Anatoly I. Kulak

Titanium and Iron Oxide-Based Magnetic Photocatalysts for Oxidation of Organic Compounds and Sulfur Dioxide

New approaches to designing magnetic photocatalysts on the basis of microheterogeneous structures built according to the scheme “magnetic core–photocatalytic shell” were proposed. A procedure for preparing the Zn0.35Ni0.65Fe2O4/SiO2/TiO2 catalyst designed for the destructive oxidation of organic compounds, as well as the Fe3O4/Fe2O3/Fe4[Fe(CN)6]3: KCo[Co(CN)6] and Fe3O4/Fe2O3/polyaniline catalysts designed for the photo-oxidation of SO2, was considered. It was shown that the reduction of molecular oxygen proceeded primarily to H2O2, as a result of doping the polyaniline shell with 18-tungstophosphoric acid, and the quantum yield of the SO2 photo-oxidation reaction was doubled by coupling heterogeneous photocatalysis with homogeneous catalysis (involving the hydrogen peroxide formed).

Ultrasound fibrin clot destruction in vitro in the presence of fibrinolytic agent

Ultrasound fibrin clot destruction was investigated in vitro using electron microscopy and by monitoring the changes in the light transmission of clot debris suspension. It has been established that in the course of a combined action of ultrasound and fibrinolytic agent at high ultrasound intensities and short sonification periods, fibrin clot is disrupted mainly due to sonomechanical treatment, while fermentative lysis takes place in parallel and at a significantly lower rate. However, the streptokinase action prevails after ultrasound switching off and results in the prevention of clot debris conglomeration.

Deposition of hydroxyapatite–incorporated TiO2 coating on titanium using plasma electrolytic oxidation coupled with electrophoretic deposition

A porous hydroxyapatite (HA)–incorporated TiO2 coating has been deposited on the titanium substrate using a plasma electrolytic oxidation coupled with electrophoretic deposition (PEO-EPD). Potassium titanium(IV) oxalate is decomposed by micro arcs generated on the anode producing TiO2 while HA particles have been simultaneously deposited on anode during EPD process. Hydroxyapatite and TiO2 particles have been coagulated into roundish conglomerates with the average diameter in a range of 200–600 nm. The microstructure, as well as elemental and phase composition of the coatings have been examined by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), glow discharge optical emission spectroscopy (GDOES), fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). XRD has showed that the coatings are composed mainly of HA, rutile and anatase phases. The composition and surface morphologies are not strongly dependent on the applied voltages. The amount of HA deposited into the coating increases with increasing the applied voltage. The wear resistance of PEO-EPD coatings has been assessed using tribological tests. The bioactivity of the obtained coatings has been investigated in a simulated blood fluid.

Photocatalytic Deposition of Hydroxyapatite onto a Titanium Dioxide Nanotubular Layer with Fine Tuning of Layer Nanoarchitecture

A new effective method of photocatalytic deposition of hydroxyapatite (HA) onto semiconductor substrates is proposed. A highly ordered nanotubular TiO2 (TNT) layer formed on titanium via its anodization is chosen as the photoactive substrate. The method is based on photodecomposition of the phosphate anion precursor, triethylphosphate (TEP), on the semiconductor surface with the following reaction of formed phosphate anions with calcium cations presented in the solution. HA can be deposited only on irradiated areas, providing the possibility of photoresist-free HA patterning. It is shown that HA deposition can be controlled via pH, light intensity, and duration of the process. Energy-dispersive X-ray spectroscopy profile analysis and glow discharge optical emission spectroscopy of HA-modified TNT prove that HA deposits over the entire TNT depth. High biocompatibility of the surfaces is proven by protein adsorption and pre-osteoblast cell growth.

Influence of wide band gap oxide substrates on the photoelectrochemical properties and structural disorder of CdS nanoparticles grown by the successive ionic layer adsorption and reaction (SILAR) method

Summary The photoelectrochemical properties of nanoheterostructures based on the wide band gap oxide substrates (ZnO, TiO2, In2O3) and CdS nanoparticles deposited by the successive ionic layer adsorption and reaction (SILAR) method have been studied as a function of the CdS deposition cycle number (N). The incident photon-to-current conversion efficiency (IPCE) passes through a maximum with the increase of N, which is ascribed to the competition between the increase in optical absorption and photocarrier recombination. The maximal IPCE values for the In2O3/CdS and ZnO/CdS heterostructures are attained at N ≈ 20, whereas for TiO2/CdS, the appropriate N value is an order of magnitude higher. The photocurrent and Raman spectroscopy studies of CdS nanoparticles revealed the occurrence of the quantum confinement effect, demonstrating the most rapid weakening with the increase of N in ZnO/CdS heterostructures. The structural disorder of CdS nanoparticles was characterized by the Urbach energy (E U), spectral width of the CdS longitudinal optical (LO) phonon band and the relative intensity of the surface optical (SO) phonon band in the Raman spectra. Maximal values of E U (100–120 meV) correspond to СdS nanoparticles on a In2O3 surface, correlating with the fact that the CdS LO band spectral width and intensity ratio for the CdS SO and LO bands are maximal for In2O3/CdS films. A notable variation in the degree of disorder of CdS nanoparticles is observed only in the initial stages of CdS growth (several tens of deposition cycles), indicating the preservation of the nanocrystalline state of CdS over a wide range of SILAR cycles.

Photoelectrochemical and Raman characterization of In2O3 mesoporous films sensitized by CdS nanoparticles.

Summary The method of successive ion layer adsorption and reaction was applied for the deposition of CdS nanoparticles onto a mesoporous In2O3 substrate. The filling of the nanopores in In2O3 films with CdS particles mainly occurs during the first 30 cycles of the SILAR deposition. The surface modification of In2O3 with CdS nanoparticles leads to the spectral sensitization of photoelectrochemical processes that manifests itself in a red shift of the long-wavelength edge in the photocurrent spectrum by 100–150 nm. Quantum-confinement effects lead to an increase of the bandgap from 2.49 to 2.68 eV when decreasing the number of SILAR cycles from 30 to 10. The spectral shift and the widening of the Raman line belonging to CdS evidences the lattice stress on the CdS/In2O3 interfaces and confirms the formation of a close contact between the nanoparticles.

Giant Incident Photon‐to‐Current Conversion with Photoconductivity Gain on Nanostructured Bismuth Oxysulfide Photoelectrodes under Visible‐Light Illumination

Nanostructured layered bismuth oxysulfide films synthesized by chemical bath deposition reveal a giant incident photon-to-current conversion efficiency (IPCE). This study shows that surprisingly for the cathodic photocurrent in the photoreduction process, the IPCE reaches ≈2500% in aqueous solutions containing [Fe(CN)6 ]3- . The giant IPCE is observed starting from a certain minimal oxidizer concentration (c > 10-3 m for [Fe(CN)6 ]3- ) and decreases nonlinearly with an increase of illumination intensity. Giant IPCE is determined by the decrease in resistivity of the bismuth oxysulfide film under illumination with photoconductivity gain, which provides the possibility of charge carriers from an external circuit to participate in the photoreduction process. Giant IPCE is observed not only in [Fe(CN)6 ]3- solutions, but also in electrolytes containing other photoelectron acceptors: Fe3+ , I3- , quinone, H2 O2 . In all, solution-processed layered bismuth oxysulfide films offer large-area coverage, nontoxicity, low cost, and compatibility with a wide range of substrates. Abnormally high photoelectrochemical activity, as well as a band gap energy value favorable for efficient conversion of solar light (1.38 eV, direct optical transitions), proves the potential of bismuth oxysulfide photoelectrodes for a new generation of high-performance photoconverters.

COMBINED LOW-FREQUENCY ULTRASOUND AND STREPTOKINASE INTRAVASCULAR DESTRUCTION OF ARTERIAL THROMBI IN VIVO

To prevent a distal embolization in the course of ultrasound (US) angioplasty, we combined US thrombus disruption in peripheral artery in vivo with simultaneous administration of streptokinase (SK). Acute thrombosis was induced in the femoral arteries of 23 dogs. Two hours after thrombus formation, thrombus destruction was performed using US (36 kHz) and by a combined US+SK (75,000 U/kg) administration. The results showed that thrombi were disrupted completely by 1.5 ± 0.5 min US. A combined US+SK action resulted in activation of fibrinolysis, as indicated by the increase in the content of fibrinogen and fibrin degradation products and D-dimers by a factor of 1.5-2.0 after 120 min from start of treatment compared with the SK lysis. The duration of clot destruction did not change; the distal embolization was not indicated; platelet aggregation activity dropped after thrombus destruction. In summary, intravascular thrombus destruction by a combined US and SK action in vivo is accompanied by enhancing the enzymatic fibrinolysis and lowering the platelet aggregation activity that assists in preventing the distal embolization of the resulting clot debris.

Magnetorheological photocatalytic systems

Preparation and properties of a novel photocatalytic system containing magnetic cores coated with subsequently applied silica and titania shells are discussed. The underlying idea is to impart magnetic properties to the semiconductor particles that permits to control the rheological properties of the photo- catalyst dispersion and makes possible its separation from treated solution without invoking procedures of ltration or centrifugation. Preparation route yielding photoactive titania coating and silica interlayer, which prevents the undesirable doping of catalyst and parasitic charge exchange between titania shell and magnetic core, is described in detail.