental thermodynamic and structural data, as good or better than that provided by specialized water potentials. In particular, QMPFF2 is the only ab initio force field to accurately reproduce the anomalous temperature dependence of water density to our knowledge. The ability of the same force field to successfully simulate the properties of both organic molecules and water suggests it will be useful for simulations of proteins and protein-ligand interactions in the aqueous environment.

Quantum mechanical polarizable force field (QMPFF3): refinement and validation of the dispersion interaction for aromatic carbon.

The authors have recently introduced a general, polarizable force field QMPFF fitted solely to high-level quantum mechanical data for simulations of biomolecular systems. Here the authors demonstrate using an advanced version QMPFF3 how the problem of insufficient accuracy of the MP2-based training set for the aromatic carbon atom type can be effectively solved by a simple model correction using state-of-the-art CCSD(T) data. The approach demonstrates excellent transferability, which is confirmed for three phases of matter by accurate calculations of the second virial coefficient for benzene vapor and various properties of liquid benzene and polyaromatic hydrocarbon crystals.