Photocatalytic porcelain grés large slabs digitally coated with AgNPs-TiO2.

TiO2 is employed as both photocatalytic and structural materials, leading to its applications in external coatings or in interior furnishing devices, including cement mortar, tiles, floorings, and glass supports. The authors have already demonstrated the efficiency of photoactive micro-sized TiO2 and here its industrial use is reported using the digital printing to coat porcelain grés slabs. Many advantages are immediately evident, namely rapid and precise deposition, no waste of raw materials, thus positively affecting the economy of the process. Data for the thin films deposited by digital printing were compared with those obtained for the conventional spray method. The use of metal-doped TiO2 is also reported so that the photoactivity of these materials can be exploited even under LED light. The digital inkjet printed coatings exhibited superior photocatalytic performance owing to both higher exposed surface area and greater volume of deposited anatase, as well as the greater areal distribution density of thinly and thickly coated regions. Moreover, the presence of TiO2 doped silver increased the efficiency of the materials in NOx degradation both under UVA and LED lights.

Oxidative and mutagenic effects of low intensity GSM 1800 MHz microwave radiation.

AIM: Despite a significant number of epidemiological studies on potential carcinogenicity of microwave radiation (MWR) from wireless devices and a bulk of experimental studies on oxidative and mutagenic effects of low intensity MWR, the discussion on potential carcinogenicity of low intensity MWR is going on. This study aims to assess oxidative and mutagenic effects of low intensity MWR from a typical commercial model of a modern smartphone. MATERIALS AND METHODS: The model of developing quail embryos has been used for the assessment of oxidative and mutagenic effects of Global System for Mobile communication (GSM) 1800 MHz MWR from a commercial model of smartphone. The embryos were exposed in ovo to 0.32 µW/cm2, discontinuously - 48 s - On, 12 s - Off, during 5 days before and 14 days through the incubation period. RESULTS: The exposure of quail embryos before and during the incubation period to low intensity GSM 1800 MHz has resulted in expressive statistically significant oxidative effects in embryonic cells, including a 2-fold increase in superoxide generation rate and 85% increase in nitrogen oxide generation rate, damages of DNA integrity and oxidative damages of DNA (up to twice increased levels of 8-oxo-dG in cells of 1-day old chicks from the exposed embryos). Finally, the exposure resulted in a significant, almost twice, increase of embryo mortality. CONCLUSION: The exposure of model biological system to low intensity GSM 1800 MHz MWR resulted in significant oxidative and mutagenic effects in exposed cells, and thus should be recognized as a significant risk factor for living cells.

Photocatalytic oxidation of nitrogen oxides over {001}TiO2: the influence of F- ions.

A series of anatase TiO2 nanosheets with different percentage of {001} facets ({001}TiO2) were synthesized through a hydrothermal route using tetrabutyltitanate as a titanium precursor and HF as a shape controlling agent. The amount of HF exhibits an obvious influence on the structures and activities of TiO2 samples. The adsorbed surface F- ions on the {001} facets of the anatase TiO2 were removed by washing them with NaOH solution. The as-prepared catalysts were characterized by X-ray diffraction, Brunner-Emmet-Teller measurements, ultraviolet-visible diffuse reflectance spectroscopy, scanning electron microscopy, transmission electron microscopy techniques, and X-ray photoelectron spectroscopy analysis. The results indicated that all the as-prepared catalysts showed an anatase crystalline and nanosheet structure, as well as a strong ultraviolet light absorbance. With the increase of HF content, the crystallite size and the percentage of {001} facets increased first and later decreased, state the opposite change observed in BET. When the content of HF was 4.4 mL, the percentage of {001} facets reached the maximum up to 61.62%. After all samples were treated with 0.1 M NaOH solution, the percentage of {001} facets increased to a maximum of 64.46%. All the samples washed by NaOH solution exhibited much higher photocatalytic activity for NOx oxidation under UV light irradiation than P25, {101}TiO2, and {001}TiO2 without NaOH washing, suggesting that the surface F- ions inhibited the photocatalytic NOx oxidation. Moreover, the results showed that the NaOH-washed {001}TiO2 has a high humidity tolerance.

Photolysis of Nitric Acid and Nitrate on Natural and Artificial Surfaces.

Photolysis of nitric acid and nitrate (HNO3/nitrate) was investigated on the surfaces of natural and artificial materials, including plant leaves, metal sheets, and construction materials. The surfaces were conditioned in the outdoor air prior to experiments to receive natural depositions of ambient HNO3/nitrate and other atmospheric constituents. The photolysis rate constant (JHNO3(s)) of the surface HNO3/nitrate was measured based on the production rates of nitrous acid (HONO) and nitrogen oxides (NOx). The JHNO3(s) values, from 6.0 × 10(-6) s(-1) to 3.7 × 10(-4) s(-1), are 1 to 3 orders of magnitude higher than that of gaseous HNO3. The HONO was the major product from photolysis of HNO3/nitrate on most plant leaves, whereas NOx was the major product on most artificial surfaces. The JHNO3(s) values decreased with HNO3/nitrate surface density and could be described by a simple analytical equation. Within a typical range of HNO3/nitrate surface density in the low-NOx forested areas, photolysis of HNO3/nitrate on the forest canopy can be a significant source for HONO and NOx for the overlying atmosphere.

Synthesis and evaluation of nitroxide-based oligoradicals for low-temperature dynamic nuclear polarization in solid state NMR.

We describe the synthesis of new nitroxide-based biradical, triradical, and tetraradical compounds and the evaluation of their performance as paramagnetic dopants in dynamic nuclear polarization (DNP) experiments in solid state nuclear magnetic resonance (NMR) spectroscopy with magic-angle spinning (MAS). Under our experimental conditions, which include temperatures in the 25-30 K range, a 9.4 T magnetic field, MAS frequencies of 6.2-6.8 kHz, and microwave irradiation at 264.0 GHz from a 800 mW extended interaction oscillator source, the most effective compounds are triradicals that are related to the previously-described compound DOTOPA-TEMPO (see Thurber et al., 2010), but have improved solubility in glycerol/water solvent near neutral pH. Using these compounds at 30 mM total nitroxide concentration, we observe DNP enhancement factors of 92-128 for cross-polarized (13)C NMR signals from (15)N,(13)C-labeled melittin in partially protonated glycerol/water, and build-up times of 2.6-3.8s for (1)H spin polarizations. Net sensitivity enhancements with biradical and tetraradical dopants, taking into account absolute (13)C NMR signal amplitudes and build-up times, are approximately 2-4 times lower than with the best triradicals.

Theoretical spectroscopy and photodynamics of a ruthenium nitrosyl complex.

Photoactive transition-metal nitrosyl complexes are particularly interesting as potential drugs that deliver nitric oxide (NO) upon UV-light irradiation to be used, e.g., in photodynamic therapy. It is well-recognized that quantum-chemical calculations can guide the rational design and synthesis of molecules with specific functions. In this contribution, it is shown how electronic structure calculations and dynamical simulations can provide a unique insight into the photodissociation mechanism of NO. Exemplarily, [Ru(PaPy3)(NO)](2+) is investigated in detail, as a prototype of a particularly promising class of photoactive metal nitrosyl complexes. The ability of time-dependent density functional theory (TD-DFT) to obtain reliable excited-state energies compared with more sophisticated multiconfigurational spin-corrected calculations is evaluated. Moreover, a TD-DFT-based trajectory surface-hopping molecular dynamics study is employed to reveal the details of the radiationless decay of the molecule via internal conversion and intersystem crossing. Calculations show that the ground state of [Ru(PaPy3)(NO)](2+) includes a significant admixture of the Ru(III)(NO)(0) electronic configuration, in contrast to the previously postulated Ru(II)(NO)(+) structure of similar metal nitrosyls. Moreover, the lowest singlet and triplet excited states populate the antibonding metal d → πNO* orbitals, favoring NO dissociation. Molecular dynamics show that intersystem crossing is ultrafast (<10 fs) and dissociation is initiated in less than 50 fs. The competing relaxation to the lowest S1 singlet state takes place in less than 100 fs and thus competes with NO dissociation, which mostly takes place in the higher-lying excited triplet states. All of these processes are accompanied by bending of the NO ligand, which is not confined to any particular state.

The use of vacuum ultraviolet irradiation to oxidize SO2 and NOx for simultaneous desulfurization and denitrification.

A simple and efficient method for simultaneous desulfurization and denitrification via vacuum ultraviolet (VUV) irradiation and with no additional chemicals is presented. The simultaneous removal of 90% SO2 and 96% NOx (NO+NO2) was achieved from the simulated flue gas under the irradiation from a low-pressure mercury lamp with main wavelengths of 185 and 254 nm, respectively. The composition, flow rate, and temperature of the simulated flue gas, as well as the VUV light intensity, were evaluated as the factors impacting on the efficiency of SO2 and NOx removal. The OH, HO2, O, and O3 produced from the photolysis of H2O and O2 were concluded as the major reactive oxygen species that oxidized SO2 and NOx. The additional OH and HO2 generated through the reactions of NO+HO2 and SO2+OH/HO2 improved treatment efficiency, while the oxidation products of NOx, e.g., NO2, HNO2, HNO3, and HNO4, consumed massive reactive oxygen species (such as O, OH, and HO2) and thereby reducing the removal efficiencies. The main reaction products were characterized as H2SO4 and HNO3 by ion chromatography, which could be used as chemical or fertilizer raw materials.

Experimental study on removals of SO2 and NO(x) using adsorption of activated carbon/microwave desorption.

UNLABELLED: Experimental studies on desulfurization and denitrification were carried out using activated carbon irradiated by microwave. The influences of the concentrations of nitric oxide (NO) and sulfur dioxide (SO2), the flue gas coexisting compositions, on adsorption properties of activated carbon and efficiencies of desulfurization and denitrification were investigated. The results show that adsorption capacity and removal efficiency of NO decrease with the increasing of SO2 concentrations in flue gas; adsorption capacity of NO increases slightly first and drops to 12.79 mg/g, and desulfurization efficiency descends with the increasing SO2 concentrations. Adsorption capacity of SO2 declines with the increasing of O2 content in flue gas, but adsorption capacity of NO increases, and removal efficiencies of NO and SO2 could be larger than 99%. Adsorption capacity of NO declines with the increase of moisture in the flue gas, but adsorption capacity of SO2 increases and removal efficiencies of NO and SO2 would be relatively stable. Adsorption capacities of both NO and SO2 decrease with the increasing of CO2 content; efficiencies of desulfurization and denitrification augment at the beginning stage, then start to fall when CO2 content exceeds 12.4%. The mechanisms of this process are also discussed. IMPLICATIONS: The prominent SO2 and NOx treatment techniques in power plants are wet flue gas desulfurization (FGD) and the catalytic decomposition method like selective catalytic reduction (SCR) or nonselective catalytic reduction (NSCR). However, these processes would have some difficulties in commercial application due to their high investment, requirement of expensive catalysts and large-scale equipment, and so on. A simple SO2 and NOx reduction utilizing decomposition by microwave energy method can be used. The pollutants control of flue gas in the power plants by the method of microwave-induced decomposition using adsorption of activated carbon/microwave desorption can meet the requirements of environmental protection, which will be stricter in the future.

Influence of inlet concentration and light intensity on the photocatalytic oxidation of nitrogen(II) oxide at the surface of Aeroxide® TiO2 P25.

Air pollution by nitrogen oxides represents a serious environmental problem in urban areas where numerous sources of these pollutants are concentrated. One approach to reduce the concentration of these air pollutants is the light-induced oxidation in the presence of molecular oxygen and a photocatalytically active building material, e.g., paints, roof tiles, or pavement stones. Herein, results of an investigation concerning the photocatalytic oxidation of nitrogen(II) oxide (NO) in the presence of molecular oxygen and UV(A) irradiated TiO(2) powder are presented. The standard operating procedure described in ISO 22197-1 which was developed to characterize the photocatalytic activity of air-cleaning products was successfully applied to determine the photocatalytic activity of a bare TiO(2) powder. The experimental data reveal that at the light intensity stipulated by the operation procedure the amount of NO removed from the gas phase by photocatalytic oxidation is strongly affected by small changes of this light intensity as well as of the NO concentration in the gas stream in the photoreactor. Therefore, these parameters have to be controlled very carefully. Based upon the experimental data obtained in this study a rate law for the photocatalytic NO oxidation inside the photoreactor is derived.

Photocatalytic NOx abatement: the role of the material supporting the TiO2 active layer.

The importance of the choice of a suitable substrate as supporting material for photoactive TiO(2), either in the form of powders or thin films or in photoactive paints, is frequently disregarded. In this paper four different supports (stainless steel, sand-blasted stainless steel, Teflon and glass) are object of investigation. The final aim is to verify the presence of interactions between the photocatalyst (AEROXIDE(®) TiO(2) P25 by Evonik Degussa Corporation) and the support, directly involved in the photocatalytic activity in the NO(x) abatement. The characterization results have been correlated with the photoactivity of the different samples. In particular, a coating of about 6-9 µm seems to allow a photocatalytic result free from any positive or negative interference with the supporting material, therefore giving reliable results about the photoactivity of the TiO(2) under investigation.

Influence of aerosol acidity on the formation of secondary organic aerosol from biogenic precursor hydrocarbons.

Secondary organic carbon (SOC) concentrations in steady-state aerosol were measured in a series of alpha-pinene/NOx and one series of beta-caryophyllene/NOx irradiation experiments. The acidity of the inorganic seed aerosol was varied while the hydrocarbon and NOx concentrations were held constant in each series of experiments. Measurements were made for acidity levels and SOC concentrations much closer to ambient levels than had been previously achieved for alpha-pinene, while there are no previous measurements for SOC increases due to acidity for beta-caryophyllene. The observed enhancement in SOC concentration linearly increases with the measured hydrogen ion concentration in air for each system. For the conditions of these studies, SOC increased by 0.04% per nmol H+ m(-3) for alpha-pinene under two conditions where the organic carbon concentration differed by a factor of 5. For alpha-pinene, this level of response to acidic aerosol was a factor of 8 lower than was reported by Surratt et al. for similar series of experiments for SOC from the photooxidation of isoprene/NOx mixtures. By contrast, SOC from beta-caryophyllene showed an increase of 0.22% per nmol H+ m(-3), roughly two-thirds of the response in the isoprene system. Mass fractions for SOC particle-phase tracers for alpha-pinene decreased slightly with increasing aerosol acidity, although remaining within previously stated uncertainties. Below 200 nmol H+ m(-3), the mass fraction of beta-caryophyllenic acid, the only identified tracer for beta-caryophyllene SOC, was constant although beta-caryophyllenic acid showed a substantial decrease for acidities greater than 400 nmol H+ m(-3).

Photoactivatable HNO-releasing compounds using the retro-Diels-Alder reaction.

We synthesized hetero-Diels-Alder cycloadducts from acyl nitroso derivatives and 9,10-dimethylanthracene, to be photo-inducible HNO-releasing agents and found that introduction of conjugated nitroaromatic groups effectively enhanced the responsiveness of HNO release to UV-A irradiation; we confirmed photoinduced HNO formation by EPR and GCMS analysis.

Kinetics and products of the gas-phase reactions of divinyl sulfoxide with OH and NO3 radicals and O3.

Using relative rate methods, rate constants for the gas-phase reactions of divinyl sulfoxide [CH 2CHS(O)CHCH 2; DVSO] with NO 3 radicals and O 3 have been measured at 296 +/- 2 K, and rate constants for the reaction with OH radicals have been measured over the temperature range of 277-349 K. Rate constants obtained for the NO 3 radical and O 3 reactions at 296 +/- 2 K were (6.1 +/- 1.4) x 10 (-16) and (4.3 +/- 1.0) x 10 (-19) cm (3) molecule (-1) s (-1), respectively. For the OH radical reaction, the temperature-dependent rate expression obtained was k = 4.17 x 10 (-12)e ((858 +/- 141)/ T ) cm (3) molecule (-1) s (-1) with a 298 K rate constant of (7.43 +/- 0.71) x 10 (-11) cm (3) molecule (-1) s (-1), where, in all cases, the errors are two standard deviations and do not include the uncertainties in the rate constants for the reference compounds. Divinyl sulfone was observed as a minor product of both the OH radical and NO 3 radical reactions at 296 +/- 2 K. Using in situ Fourier transform infrared spectroscopy, CO, CO 2, SO 2, HCHO, and divinyl sulfone were observed as products of the OH radical reaction, with molar formation yields of 35 +/- 11, 2.2 +/- 0.8, 33 +/- 4, 54 +/- 6, and 5.4 +/- 0.8%, respectively, in air. For the experimental conditions employed, aerosol formation from the OH radical-initiated reaction of DVSO in the presence of NO was minor, being approximately 1.5%. The data obtained here for DVSO are compared with literature data for the corresponding reactions of dimethyl sulfoxide.

Light intensity and light source influence on secondary organic aerosol formation for the m-xylene/NO(x) photooxidation system.

A series of m-xylene/NO(x) photooxidation experiments were conducted to determine the influence of light intensity and radiation spectrum on secondary organic aerosol (SOA) formation within the UC Riverside/CE-CERT environmental chamber. The environmental chamber is equipped with 80 115-W black lights and a variable voltage 200 kW argon arc lamp that emits a wavelength spectrum more similar to natural light. SOA formation increased significantly with light intensity, measured as the photolysis rate of NO2 to NO (k1), increased from 0.09 to 0.26 min(-1). The argon arc lamp produced approximately 20% more SOA than black lights at a k1 of 0.09 min(-1) for similar amounts of m-xylene consumed. These results may help explain the variation of SOA formation between environmental chambers and the differences between measured SOA in the ambient atmosphere versus environmental chamber predictions.

Photocatalytic degradation of NOx gases using TiO2-containing paint: a real scale study.

An indoor car park was appropriately equipped in order to test the de-polluting efficiency of a TiO(2)-containing paint in an indoor polluted environment, under real scale configuration. Depollution tests were performed in an artificially closed area of the parking, which was polluted by a car exhaust during the testing period. The ceiling surface of the car park was covered with white acrylic TiO(2)-containing paint (PP), which was developed in the frame of the EU project 'PICADA' (Photocatalytic Innovative Coverings Application for Depollution Assessment). The closed area was fed with car exhaust gases. As soon as the system reached steady state, the UV lamps were turned on for 5h. The difference between the final and the initial steady state concentration indicates the removal of the pollutants due to both the photocatalytic paint and car emission reduction. Results showed a significant photocatalytic oxidation of NO(x) gases. The photocatalytic removal of NO and NO(2) was calculated to 19% and 20%, respectively, while the photocatalytic rate (microgm(-2)s(-1)) ranged between 0.05 and 0.13 for NO and between 0.09 and 0.16 for NO(2).

Biomarker response to galactic cosmic ray-induced NOx and the methane greenhouse effect in the atmosphere of an Earth-like planet orbiting an M dwarf star.

Planets orbiting in the habitable zone of M dwarf stars are subject to high levels of galactic cosmic rays (GCRs), which produce nitrogen oxides (NOx) in Earth-like atmospheres. We investigate to what extent these NO(Mx) species may modify biomarker compounds such as ozone (O3) and nitrous oxide (N2O), as well as related compounds such as water (H2O) (essential for life) and methane (CH4) (which has both abiotic and biotic sources). Our model results suggest that such signals are robust, changing in the M star world atmospheric column due to GCR NOx effects by up to 20% compared to an M star run without GCR effects, and can therefore survive at least the effects of GCRs. We have not, however, investigated stellar cosmic rays here. CH4 levels are about 10 times higher on M star worlds than on Earth because of a lowering in hydroxyl (OH) in response to changes in the ultraviolet. The higher levels of CH4 are less than reported in previous studies. This difference arose partly because we used different biogenic input. For example, we employed 23% lower CH4 fluxes compared to those studies. Unlike on Earth, relatively modest changes in these fluxes can lead to larger changes in the concentrations of biomarker and related species on the M star world. We calculate a CH4 greenhouse heating effect of up to 4K. O3 photochemistry in terms of the smog mechanism and the catalytic loss cycles on the M star world differs considerably compared with that of Earth.

Characterization of metal doped-titanium dioxide and behaviors on photocatalytic oxidation of nitrogen oxides.

A series of nanosized ion-doped TiO2 catalysts with different ion content (between 0.1 at .% and 1.0 at .%) have been prepared by wet impregnation method and investigated with respect to their behavior for UV photocatalytic oxidation of nitric oxide. The catalytic activity was correlated with structural, electronic and surface examinations of the catalysts using X-ray diffraction analysis (XRD), ultraviolet-visible (UV-Vis) absorption spectroscopy, transmission electron microscopy (TEM), energy disperse spectrometer (EDS) and high resolution-transmission electron microscopy (HR-TEM) techniques. An enhancement of the photocatalytic activity was observed for Zn2+ doping catalyst ranged from 0.1 at .% to 1.0 at .% which was attributed to the lengthened lifetime of electrons and holes. The improvement in photocatalytic activity could be also observed with the low doping concentration of Cr3+ (0.1 at .%). However, the doping of Fe3+, Mo6+, Mn2+ and the high doping concentration of Cr3+ had no contribution to photocatalytic activity of nitric oxide.

Identification and quantification of aerosol polar oxygenated compounds bearing carboxylic or hydroxyl groups. 2. Organic tracer compounds from monoterpenes.

In this study, a comparison is made of polar organic compounds found in the field with those produced in secondary organic aerosol from laboratory irradiations of natural hydrocarbons and oxides of nitrogen (NOx). The field samples comprised atmospheric particulate matter (PM2.5) collected at Research Triangle Park (RTP), NC, during the summer of 2003, and the laboratory samples originated from the photooxidation of the following monoterpenes: alpha-pinene, beta-pinene, and d-limonene. To determine the structural characteristics of the polar compounds, the filter samples were solvent extracted and derivatized using a technique based on single and multistep derivatizations. The resulting compound derivatives were analyzed by GC-MS in the methane-Cl and El modes. In addition to previously reported biogenic oxidation products (pinic acid, pinonic acid, norpinic acid, nopinone, and pinonaldehyde), seven multifunctional organic compounds were found in both field and laboratory samples. These compounds, which are proposed as possible atmospheric tracers for secondary organic aerosol from monoterpenes, were consistent with the following identifications: 3-isopropyl pentanedioic acid; 3-acetyl pentanedioic acid; 3-carboxy heptanedioic acid; 3-acetyl hexanedioic acid; 2-isopropyl-1,2-dihydroxybutanol; 4-isopropyl-2,4-dihydroxyhexanol; and 3-(2-hydroxy-ethyl)-2,2-dimethyl-cyclobutane carboxylic acid. Initial attempts have been made to quantify the concentrations of these tracer compounds on the basis of surrogate compound calibrations. The occurrence of these compounds in both laboratory and field measurements suggests that secondary organic aerosol originating from biogenic hydrocarbons are contributing to the regional aerosol burden in the southeastern United States. Several of these compounds also appear to contribute to the global aerosol burden in that they have also been identified in Europe and Brazil.

Nitroxide conjugate of a thermally responsive elastin-like polypeptide for noninvasive thermometry.

Hyperthermia, as an adjuvant with radiation and chemotherapy, has shown promise in the treatment of cancer. The relevant biological effects of a hyperthermia treatment are both time and temperature-dependent, creating a need for accurate thermometry. We present a novel noninvasive thermometry modality that combines a temperature responsive biopolymer, the elastin-like polypeptide (ELP), and nitroxide to produce an ELP-nitroxide conjugate. When examined with electron paramagnetic resonance (EPR) spectroscopy, the ELP-nitroxide conjugate has temperature-dependent spectral line widths whose predictive accuracy is approximately 0.3 degrees C (80 microM). We believe that the temperature-dependent changes observed in the EPR spectrum are due to the combined effect of temperature, viscosity and effective radius on the rotational correlation time of the ELP-nitroxide conjugate.