Photothermal switch by gallic acid-calcium grafts synthesized by coordination chemistry for sequential treatment of bone tumor and regeneration.

The residual bone tumor and defects which is caused by surgical therapy of bone tumor is a major and important problem in clinicals. And the sequential treatment for irradiating residual tumor and repairing bone defects has wildly prospects. In this study, we developed a general modification strategy by gallic acid (GA)-assisted coordination chemistry to prepare black calcium-based materials, which combines the sequential photothermal therapy of bone tumor and bone defects. The GA modification endows the materials remarkable photothermal properties. Under the near-infrared (NIR) irradiation with different power densities, the black GA-modified bone matrix (GBM) did not merely display an excellent performance in eliminating bone tumor with high temperature, but showed a facile effect of the mild-heat stimulation to accelerate bone regeneration. GBM can efficiently regulate the microenvironments of bone regeneration in a spatial-temporal manner, including inflammation/immune response, vascularization and osteogenic differentiation. Meanwhile, the integrin/PI3K/Akt signaling pathway of bone marrow mesenchymal stem cells (BMSCs) was revealed to be involved in the effect of osteogenesis induced by the mild-heat stimulation. The outcome of this study not only provides a serial of new multifunctional biomaterials, but also demonstrates a general strategy for designing novel blacked calcium-based biomaterials with great potential for clinical use.

Formation of Hydroxyapatite-Based Hybrid Materials in the Presence of Platelet-Poor Plasma Additive.

Biomaterials based on hydroxyapatite with controllable composition and properties are promising in the field of regenerative bone replacement. One approach to regulate the phase composition of the materials is the introduction of biopolymer-based additives into the synthesis process. The purpose of present study was to investigate the formation of hydroxyapatite-based hybrid materials in the presence of 6-24% platelet-poor plasma (PPP) additive, at a [Ca2+]/[PO43-] ratio of 1.67, pH 11, and varying maturing time from 4 to 9 days. The mineral component of the materials comprised 53% hydroxyapatite/47% amorphous calcium phosphate after 4 days of maturation and 100% hydroxyapatite after 9 days of maturation. Varying the PPP content between 6% and 24% brought about the formation of materials with rather defined contents of amorphous calcium phosphate and biopolymer component and the desired morphology, ranging from typical apatitic conglomerates to hybrid apatite-biopolymer fibers. The co-precipitated hybrid materials based on hydroxyapatite, amorphous calcium phosphate, and PPP additive exhibited increased solubility in SBF solution, which defines their applicability for repairing rhinoplastic defects.

Bismuth oxysulfide film electrodes with giant incident photon-to-current conversion efficiency: the dynamics of properties with deposition time.

It was demonstrated in our previous work that the photoelectrochemical (PEC) reduction processes occur with a giant incident photon-to-current conversion efficiency (IPCE ≫ 100%) at bismuth oxysulfide (BOS) semiconductor films in aqueous solutions containing acceptors of photoelectrons ([Fe(CN)6]3-). The anomalously high IPCE was related to the photoconductivity of the semiconductor. In this work, we analyze the dynamics of the chemical and phase composition of BOS films with variation of their deposition time, as well as the dependence of photocurrent on the film thickness and wavelength of the incident light. We demonstrate that in the case of illumination with a short-wavelength light (λ = 465 nm), the photocurrent is reduced down to a complete disappearance with an increase in the film thickness in the range of 0.3-1.3 µm, and for a fixed thickness of the bismuth oxysulfide film, the photocurrent decreases with the reduction of the wavelength indicating that photogeneration of the charge carriers over the entire thickness of the film is necessary for the giant IPCE effect. Using the light induced transient grating (LITG) method, the lifetime of the charge carriers (τ) was determined in the range of 25-80 ps depending on the film thickness, whereas the diffusion coefficient (D) does not exceed 1 cm2 s-1 meaning that the charge transport across the films is determined only by drift.

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.

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.

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.

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.

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.

Heterogeneous photocatalysis in titania-containing liquid foam.

The possibility of effective photodegradation of chemical substrates and photoinactivation of microorganisms in liquid foam containing colloidal TiO(2) has been demonstrated.

Magnetic photocatalysts of the core-shell type.

Two magnetic core-shell type photocatalytic systems are presented: first, Zn0.35Ni0.65Fe2,O4-SiO2-TiO2, showed high activity in the photooxidation of oxalate, and the other, Fe3O4-Fe2O3-polyaniline: P2W18O62(6-), was tested in the reaction of SO2 photooxidation.