in Situ X-ray Photoelectron Spectroscopic and Electrochemical Studies of the Bromide Anions Dissolved in 1-Ethyl-3-Methyl Imidazolium Tetrafluoroborate.

Influence of electrode potential on the electrochemical behavior of a 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) solution containing 5 wt % 1-ethyl-3-methylimidazolium bromide (EMImBr) has been investigated using electrochemical and synchrotron-initiated high-resolution in situ X-ray photoelectron spectroscopy (XPS) methods. Observation of the Br 3d5/2 in situ XPS signal, collected in a 5 wt % EMImBr solution at an EMImBF4⁻vacuum interface, enabled the detection of the start of the electrooxidation process of the Br⁻ anion to Br3⁻ anion and thereafter to the Br2 at the micro-mesoporous carbon electrode, polarized continuously at the high fixed positive potentials. A new photoelectron peak, corresponding to B⁻O bond formation in the B 1s in situ XPS spectra at E ≤ ⁻1.17 V, parallel to the start of the electroreduction of the residual water at the micro-mesoporous carbon electrode, was observed and is discussed. The electroreduction of the residual water caused a reduction in the absolute value of binding energy vs. potential plot slope twice to ca. dBE dE-1 = ⁻0.5 eV V-1 at E ≤ ⁻1.17 V for C 1s, N 1s, B 1s, F 1s, and Br 3d5/2 photoelectrons.

UVA-induced antimicrobial activity of ZnO/Ag nanocomposite covered surfaces.

Application of efficient antimicrobial surfaces has been estimated to decrease both, the healthcare-associated infections and the spread of antibiotic-resistant bacteria. In this paper, we prepared ZnO and ZnO/Ag nanoparticle covered surfaces and evaluated their antimicrobial efficacy towards a Gram-negative bacterial model (Escherichia coli), a Gram-positive bacterial model (Staphylococcus aureus) and a fungal model (Candida albicans) in the dark and under UVA illumination. The surfaces were prepared by spin coating aliquots of ZnO and ZnO/Ag nanoparticle suspensions onto glass substrates. Surfaces contained 2 or 20 µg Zn/cm2 and 0-0.02 µg Ag/cm2. No significant antimicrobial activity of the surfaces, except of those with the highest Ag or Zn content was observed in the dark. On the other hand, UVA illuminated surfaces containing 20 µg Zn/cm2 and 2 µg Zn plus 0.02 µg Ag/cm2 caused >3 log decrease in the viable counts of E. coli and S. aureus in 30 min. As proven by brilliant blue FCF dye degradation and elemental analysis of the surfaces, this remarkable antimicrobial activity was a combined result of photocatalytic effect and release of Zn and Ag ions from surfaces. Surfaces retained significant antibacterial and photocatalytic properties after several usage cycles. Compared to bacteria, yeast C. albicans was significantly less sensitive to the prepared surfaces and only about 1 log reduction of viable count was observed after 60 min UVA illumination. In conclusion, the developed ZnO/Ag surfaces exhibit not only high antibacterial activity but also some antifungal activity.

Photofragmentation of gas-phase acetic acid and acetamide clusters in the vacuum ultraviolet region.

Photofragmentation of gas-phase acetamide and acetic acid clusters produced by a supersonic expansion source has been studied using time-of-flight mass spectrometry and the partial ion yield (PIY) technique combined with tunable vacuum-ultraviolet synchrotron radiation. Appearance energies of the clusters and their fragments were experimentally determined from the PIY measurements. The effect of clusterization conditions on the formation and fragmentation of acetic acid clusters was investigated. Ab initio quantum mechanical calculations were performed on both samples' dimers to find their neutral and ionized geometries as well as proton transfer energy barriers leading to the optimal geometries. In the case of the acetamide dimer, the reaction resulting in the production of ammoniated acetamide was probed, and the geometry of the obtained ion was calculated.

Colorimetric gas detection by the varying thickness of a thin film of ultrasmall PTSA-coated TiO2 nanoparticles on a Si substrate.

Colorimetric gas sensing is demonstrated by thin films based on ultrasmall TiO2 nanoparticles (NPs) on Si substrates. The NPs are bound into the film by p-toluenesulfonic acid (PTSA) and the film is made to absorb volatile organic compounds (VOCs). Since the color of the sensing element depends on the interference of reflected light from the surface of the film and from the film/silicon substrate interface, colorimetric detection is possible by the varying thickness of the NP-based film. Indeed, VOC absorption causes significant swelling of the film. Thus, the optical path length is increased, interference wavelengths are shifted and the refractive index of the film is decreased. This causes a change of color of the sensor element visible by the naked eye. The color response is rapid and changes reversibly within seconds of exposure. The sensing element is extremely simple and cheap, and can be fabricated by common coating processes.

Photoinduced intermolecular dynamics and subsequent fragmentation in VUV-ionized acetamide clusters.

Photofragmentation of small gas-phase acetamide clusters (CH3CONH2)n (n ≤ 10) produced by a supersonic expansion source has been studied using time-of-flight ion mass spectroscopy combined with tunable vacuum-ultraviolet (VUV) synchrotron radiation. Fragmentation channels of acetamide clusters under VUV photoionization resulting in protonated and ammoniated clusters formation were identified with the discussion about the preceding intramolecular rearrangements. Acetamide-2,2,2-d3 clusters were also studied in an experiment with a gas discharge lamp as a VUV light source; comparison with the main experiment gave insights into the mechanism of formation of protonated acetamide clusters, indicating that proton transfer from amino group plays a dominant role in that process. Geometry of the acetamide dimer was discussed and the most stable arrangement was concluded to be achieved when subunits of the dimer are connected via two N-H⋯O -C hydrogen bonds. Also, the influence of the photon energy on the stability of the clusters and their fragmentation channels has been examined.

Photocatalytic antibacterial activity of nano-TiO2 (anatase)-based thin films: effects on Escherichia coli cells and fatty acids.

Titanium dioxide is a photocatalyst with well-known ability to oxidise a wide range of organic contaminants as well as to destroy microbial cells. In the present work TiO2 nanoparticles with high specific surface area (150m(2)/g) were used to prepare nanostructured films. The TiO2 nanoparticle-based film in combination with UV-A illumination with intensity (22W/m(2)) comparable to that of the sunlight in the UV-A region was used to demonstrate light-induced antibacterial effects. Fast and effective inactivation of Escherichia coli cells on the prepared thin films was observed. Visualization of bacterial cells under scanning electron microscopy (SEM) showed enlargement of the cells, distortion of cellular membrane and possible leakage of cytoplasm after 10min of exposure to photoactivated TiO2. According to the plate counts there were no viable cells as early as after 20min of exposure to UV-A activated TiO2. In parallel to effects on bacterial cell viability and morphology, changes in saturated and unsaturated fatty acids - important components of bacterial cell membrane-were studied. Fast decomposition of saturated fatty acids and changes in chemical structure of unsaturated fatty acids were detected. Thus, we suggest that peroxidation and decomposition of membrane fatty acids could be one of the factors contributing to the morphological changes of bacteria observed under SEM, and ultimately, cell death.

Biofunctional hybrid materials: bimolecular organosilane monolayers on FeCr alloys.

Hybrid organic-inorganic interfaces are the key to functionalization of stainless steel (SS). We present a solution-based deposition method for fabricating uniform bimolecular organosilane monolayers on SS and show that their properties and functionalities can be further developed through site-specific biotinylation. We correlate molecular properties of the interface with its reactivity via surface sensitive synchrotron radiation mediated high-resolution photoelectron spectroscopy (HR-PES) and chemical derivatization (CD), and we demonstrate specific bonding of streptavidin proteins to the hybrid interface. The method facilitates efficient growth of uniform bimolecular organosilane monolayers on SS under ambient conditions without the need to prime the SS surface with vacuum-deposited inorganic buffer layers. The obtained insights into molecular bonding, orientation, and behaviour of surface-confined organofunctional silanes on SS enable a new generic approach to functionalization of SS surfaces with versatile nanomolecular organosilane layers.