Interaction between titanium dioxide nanoparticles and human serum albumin revealed by fluorescence spectroscopy in the absence of photoactivation

Titanium dioxide (TiO₂) nanoparticles (NPs) are widely used as an important kind of biomaterials. The interaction between TiO₂ (P25) at 20 nm in diameter and human serum albumin (HSA) was studied by fluorescence spectroscopy in this work. Under the simulative physiological conditions, fluorescence data revealed the presence of a single class of binding site on HSA and its binding constants (K_a) were 2.18±0.04×10⁴, 0.87±0.05×10⁴, 0.68±0.06×10⁴ M⁻¹ at 298, 304 and 310 K, respectively. In addition, according to the Van’t Hoff equation, the thermodynamic functions standard enthalpy (ΔH⁰) and standard entropy (ΔS⁰) for the reaction were calculated to be −75.18±0.15 kJ mol⁻¹ and −170.11±0.38 J mol⁻¹ K⁻¹. These results indicated that TiO₂ NPs bond to HSA mainly by van der Waals force and hydrogen bonding formation in low dielectric media, and the electrostatic interactions cannot be excluded. Furthermore, the effects of common ions on the binding constant of TiO₂ NPs-HSA complex were discussed.     

Effect of Sn concentration on structural and optical properties of zinc oxide nanobelts

We investigated structural and optical properties of Sn-doped ZnO nanobelts with different Sn concentrations. X-ray diffraction and Raman spectra showed that the Sn-doped ZnO nanobelts have wurtzite structure at low Sn concentration (<2.1 at%) and over 2.1 at% a part of them starts to have the inverse spinel Zn₂SnO₄ structure phase. In addition, for Sn-doped ZnO nanobelts, the photoluminescence spectra indicate that ultraviolet emission peak appears first a blue shift with the increase of Sn concentration due to Burstein-Moss effect and then exhibits a red shift due to band gap renormalization effect.     

Targeted sonodynamic therapy using protein-modified TiO2 nanoparticles

Our previous study suggested new sonodynamic therapy for cancer cells based on the delivery of titanium dioxide (TiO₂) nanoparticles (NPs) modified with a protein specifically recognizing target cells and subsequent generation of hydroxyl radicals from TiO₂ NPs activated by external ultrasound irradiation (called TiO₂/US treatment). The present study first examined the uptake behavior of TiO₂ NPs modified with pre-S1/S2 (model protein-recognizing hepatocytes) by HepG2 cells for 24 h. It took 6 h for sufficient uptake of the TiO₂ NPs by the cells. Next, the effect of the TiO₂/US treatment on HepG2 cell growth was examined for 96 h after the 1 MHz ultrasound was irradiated (0.1 W/cm², 30 s) to the cells which incorporated the TiO₂ NPs. Apoptosis was observed at 6 h after the TiO₂/US treatment. Although no apparent cell-injury was observed until 24 h after the treatment, the viable cell concentration had deteriorated to 46% of the control at 96 h. Finally, the TiO₂/US treatment was applied to a mouse xenograft model. The pre-S1/S2-immobilized TiO₂ (0.1 mg) was directly injected into tumors, followed by 1 MHz ultrasound irradiation at 1.0 W/cm² for 60 s. As a result of the treatment repeated five times within 13 days, tumor growth could be hampered up to 28 days compared with the control conditions.     

Growth research of Sn nanoparticles deposited on Si(0 0 1) substrate by solid phase epitaxy

High density of Sn nanoparticles (NPs) had been obtained directly on Si(0 0 1) substrate by solid phase epitaxy. The dependence of the morphology and crystallinity of Sn NPs on Sn coverage, annealing temperature and annealing time was investigated by atomic force microscope (AFM) and X-ray diffraction (XRD). Uniform and densely packed (∼10¹⁰ cm⁻²) Sn NPs were obtained at low Sn coverage, low annealing temperature and short annealing time, respectively. The XRD results showed that, the formed Sn NPs were in the form of crystalline β-Sn, with a distinct orientation of Sn(1 1 0)//Si(0 0 1). The nucleation activation energy of Sn adatoms on Si(0 0 1) surface was estimated to be 0.41 ± 0.05 eV.     

Room and high-temperature scanning tunnelling microscopy and spectroscopy (HT-STM/STS) investigations of surface nanomodifications created on the TiO2(1 1 0) surface

High-temperature scanning tunnelling microscopy, scanning tunnelling spectroscopy and current imaging tunnelling spectroscopy (HT-STM/STS/CITS) were used to study the topographic and electronic structures changes due to surface modifications of the TiO₂(1 1 0) surface caused by the STM tip. In situ high-temperature STM results showed that the created modifications were stable even at elevated temperatures. The STS/CITS results showed the presence of energy gap below the Fermi level on the untreated regions. The disappearance of energy gap below the Fermi level on the modifications created by the tip was observed. It is assumed that the presence of the tip can change the chemical stoichiometry of the surface from TiO_2−x towards Ti₂O₃.     

Low temperature thermoelectric properties of Pb- or Sn-doped Bi-Sb alloys

Pb- or Sn-doped Bi₈₈Sb₁₂ alloys were prepared by direct melting, quenching, and annealing. The Bi-Sb alloy phase was predominant in all samples. Pb or Sn atoms were distributed almost uniformly in Bi₈₈Sb_12, while some segregation was confirmed at the grain boundaries when Pb or Sn was involved heavily. The thermoelectric properties of these doped materials were investigated by measuring the Hall coefficient, electrical resistivity, and Seebeck coefficient between 20 K and 300 K. The Hall and Seebeck coefficients of Pb- or Sn-doped samples were positive at low temperatures, indicating that the doping element acted as an acceptor. Temperatures resulting in positive Hall and Seebeck coefficients further increased with increasing doping amount and with respect to the annealing process. As a result, a large power factor of 1.2 W/mK² could be obtained in the 3-at% Sn-doped sample at 220 K, with a large positive Seebeck coefficient.     

The synthesis of Ag/polypyrrole coaxial nanocables via ion adsorption method using different oxidants

Ag/polypyrrole (PPy) coaxial nanocables (NCs) were synthesized by an ion adsorption method. In this method, the pre-made Ag nanowires (NWs) were dispersed in the aqueous solution of copper acetate (Cu(Ac)₂), and the Cu²⁺ ions adsorbed onto the surface of Ag NWs can oxidize pyrrole monomers to polymerize into uniform PPy sheath outside Ag NWs after the Cu(Ac)₂-treated Ag NWs were re-dispersed in the aqueous solution of pyrrole. The morphology of NCs was characterized by transmission electron microscope (TEM) and scanning electron microscope (SEM). The relationship between the thickness of polymer sheath and the concentration of Cu(Ac)₂ was established. As Cu(Ac)₂ which served as the oxidant can also be replaced by AgNO₃ in this synthesis, the differences on the structure of polymer sheath caused by different oxidants were studied by surface-enhanced Raman scattering (SERS), high-resolution transmission electron microscope (HR-TEM), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). Comparing with the characterization results of Ag/PPy NCs synthesized using AgNO₃ as the oxidant which indicates the random arrangement of PPy chains at the interface between polymer sheath and Ag NWs, PPy chain oxidized by Cu²⁺ tends to show a relatively ordered conformation at the interface with the pyrrole rings identically taking the plane vertical to the surface of Ag NWs. In addition, although the main part of the polymer sheath was composed of PPy whatever kind of oxidant was used, the sheath of the NCs oxidized by Cu²⁺ is typical for the existence of Cu(I)–pyrrole coordinate structures with strong Cu(I)–N bond signal shown in XPS characterization.     

Valence band offset of MgO/TiO2 (rutile) heterojunction measured by X-ray photoelectron spectroscopy

The valence band offset (VBO) of MgO/TiO₂ (rutile) heterojunction has been directly measured by X-ray photoelectron spectroscopy. The VBO of the heterojunction is determined to be 1.6 ± 0.3 eV and the conduction band offset (CBO) is deduced to be 3.2 ± 0.3 eV, indicating that the heterojunction exhibits a type-I band alignment. These large values are sufficient for MgO to act as tunneling barriers in TiO₂ based devices. The accurate determination of the valence and conduction band offsets is important for use of MgO as a buffer layer in TiO₂ based field-effect transistors and dye-sensitized solar cells.     

Preparation and electrochemistry of one-dimensional nanostructured MnO2/PPy composite for electrochemical capacitor

One-dimensional nanostructured manganese dioxide/polypyrrole (MnO₂/PPy) composite was prepared by in situ chemical oxidation polymerization of pyrrole in the host of inorganic matrix of MnO₂, using complex of methyl orange (MO)/FeCl₃ as a reactive self-degraded soft-template. The morphology and structure of the composite were characterized by infrared spectroscopy (IR) X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that the MnO₂/PPy composite consists of α-MnO₂ and PPy with nanotube-like structure. Electrochemical properties of the composite demonstrated the material showed good electrochemical reversibility after 500 charge-discharge cycles in the potential range of −0.4 to 0.6 V, the tube-like nanocomposite has the potential application in electrochemical capacitor.     

Fabrication of TiO2 μ-donuts by sol-gel spin coating using a polymer mask

TiO₂ μ-donuts have been fabricated on glass and silicon substrates using polymer masks in combination with a sol-gel technique. Cylindrical poly(methyl methacrylate) (PMMA) nanopillars have been created using a composite polymer of polystyrene (PS) and PMMA followed by careful removal of the PS. Atomic force microscopy (AFM) analyses show that the height and diameter of the PMMA cylinders used as the mask are 440 ± 5 nm and 2.1 ± 0.2 μm, respectively. The cylindrical PMMA nanopillars have been coated with the sol of the TiO₂ precursor by a spin coating technique and annealed in air at elevated temperature to remove the PMMA mask. Removal of the PMMA mask has resulted in the formation of well ordered μ-donuts of TiO₂ on silicon surfaces. The interior and exterior heights of the TiO₂ μ-donuts are found to be 373 ± 152 nm and 457 ± 136 nm, respectively; and the interior and exterior diameters of the TiO₂ μ-donuts are found to be 1.33 ± 0.63 μm and 2.82 ± 0.50 μm, respectively. X-ray photoelectron spectroscopy (XPS) spectra of the TiO₂ μ-donuts as well as the smooth TiO₂ thin film showed signals from Ti and O confirming the presence of TiO₂ with Ti 2p_3/2 and O 1s peaks at 458.8 eV and 530.4 eV, respectively. The O 1s peak of the TiO₂ μ-donuts shows another peak at binding energy 532.0 eV due to SiO₂, as during annealing, the PMMA evaporates and the Si substrate is exposed. The X-ray diffractometer (XRD) pattern of the smooth TiO₂ thin film indicates that the anatase phase is present, with the characteristic peaks observed at 2θ values of 25.4°, 37.4°, and 48° corresponding to (1 0 1), (0 0 4), and (2 0 0) planes, respectively. UV-vis absorption spectra of TiO₂ μ-donuts on glass showed an unusual absorption of light in the visible region at ∼524 nm in addition to the usual UV absorption at ∼337 nm.     

Optical properties of ITO/TiO2 single and double layer thin films deposited by RPLAD

Indium tin oxide (ITO) and titanium dioxide (TiO₂) single layer and double layer ITO/TiO₂ films were prepared using reactive pulsed laser ablation deposition (RPLAD) with an ArF excimer laser for applications in dye-sensitized solar cells (DSSCs). The films were deposited on SiO₂ substrates either at room temperatures (RT) or heated to 200-400 °C. Under optimized conditions, transmission of ITO films in the visible (vis) range was above 89% for films produced at RT and 93% for the ones deposited at higher temperatures. Increasing the substrate temperature from RT to 400 °C enhances the transmission of TiO₂ films in the vis-NIR from about 70% to 92%. High transmission (≈90%) was observed for the double layer ITO/TiO₂ with a transmission cut-off above 900 nm. From the transmission data, the energies gaps (E_g), as well as the refractive indexes (n) for the films were estimated. n ≈ 2.03 and 2.04, respectively for ITO films and TiO₂ film deposited at 400 °C in the visible region. Post-annealing of the TiO₂ films for 3 h at 300 and 500 °C was performed to enhance n. The refractive index of the TiO₂ films increases with the post-annealing temperature. The direct band gap is 3.6, 3.74 and 3.82 eV for ITO films deposited at RT, 200, and 400 °C, respectively. The TiO₂ films present a direct band gap of 3.51 and 3.37 eV for as deposited TiO₂ films and when annealed at 400 °C, respectively. There is a shift of about 0.1 eV between ITO and ITO/TiO₂ films deposited at 200 °C. The shift decreases by half when the TiO₂ film was deposited at 400 °C. Post-annealing was also performed on double layer ITO/TiO₂.     

The correlation between structure and magnetism of Ni-implanted TiO2 annealed at different temperatures

In this paper, the structural and magnetic properties of Ni metal implanted TiO₂ single crystals are discussed. Ni nanocrystals (NCs) have been formed in TiO₂ after ion implantation. Their crystallite sizes increased with increasing post-annealing temperature. Metallic Ni nanocrystals inside the TiO₂ matrix are stable up to an annealing temperature of 1073 K. The Ni NCs formed inside TiO₂ make the major contribution to the measured ferromagnetism.     

Temperature-dependent optical absorption measurements and Schottky contact behavior in layered semiconductor n-type InSe(:Sn)

The layered n-InSe(:Sn) single crystal samples have been cleaved from a large crystal ingot grown from non-stoichiometric melt by the Bridgman-Stockbarger method. It has been made the absorption measurements of these samples without Schottky contact under electric fields of 0.0 and 6000 V cm⁻¹. The band gap energy value of the InSe:Sn has been calculated as 1.36 ± 0.01 eV (at 10 K) and 1.28 ± 0.01 eV (at 300 K) under zero electrical field, and 1.31 ± 0.01 eV (at 10 K) and 1.26 ± 0.01 eV (at 300 K) under 6000 Vcm⁻¹. The current-voltage (I-V) characteristics of Au-Ge/InSe(:Sn)/In Schottky diodes have been measured in the temperature range 80-320 K with a temperature step of 20 K. An experimental barrier height (BH) Φ_ap value of about 0.70 ± 0.01 eV was obtained for the Au-Ge/InSe(:Sn)/In Schottky diode at the room temperature (300 K). An abnormal decrease in the experimental BH Φ_b and an increase in the ideality factor n with a decrease in temperature have been explained by the barrier inhomogeneities at the metal-semiconductor interface. From the temperature-dependent I-V characteristics of the Au-Ge/InSe(:Sn)/In contact, that is, and A^* as 0.94 ± 0.02 and 0.58 ± 0.02 eV, and 27 ± 2 and 21 ± 1 (A/cm² K²), respectively, have been calculated from a modified versus 1/T plot for the two temperature regions. The Richardson constant values are about two times larger than the known value of 14.4 (A/cm² K²) known for n-type InSe. Moreover, in the temperature range 80-320 K, we have also discussed whether or not the current through the junction has been connected with TFE.     

Adsorption structure of glycine on TiO2(1 1 0): A photoelectron diffraction determination

High-resolution core-level photoemission and scanned-energy mode photoelectron diffraction (PhD) of the O 1s and N 1s states have been used to investigate the interaction of glycine with the rutile TiO₂(1 1 0) surface. Whilst there is clear evidence for the presence of the zwitterion CH₂COO⁻ with multilayer deposition, at low coverage only the deprotonated glycinate species, NH₂CH₂COO is present. Multiple-scattering simulations of the O 1s PhD data show the glycinate is bonded to the surface through the two carboxylate O atoms which occupy near-atop sites above the five-fold-coordinated surface Ti atoms, with a Ti-O bondlength of 2.12 ± 0.06 Å. Atomic hydrogen arising from the deprotonation is coadsorbed to form hydroxyl species at the bridging oxygen sites with an associated Ti-O bondlength of 2.01 ± 0.03 Å. Absence of any significant PhD modulations of the N 1s emission is consistent with the amino N atom not being involved in the surface bonding, unlike the case of glycinate on Cu(1 1 0) and Cu(1 0 0).     

Synthesis and characterization of TiO2/Fe2O3 core-shell nanocomposition film and their photoelectrochemical property

TiO₂/Fe₂O₃ core-shell nanocomposition film has been fabricated via two-step method. TiO₂ nanorod arrays are synthesized by a facile hydrothermal method, and followed by Fe₂O₃ nanoparticles deposited on TiO₂ nanorod arrays through an ordinary chemical bath deposition. The phase structures, morphologies, particle size, chemical compositions of the composites have been characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM) and ultraviolet-visible (UV-vis) spectrophotometer. The results confirm that Fe₂O₃ nanoparticles of mean size ca. 10 nm coated on the surface of TiO2 NRs. After depositing Fe₂O₃, UV-vis absorption property is induces the shift to the visible-light range, the annealing temperature of 600 °C is the best condition for UV-vis absorption property of TiO₂/Fe₂O₃ nanocomposite film, and increasing Fe content, optical activity are enhanced one by one. The photoelectrochemical (PEC) performances of the as-prepared composite nanorods are determined by measuring the photo-generated currents under illumination of UV-vis light. The TiO₂ NRs modified by Fe₂O₃ show the photocurrent value of 1.36 mA/cm² at 0 V vs Ag/AgCl, which is higher than those of unmodified TiO₂ NRs.     

Synthesis and characterization of hybrid nanocomposites of polypyrrole filled with iron oxide nanoparticles

Hybrid polypyrrole (PPy)/α-Fe₂O₃ nanocomposite films were fabricated by spin coating on a glass substrate. X-Ray diffraction analysis revealed the crystalline structure of α-Fe₂O₃ nanostructures and the nanocomposites. The broad PPy peak weakened in intensity as the α-Fe₂O₃ content increased in PPy/α-Fe₂O₃ nanocomposites. Characteristic Fourier-transform IR peaks for pure PPy shifted to higher wavenumbers on addition of α-Fe₂O₃ to PPy/α-Fe₂O₃ nanocomposites. This can be attributed to better conjugation and interactions between PPy and α-Fe₂O₃ nanoparticles. Field-emission scanning electron microscopy, transmission electron microscopy, and atomic force microscopy images of the nanocomposites reveal a uniform distribution of α-Fe₂O₃ nanoparticles in the PPy matrix. UV-vis absorption spectroscopy revealed a blue shift from λ_max= 441 nm for PPy to λ_max= 392 nm for PPy/α-Fe₂O₃, reflecting strong interactions between PPy and α-Fe₂O₃ nanoparticles. The room-temperature dc electrical conductivity increased from 4.33×10⁻⁹ to 1.81×10⁻⁸ S/cm as the α-Fe₂O₃ nanoparticle content increased from 10 to 50 wt.% in PPy/α-Fe₂O₃ nanocomposites.     

Shape tailoring of hexagonally ordered triangular gold nanoparticles with nanosecond-pulsed laser light

In this contribution recent results on selective and precise tailoring of triangular gold nanoparticles (NPs) using ns-pulsed laser light are presented. The NPs were prepared by nanosphere lithography and subsequently tailored with ns-pulsed laser light using different fluences and wavelengths. The method is based on the size and shape dependent localized surface plasmon polariton resonance (SPR) of the NPs. We will demonstrate that the gap size between triangular NPs can be tuned from approximately 102±14 nm to 122±11 nm, due to a shape change of the NP from triangular to oblate. These morphological changes are accompanied by a significant shift of the surface plasmon resonance from λ_SPR=730 nm to λ_SPR=680 nm. Most importantly if the laser wavelength is chosen such that the dipolar SPR is excited, the hexagonal order of the NPs remains intact after irradiation, in contrast to excitation via the quadrupole SPR or within the interband transition. A tuneable gap size and the conservation of the hexagonal order of the NP array is the precondition for applications, where the NPs should serve as anchor points, e.g. for functional molecular nanowires, which can be used to utilize molecular devices.     

A simple and low temperature process for super-hydrophilic rutile TiO2 thin films growth

We investigate an environmentally friendly aqueous solution system for rutile TiO₂ violet color nanocrystalline thin films growth on ITO substrate at room temperature. Film shows considerable absorption in visible region with excitonic maxima at 434 nm. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), UV-vis, water surface contact angle and energy dispersive X-ray analysis (EDX) techniques in addition to actual photo-image that shows purely rutile phase of TiO₂ with violet color, super-hydrophilic and densely packed nanometer-sized spherical grains of approximate diameter 3.15 ± 0.4 nm, characterize the films. Band gap energy of 4.61 eV for direct transition was obtained for the rutile TiO₂ films. Film surface shows super-hydrophilic behavior, as exhibited water contact angle was 7°. Strong visible absorption (not due to chlorine) leaves future challenge to use these films in extremely thin absorber (ETA) solar cells.     

Band offsets at the epitaxial anatase TiO2/n-SrTiO3(0 0 1) interface

We have used high-energy resolution X-ray photoelectron spectroscopy to measure valence band offsets at the epitaxial anatase TiO₂(0 0 1)/n-SrTiO₃(0 0 1) heterojunction prepared by molecular beam epitaxy. The valence band offsets range between −0.06 ± 0.05 and +0.16 ± 0.05 eV for anatase thicknesses between 1 and 8 monolayers and three different methods of substrate surface preparation, with no systematic dependence on film thickness. The conduction band offset (CBO) varies over a comparable range by virtue of the fact that anatase and SrTiO₃ exhibit the same bandgap (∼3.2 eV). In contrast, density functional theory predicts the VBO to be +0.55 eV. The lack of agreement between theory and experiment suggests that either some unknown factor in the interface structure or composition excluded from the modeling is influencing the band offset, or that density functional theory cannot accurately calculate band offsets in these oxide materials. The small experimental band offsets have important implications for the use of this interface for fundamental investigations of surface photocatalysis. Neither electrons nor holes are likely to become trapped in the substrate and thus be unable to participate in surface photocatalytic processes.     

Simple one-step ultrasonic synthesis of anatase titania/polypyrrole nanocomposites

In this work, hybrid nanocomposites based on anatase titania:polypyrrole (TiO₂:PPy) were directly obtained from a simple, one-step, ultrasonic (UT)-assisted synthesis. The properties of these crystalline nanocomposites were compared with those of others fabricated using cold (Cold)-assisted synthesis without any UT assistance, which required a hydrothermal treatment (HT) to yield crystalline anatase titania in the nanocomposite (TiO₂:PPy) at low temperature (130 °C) and in a short time (3 h). The SEM results demonstrated that the UT-assisted synthesis is a feasible method to obtain anatase TiO₂:PPy nanocomposites with controlled morphology using low energy. The Fourier transform infrared (FT-IR) bands of the crystalline nanocomposites exhibited a shift with respect to neat components, which was attributed to the strong interaction between the secondary amine groups (N–H) of PPy and the oxygen from TiO₂. The acceptable absorption in the visible region (λ_max = 670 nm) indicates that these nanocomposites are good candidates for harvesting energy in solar cells. Devices based on these nanocomposites were built to evaluate their electrical properties. An increase in the photocurrent was observed for the devices prepared with the nanocomposites from the UT-assisted synthesis.