Factor analysis of spectroelectrochemical reduction of FAD reveals the pKa of the reduced state and the reduction pathway

The free flavin adenine dinucleotide (FAD) cofactor is known to exhibit a pH‐dependent midpoint potential involving a simultaneous two‐electron transfer step (n = 2). Uv‐vis spectroelectrochemical reductions of FAD at constant pH, ranging from 5 to 9, were recorded and analyzed by factor analysis. Principal factor analysis was used to determine the number of species present at each pH. The results indicate that only two composite forms of FAD are present: the oxidized and the reduced forms. Window factor analysis was used to extract the concentration profiles of the controlling species. The oxidized form was found to be a single pH‐independent species, whereas the reduced form consists of two species. The pH‐dependent spectroscopic changes of reduced FAD were best modeled by a single proton transfer step involving two different ionization states with an apparent pK_a = 6.3. This value compares favorably with those obtained from NMR and from midpoint potential measurements. At pH 6, the reduction of FAD was found to be first order, whereas at pH 9 the reduction is zero order; these observations are explained in terms of the reaction pathway involving xanthine oxidase, its substrate, and the pH. Copyright © 2007 John Wiley & Sons, Ltd.     

Transmission of return-to-zero pulses in an optical split-step system based on reflecting fiber gratings

A new variety of the “soliton management” in heterogeneous optical media is proposed. The system is composed as a periodic chain of nonlinear fibers with negligible intrinsic group-velocity dispersion (GVD), alternating with sections of unchirped fiber Bragg gratings (FBGs) operating in the reflection regime. Losses due to incomplete reflection are compensated by linear amplifiers. The model may apply to fiber-optic telecommunication links with periodically installed FBG modules, and it may be used for the design of laser setups. By means of extended simulations, we identify small regions in the underlying parameter space where this model, featuring the periodic separation of the Kerr nonlinearity and FBG-induced GVD (hence the name of the “split-step” system), supports stable transmission of RZ (return-to-zero) pulses, i.e., quasi-solitons. The effect of nonzero fiber’s GVD on the stable transmission regime is considered too. Moderately unstable (partly usable) transmission regimes are found in larger regions of the parameter space; they may be of two different types, with the average nonlinearity either undercompensating or overcompensating the GVD. Interactions between the stable RZ pulses are also studied, leading to the identification of a minimum separation between them necessary for the suppression of interaction effects.     

Positron annihilation in large polyatomic molecules. The role of vibrational Feshbach resonances and binding

We analyse the process of rapid positron annihilation in large polyatomic molecules due to positron capture into vibrational Feshbach resonances. Resonant annihilation occurs in molecules which can bind positrons, and we analyse positron binding to alkanes using zero-range potentials. Related questions of spectra of annihilation gamma quanta and molecular fragmentation following annihilation, are discussed briefly.     

Selective growth of carbon nantoubes on SiO2/Si substrate

Three-step raising temperature process was employed to fabricate carbon nanotubes by pyrolysis of ferrocene/melamine mixtures on silica and single crystalline silicon wafers respectively. Then the morphologies, structures and compositions of obtained carbon nanotubes are investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscope (EDX) and electron energy-loss spectroscopy (EELS). TEM and SEM observation shows that on silica substrate, high-oriented carbon nanotube can grow compactly to form continuous film on both frontal and cross-section surfaces, but on silicon substrate, only can form on cross-section surface. These carbon nanotubes have much irregular cup-like structure, and with outer diameter varying from 25 nm to 35 nm. At the top end of carbon nanotube there is a catalyst particle. EDX analysis reveals that the particle are iron cluster, and EELS spectrum indicates that the nanotube is composed of pure carbon. Finally, the effect of substrate surface roughness on the growth behavior of carbon nanotubes has been discussed.     

Organic modification of TEOS based silica aerogels using hexadecyltrimethoxysilane as a hydrophobic reagent

The experimental results on the synthesis and characterization of tetraethoxysilane (TEOS) based hydrophobic silica aerogels using hexadecyltrimethoxysilane (HDTMS) as a hydrophobic reagent by two step sol-gel process, are described. The molar ratio of tetraethoxysilane (TEOS), methanol (MeOH), acidic water (0.001 M, oxalic acid) and basic water (10 M, NH₄OH) was kept constant at 1:55:3.25:1.25 and the molar ratio of HDTMS/TEOS (M) was varied from 0 to 28.5 × 10⁻². The organic modification was confirmed by infrared spectroscopic studies, and the hydrophobicity of the aerogels was tested by the contact angle measurements. The maximum contact angle of 152° was obtained for M = 22.8 × 10⁻². The aerogels retained the hydrophobicity up to a temperature of 240 °C and above this temperature the aerogels became hydrophilic. The aerogels were characterized by the thermal conductivity, density, contact angle measurements, optical transmission and scanning electron micrographs.     

The azimuthal dependent oxidation process on Cu(110) by energetic oxygen molecules

We report a study on the oxidation process induced by a hyperthermal oxygen molecular beam (HOMB) on Cu(110) using X-ray photoemission spectroscopy in conjunction with a synchrotron radiation source. The oxidation process induced by energetic O₂ beams on Cu(110), depending on the azimuthal angle of incidence, suggests that the –Cu–O– added row structure has a role in inhibiting adsorption as a steric obstacle for incident O₂ molecules.     

Determination of X-ray compression efficiency of a thin film X-ray waveguide structure using marker layer fluorescence

We demonstrate that a thin marker layer, sandwiched in the guiding medium of a thin film planner X-ray waveguide structure, can be used to determine X-ray compression efficiency for a particular excitation mode. It can also be used in evaluating the transmission efficiency of waveguide structure and for the determination of X-ray intensities reaching the waveguide exit. This approach has been applied for determining X-ray compression and transmission efficiency of a Mo/B₄C/Mo based X-ray waveguide structure, by inserting a thin Fe marker layer.     

Boron distribution in the subsurface region of heavily doped IIb type diamond

For the first time investigations of the boron distribution in the subsurface region of HPHT boron-doped diamond that is promising for applications in electronics were carried out by X-ray photoelectron (XPS) and Raman spectroscopy. It was found from XPS data that the boron content decreased gradually more than one order of magnitude in depth of surface. The first-principle calculations have shown that the Raman polarizability in the crossed polarization configuration should increase considerably with boron doping. The Raman spectra from as-grown and polished surfaces of heavily boron-doped diamond are discussed in the context of theoretical results.     

Plasmon energy chemical phase mapping of reactive multilayers

An analytical method of quantitative phase identification and mapping on the nanoscale is presented based on correlative similarity mapping from spectrum images within electron energy loss spectroscopy across the low‐loss plasmon region. The method is applied to map the reaction layer formation for heat treated Cu–Al–Al₂O₃ thin films. Coexistence of residual Al pockets next to polycrystalline but epitaxial CuAl₂ as main reaction product is found as well as a distinctive interfacial plasmon region. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Gene delivery process in a single animal cell after femtosecond laser microinjection

Microinjection of extracellular molecules into a single animal cell was performed by an amplified femtosecond laser irradiation. When a single-shot laser pulse was focused on the plasma membrane of a single fibroblast from the mouse cell line NIH3T3 with a high-numerical aperture objective lens, a transient hole with a diameter of 1 μm was formed. The delivery process of extracellular molecules immediately after the hole formation was monitored by a fluorescence staining with fluoresceinisothiocyanate-dextran (FITC-dextran). Then the gene expression was confirmed using a DNA plasmid of an enhanced green fluorescent protein (EGFP). The gene expression was observed when the laser pulse was focused first on the cellular membrane and then on the nuclear membrane, while the gene was not expressed when the laser was focused only on the cellular membrane. On the basis of these results, the efficiency of gene delivery by the femtosecond laser microinjection and the subsequent gene expression were clarified.