Photoelectrolytic oxidation of organic species at mesoporous tungsten trioxide film electrodes under visible light illumination

Operation of a photoelectrolyser fitted with a semitransparent semiconducting WO3 film photoanode is described. Due to its band-gap energy of 2.5eV, the photoresponse of the WO3 electrode extends into the blue part of the visible spectrum up to 500nm. The WO3 photoanode exhibits particularly high incident photon-to-current efficiencies for the oxidation of several organic species with the maximum occurring at ca. 400nm. Experiments conducted under simulated AM 1.5 solar illumination demonstrated efficient photodegradation of a variety of organic chemicals including small organic molecules as well as EDTA and anthraquinonic Acid Blue 80 dye. Although, due to the inherent mass transport limitations, the described device appears best suited to the treatment of industrial wastewater containing from 100ppm to few gL−1 of impurities, almost complete removal of organic carbon was observed in several photoelectrolysis runs. This is apparently associated with the concomitant photooxidation of sulphate-based supporting electrolyte resulting in the formation of a powerful chemical oxidant-persulphat

HOCl-modified phosphatidylcholines induce apoptosis and redox imbalance in HUVEC-ST cells

Electrophilic attack of hypochlorous acid on unsaturated bonds of fatty acyl chains is known to result mostly in chlorinated products that show cytotoxicity to some cell lines and were found in biological systems exposed to HOCl. This study aimed to investigate more deeply the products and the mechanism underlying cytotoxicity of phospholipid-HOCl oxidation products, synthesized by the reaction of HOCl with 1-stearoyl-2-oleoyl-, 1-stearoyl-2-linoleoyl-, and 1-stearoyl-2-arachidonyl-phosphatidylcholine. Phospholipid chlorohydrins were found to be the most abundant among obtained products. HOCl-modified lipids were cytotoxic towards HUVEC-ST (endothelial cells), leading to a decrease of mitochondrial potential and an increase in the number of apoptotic cells. These effects were accompanied by an increase of the level of active caspase-3 and caspase-7, while the caspase-3/-7 inhibitor Ac-DEVD-CHO dramatically decreased the number of apoptotic cells. Phospholipid-HOCl oxidation products were shown to affect cell proliferation by a concentration-dependent cell cycle arrest in the G/G phase and activating redox sensitive p38 kinase. The redox imbalance observed in HUVEC-ST cells exposed to modified phosphatidylcholines was accompanied by an increase in ROS level, and a decrease in glutathione content and antioxidant capacity of cell extracts

Metal oxide photoanodes for water splitting

Solar hydrogen production through photocatalytically assisted water splitting has attracted a great deal of attention since its first discovery almost 30 years ago. The publication of investigations into the use of TiO 2 photoanodes has continued apace since and a critical review of current trends is reported herein. Recent advances in the understanding of the behaviour of nanoparticulate TiO 2 films is summarized along with a balanced report into the utility and nature of titania films doped with non-metallic elements and ordered, nanostructured films such as those consisting of nanotubes. Both of these are areas that have generated a not insignificant degree of activity. One goal of doping TiO 2 has been to extend the photoresponse of the material to visible light. A similar goal has seen a resurgence in interest in Fe 2 O 3 photoanodes. Herein, the influence of dopants on the photocurrent density observed at Fe 2 O 3 photoanodes and, in this regard, the role of silicon has attracted much attention, and a little debate. Finally, we look beyond the binary oxides. Photoanodes made from new materials such as mixed metal oxides, perovskite structured semiconductors, metal (oxy)nitrides or composite electrodes offer the potential to either tailor the optical band gap or tune the conduction or valence band energetics. Recent work in this area is detailed here

Tailoring the morphology of WO₃films with substitutional cation doping: Effect on the photoelectrochemical properties

With the aim of improving the performance and extending the range of applications of mesoporous WO₃films, which were initially developed for the photoelectrochemical oxidation of water, we investigated the effect of a number of dopants (lithium, silicon, ruthenium, molybdenum and tin) upon the transparency, crystallinity, porosity and conductivity of the modified films. Tin, molybdenum and silicon were shown to improve the electrochromic behaviour of the layers whereas ruthenium enhanced considerably the electronic conductivity of the WO₃films. Interestingly, most of the dopants also affected the film morphology and the size of WO₃nanocrystals. X-ray photoelectron spectra revealed absence of significant segregation of doping elements within the film. Raman analyses confirmed that the monoclinic structure of WO₃films does not change upon substitutional cation doping; thus, the crystallinity of WO₃films is maintained

Enhancement of Photoelectrochemical Water Splitting and Solar Energy Induced Electroreduction of Carbon Dioxide through Utilization of Plasmonic and Electrocatalytic Metal Nanoparticles

In the present study, we utilize phosphomolybdate (PMo12O40 3-) modified gold nanoparticle (diameters, 30-40 nm) deposits on mesoporous tungsten oxide photoanodes to study plasmon-assisted photoelectrochemical water splitting. Such n-type semiconducting oxide as WO3 (band gap, 2.5 eV) suffers from inadequate solar light absorption and, therefore, there is a need to use of a thin plasmon active layer of nanostructured Au of proper architecture to enhance the interfacial light trapping and conversion. A remarkable increase in the solar energy conversion efficiency as well as in the photooxidation current (oxygen evolution) are believed to be induced by the plasmonic excitation of Au nanoparticles occurring within WO3 absorption range. The polyoxometallate (PMo12O40 3-) monolayer-type nanostructures may play electrocatalytic role, improve charge distribution, in addition to the stabilization effect. In the other study, the PMo12O40 3- modified Au nanoparticles, when deposited on step-bunched silicon Si(111) surface have also acted as electrocatalytic centers during photoelectrochemically induced reduction of carbon oxide (IV). The applicability of phosphomolybdate-protected gold nanoparticles to create porous matrix for photoelectrochemically assisted reduction of carbon dioxide is even more pronounced when the system is further decorated with copper. We also present the result of decorating multi-walled carbon nanotubes with gold and copper nanoparticles (by chemical reduction method and through electrodeposition) acting as catalytic systems active towards CO2 electroreduction under voltammetric conditions. Carbon nanotubes have been chemically modified here with surface oxygen complexes using HNO3 and H3PMo12O40 solutions.</jats:p

The Occurrence of Mycotoxins in Organic Spelt Products

Mycotoxins have a proven toxic effect on the health of humans and animals. Nowadays, there is a focus on having a healthy lifestyle and consuming organic foods. High quality grain products, especially spelt products, which are an important element of a well-balanced diet have become more popular. The aim of this study was to determine the mycotoxin content in spelt products available on the Polish market. Spelt products were collected in 2009 and 2010 in eastern Poland. The Enzyme-Linked ImmunoSorbent Assay (ELISA) method was used to identify aflatoxins, ochratoxin A, T-2 toxin, deoxynivalenol, and zearalenone. The study confirmed that all investigated mycotoxins were present in spelt products