Innovative Ti1- xNb xN-Ag Films Inducing Bacterial Disinfection by Visible Light/Thermal Treatment.

This study presents innovative Ti1- xNb xN-Ag films obtained by a suitable combination of low-energy and high-energy sputtering leading to bacterial inactivation. The bacterial inactivation kinetics by the TiNbN layers was drastically enhanced by the addition of 6-7% Ag and proceeded to completion within 3 h after the film autoclaving. By X-ray photoelectron spectroscopy (XPS), the samples after autoclaving presented in their upper layers TiO2, Nb2O5 and Ag2O with a surface composition of Ti0.81Nb0.19N0.99Ag0.068. Surface potential/pH changes in the Ti1- xNb xN-Ag films were monitored during bacterial inactivation. Surface redox processes during the bacterial inactivation were detected by XPS. The diffusion of Ag in the Ti1- xNb xN-Ag films was followed at 50 and 70 °C pointing. The beneficial thermal treatment points out to the bifunctional bacterial inactivation properties of these films and their potential application in healthcare facilities. Interfacial charge transfer (IFCT) under light irradiation between Ag2O, Nb2O5 and TiO2 is suggested consistent with the data found during the course of this study. The TiO2/Nb2O5 lattice mechanism is discussed in the framework of the Verwey's controlled valence model. The surface properties of the Ti1- xNb xN-Ag films were investigated by X-ray diffraction, atomic force microscopy, and scanning electron microscopy.

Quasi-Instantaneous Bacterial Inactivation on Cu-Ag Nanoparticulate 3D Catheters in the Dark and Under Light: Mechanism and Dynamics.

The first evidence for Cu-Ag (50%/50%) nanoparticulate hybrid coatings is presented leading to a complete and almost instantaneous bacterial inactivation in the dark (≤5 min). Dark bacterial inactivation times on Cu-Ag (50%/50%) were observed to coincide with the times required by actinic light irradiation. This provides the evidence that the bimetal Cu-Ag driven inactivation predominates over a CuO/Cu2O and Ag2O oxides inducing a semiconductor driven behavior. Cu- or Ag-coated polyurethane (PU) catheters led to bacterial inactivation needing about ∼30 min. The accelerated bacterial inactivation by Cu-Ag coated on 3D catheters sputtered was investigated in a detailed way. The release of Cu/Ag ions during bacterial inactivation was followed by inductively coupled plasma mass-spectrometry (ICP-MS) and the amount of Cu and Ag-ions released were below the cytotoxicity levels permitted by the sanitary regulations. By stereomicroscopy the amount of live/dead cells were followed during the bacterial inactivation time. By Fourier transform infrared spectroscopy (FTIR), the systematic shift of the -(CH2) band stretching of the outer lipo-polysaccharide bilayer (LPS) was followed to monitor the changes leading to cell lysis. A hydrophobic to hydrophilic transformation of the Cu-Ag PU catheter surface under light was observed within 30 min followed concomitantly to a longer back transformation to the hydrophobic initial state in the dark. Physical insight is provided for the superior performance of Cu-Ag films compared to Cu or Ag films in view of the drastic acceleration of the bacterial inactivation observed on bimetal Cu-Ag films coating PU catheters. A mechanism of bacterial inactivation is suggested that is consistent with the findings reported in this study.

Microstructure of Cu-Ag Uniform Nanoparticulate Films on Polyurethane 3D Catheters: Surface Properties.

The preparation, characterization, and antibacterial testing of Cu-Ag sputtered polyurethane (PU) catheters are addressed in this study. PU catheters with different atomic ratios Cu:Ag have been sputtered and led to different optical properties as followed by diffuse reflectance spectroscopy (DRS) and the surface redox properties were also different for different Cu-Ag ratios as observed by X-ray photoelectron spectroscopy (XPS). The surface atomic percentage concentration of the oxidized/reduced C-species originating from bacterial cultures before and after bacterial inactivation were determined on the Cu-Ag PU catheters. The crystallographic properties were determined by X-ray diffraction (XRD). The XRD-diffractogram showed the presence of Cu2O (111), Cu (200), CuO (020), and Ag (111) indicating that Cu nanoparticles present a more crystalline character compared to Ag nanoparticles. Increasing the percentage of Ag in the Cu-Ag films, bigger Ag-particle agglomerates were detected by scanning transmission electron microscopy (STEM) microanalysis confirming the results obtained by AFM. The bacterial inactivation kinetics of the sputtered Cu-Ag films on PU catheters was investigated in detail. Quasi-instantaneous bacterial inactivation kinetics was induced by the sputtered films on PU catheters after optimization of the Cu-Ag film thickness.

Preparation and Mechanism of Cu-Decorated TiO2-ZrO2 Films Showing Accelerated Bacterial Inactivation.

Antibacterial robust, uniform TiO2-ZrO2 films on polyester (PES) under low intensity sunlight irradiation made up by equal amounts of TiO2 and ZrO2 exhibited a much higher bacterial inactivation kinetics compared to pure TiO2 or ZrO2. The TiO2-ZrO2 matrix was found to introduce a drastic increase in the Cu-dopant promoter enhancing bacterial inactivation compared to Cu sputtered in the same amount on PES. Furthermore, the bacterial inactivation was accelerated by a factor close to three, by Cu- on TiO2-ZrO2 at extremely low levels ∼0.01%. Evidence is presented by X-ray photoelectron spectroscopy for redox catalysis taking place during bacterial inactivation. The TiO2-ZrO2-Cu band gap is estimated and the film properties were fully characterized. Evidence is provided for the photogenerated radicals intervening in the bacterial inactivation. The photoinduced TiO2-ZrO2-Cu interfacial charge transfer is discussed in term of the electronic band positions of the binary oxide and the Cu TiO2 intragap state.

Effect of surface pretreatment of TiO2 films on interfacial processes leading to bacterial inactivation in the dark and under light irradiation.

Evidence is presented for radio-frequency plasma pretreatment enhancing the amount and adhesion of TiO2 sputtered on polyester (PES) and on polyethylene (PE) films. Pretreatment is necessary to attain a suitable TiO2 loading leading to an acceptable Escherichia coli reduction kinetics in the dark or under light irradiation for PES-TiO2 and PE-TiO2 samples. The amount of TiO2 on the films was monitored by diffuse reflectance spectroscopy and X-ray fluorescence. X-ray electron spectroscopy shows the lack of accumulation of bacterial residues such as C, N and S during bacterial inactivation since they seem to be rapidly destroyed by TiO2 photocatalysis. Evidence was found for Ti(4+)/Ti(3+) redox catalysis occurring on PES-TiO2 and PE-TiO2 during the bacterial inactivation process. On PE-TiO2 surfaces, Fourier transform infrared spectroscopy (ATR-FTIR) provides evidence for a systematic shift of the na(CH2) stretching vibrations preceding bacterial inactivation within 60 min. The discontinuous IR-peak shifts reflect the increase in the C-H inter-bond distance leading to bond scission. The mechanism leading to E. coli loss of viability on PES-TiO2 was investigated in the dark up to complete bacterial inactivation by monitoring the damage in the bacterial outer cell by transmission electron microscopy. After 30 min, the critical step during the E. coli inactivation commences for dark disinfection on 0.1-5% wt PES-TiO2 samples. The interactions between the TiO2 aggregates and the outer lipopolysaccharide cell wall involve electrostatic effects competing with the van der Waals forces.

Accelerated Escherichia coli inactivation in the dark on uniform copper flexible surfaces.

The bacterial inactivation of Escherichia coli on Cu/CuO-polyester surfaces prepared by direct current magnetron sputtering was investigated in the dark and under actinic light (360 nm≤ λ ≤ 720 nm; 4.1 mW/cm(2)) as used commonly in hospital facilities. In the dark, complete bacterial inactivation (6log10 reduction) was observed within 150 min and under actinic light within 45 min. Sputtered samples led to nanoparticulate uniform Cu/CuO films ~70 nm thick. The deposition rate used was 2.2×10(15) atoms/cm(2) s as determined by profilometry. X-ray fluorescence was used to determine the sample Cu-content and transmission electron microscopy determined Cu-particles ~20 ± 5 nm in size. The film optical absorption was observed to increase with Cu-content of the sample by diffuse reflection spectroscopy. The bacterial inactivation involved redox processes between Cu/CuO-polyester and the bacteria as observed by x-ray photoelectron spectroscopy. During sample recycling, the amount of Cu-release was determined by inductively coupled plasma-mass spectroscopy. The values required for E. coli inactivation were below the cytotoxicity level threshold allowed for mammalian cells. The E. coli inactivation by Cu/CuO-polyester seems to involve an oligodynamic effect since bacterial inactivation was achieved at very low Cu-concentrations.

LaTiO2N/In2O3 photoanodes with improved performance for solar water splitting.

LaTiO(2)N photoanodes for solar water splitting were prepared by electrophoretic deposition and demonstrated the best photocurrents ever reported for this material. Further important enhancement of the performance was obtained by the use of a sputtered In(2)O(3) overlayer.

Preparation and characterization of silver substrates coated with antimony-doped SnO2 thin films for surface plasmon resonance studies.

This paper reports on the preparation of silver/antimony-doped tin oxide (Ag/SnO(2):Sb) hybrid interfaces using magnetron sputtering and their characterization. The influence of the Sn target composition (doping with 2 or 5% Sb) on the electrochemical and electrical characteristics of the hybrid interface was investigated using X-ray photoelectron spectroscopy (XPS), sheet resistance measurements, cyclic voltammetry, scanning tunneling microscopy (STM) and surface plasmon resonance (SPR). The best interface in terms of electrical conductivity and SPR signal is a hybrid interface with a 8.5 +/- 0.3 nm thick SnO(2):Sb layer obtained from a Sn target with 2% Sb deposited on 38 nm thick silver film. Different strategies to link functional groups onto the Ag/SnO(2):Sb interface are also presented.