A comparative study of doped and un-doped sol-gel TiO2 and P25 TiO2 (photo)electrodes.

Doped and undoped titanium dioxide films have been deposited on indium tin oxide glass using the sol-gel technique. The percentage of rutile in the prepared TiO2, calcined at 823 K and determined by X-ray diffraction, was 23% compared to 24% of rutile in P25-TiO2. Cerium doped TiO2 showed mainly the anatase phase, as characterised by both X-ray diffraction and Raman spectroscopy. The electrochemical and photoelectrochemical properties of the films were studied by cyclic voltammetry and electrochemical impedance spectroscopy. The (photo)electrochemical characteristics of the different films are reported and discussed.

Environmental hypoxia influences hemoglobin subunit composition in the branchiopod crustacean Triops longicaudatus.

Hemoglobin (Hb) is a highly conserved protein that provides a vital link between environmental oxygen and its use and/or storage within an organism. While ubiquitous among vertebrates, Hb occurs frequently in invertebrate phyla as well. Many arthropod species use the copper-binding pigment hemocyanin, but unique in this phylum are the branchiopod crustaceans, which express Hb. Branchiopod Hb concentration and structure are exquisitely sensitive to environmental oxygen availability. Hemoglobin concentration and oxygen-binding affinity increase with decreasing oxygen tension in Daphnia, Artemia and Triops. The change in binding affinity is attributed to differential Hb subunit expression in Daphnia and Artemia but remains unclear for Triops. This is the first study to demonstrate developmental plasticity of Hb subunit expression in a notostracan, Triops longicaudatus, reared under conditions of varying oxygen availability. In response to variable oxygen environments, T. longicaudatus differentially express four primary Hb subunits ranging between 30 and 34 kDa, with normoxic-reared animals expressing primarily the heavier subunits, and hypoxic-reared animals expressing increased proportions of the lower molecular mass subunits. Moreover, differential Hb subunit expression is induced upon transfer of normoxic-reared adults to a hypoxic environment, such that the distribution of Hb subunits in the transferred adults becomes similar to that of hypoxic-reared animals. Two-dimensional gel electrophoresis and follow-up analyses revealed several isoforms of Hb subunits that may represent differential gene expression and/or post-translational modification. Unlike Daphnia and Artemia, the Hb hypoxic response in Triops is not reversible in that there was no significant decrease in Hb concentration or change in Hb subunit expression pattern when hypoxic-reared adults were transferred to a normoxic environment.

New insights into the mechanisms of the thermal Fenton reactions occurring using different iron(II)-complexes.

Although the Fenton reagent (a mixture of hydrogen peroxide and an iron(II) salt) has been known for more than a century, the manifold mechanisms occurring during the thermal Fenton reaction are still under discussion. Indeed, this discussion served as a powerful driving force for the steadily increasing insight into the field of inorganic radical and electron transfer chemistry. In this work, an experimental approach towards the elucidation of the first steps taking place in the reaction between several iron(II)-complexes and hydrogen peroxide (H2O2) in water at pH = 3.0 is presented. 2,4-xylidine (2,4-dimethylaniline) reacts differently with reactive intermediates via the addition or hydrogen abstraction by the hydroxyl radical (HO*) or electron transfer reactions to higher valent iron-species, such as a hydrated ferryl-complex (Fe(IV)). The chemical reactivity of the employed iron(II)-complexes with H2O2 differed strongly depending on their ground-state one-electron oxidation potentials. The results are interpreted in accordance with the paradigm originally developed by Goldstein et al. which is based on the evidence obtained from the Marcus theory that outer-sphere electron transfer reactions between metal complexes are not likely to occur because they are too slow. Therefore, most of the "Fenton-reagents" form transient metal complexes, which can be described as [LnFe-H2O2]m+. They form, depending on the reaction conditions, either the hydroxyl radical or higher-valent iron complex species.

Technical development of UV-C- and VUV-photochemically induced oxidative degradation processes.

Technical development work is presented, where the VUV photochemically induced oxidative degradation is used: (i) for analytic purposes, and (ii) for small to medium scale (< 10 m2/d) waste water treatment processes or ultrapure water production. In the first case, small Xe-excimer radiation sources with an integrated reaction space designed for optimal conditions, as far as incident photon flux density, turbulence and concentration of dissolved molecular oxygen are concerned, have been built and tested. Under conditions of exhaustive oxidation and/or mineralization of pollutants in a continuous regime, they may be used for sample pre-treatment modules prior TOC, TOX and electrochemical trace metal analysis. Under conditions of partial oxidation or mineralization, the same lamp/reactor combination may be used for functionalization purposes prior to e.g. GC or HPLC analyses. In the second case, mass transfer limitations between the non-irradiated bulk volume and the irradiated volume are overcome by the electrochemical generation of molecular oxygen within or close to the irradiated volume and by the design of the photochemical part of the reactor.

Intense, narrow atomic-clock resonances.

We present experimental and theoretical results showing that magnetic resonance transitions from the "end" sublevels of maximum or minimum spin in alkali-metal vapors are a promising alternative to the conventional 0-0 transition for small-size gas-cell atomic clocks. For these "end resonances," collisional spin-exchange broadening, which often dominates the linewidth of the 0-0 resonance, decreases with increasing spin polarization and vanishes for 100% polarization. The end resonances also have much stronger signals than the 0-0 resonance, and are readily detectable in cells with high buffer-gas pressure.

Degradation of polyvinyl alcohol (PVA) by homogeneous and heterogeneous photocatalysis applied to the photochemically enhanced Fenton reaction.

The reaction mechanism of the oxidative degradation of polyvinyl alcohol (PVA) by the photochemically enhanced Fenton reaction was studied using a homogeneous (Fe2+(aq) + H2O2) and a heterogeneous reaction system (iron(III)-exchanged zeolite Y+ H2O2). In the homogeneous Fenton system, efficient degradation was observed in a batch reactor, equipped with a medium pressure mercury arc in a Pyrex envelope and employing 80% of the stoichiometric amount of H2O2 required for the total oxidation of PVA and a concentration ratio as low as I mole of iron(II) sulfate per 20 moles of PVA sub-units (C2H40). Model PVA polymers of three different molecular weights (15,000, 49,000 and 100,000 g mol(-1)) were found to follow identical degradation patterns. Strong experimental evidence supports the formation of supermacromolecules (MW: 1-5 x 10(6) g/mol) consisting of oxidized PVA and trapped iron(III) at an early reaction stage. Low molecular weight intermediates, such as oxalic acid, formic acid or formaldehyde were not found during PVA degradation in the homogeneous Fenton system, and we may deduce that the manifold of degradation reactions is mainly taking place within the super-macromolecules from which CO2 is directly released. However, in the heterogeneous Fenton system, the reaction behavior was found to be distinctly different: a decrease of the molecular weights of all three tested monodisperse PVA samples was observed by the broadening of the GPC-traces during irradiation, and oxalic acid was formed. The results lead to the mechanistic hypothesis that during the heterogeneous Fenton process, the cleavage of the PVA-chains may occur at random positions, the reactive centres being located inside the iron(III)-doped zeolite Y photocatalysts.

Optimal experimental design and artificial neural networks applied to the photochemically enhanced Fenton reaction.

Among advanced oxidation processes (AOPs), the photochemically enhanced Fenton reaction may be considered as one of the most efficient for the degradation of contaminants in industrial wastewater. This process involves a series of complex reactions. Therefore, an empirical model based on artificial neural networks has been developed for fitting the experimental data obtained in a laboratory batch reactor for the degradation of 2,4-dimethyl aniline (2,4-xylidine), chosen as a model pollutant. The model describes the evolution of the pollutant concentration during irradiation time as a function of the process conditions. It has been used for simulating the behavior of the reaction system in sensitivity studies aimed at optimizing the amounts of reactants employed in the process, an iron(III) salt and hydrogen peroxide, as well as the temperature. The results show that the process is most sensitive to the concentration of iron(III) salt and temperature, whereas the concentration of hydrogen peroxide has a minor effect.

Lanthanide oxide-doped titanium dioxide photocatalysts: novel photocatalysts for the enhanced degradation of p-chlorophenoxyacetic acid.

The photocatalytic degradation of p-chlorophenoxyacetic acid has been investigated in oxygenated aqueous suspensions of lanthanide oxide-doped TiO2 photocatalysts. Complete mineralization was achieved. The enhanced degradation is attributed to the formation of Lewis acid-base complex between the lanthanide ion and the substrate.

An N,N'-dialkyl-4,4'-bipyridinium-modified titanium-dioxide photocatalyst for water remediation--observation and application of supramolecular effects in photocatalytic degradation of pi-donor organic compounds.

The photocatalytic activity of TiO2 (Degussa P-25) modified with a 4,4'-bipyridinium monolayer (V2+-TiO2) has been compared with that of conventional TiO2-P-25 by investigating the efficiency of degradation of a series of four organic model compounds with increasing pi-donor capacity (2,4-xylidine, 2,4-dimethylphenol, hydroquinone, and dimethylhydroquinone). As far as the mechanism of the first oxidation reaction is concerned, evidence for the formation of supramolecular donor-acceptor complexes with the bipyridinium units at the semiconductor surface was obtained by comparison of the Langmuir-adsorption characteristics and the efficiencies of photodegradation of the different substrates. Furthermore, the main intermediates of the photocatalytic degradation of 2,4-xylidine were identified, and the presence of 2,4-dimethylphenol indicates that the main pathway of substrate oxidation proceeds via electron transfer from the adsorbed organic substrate to the "holes" within the valence band of the photoexcited semiconductors V2+-TiO2 and TiO2. The efficiencies of photocatalytic degradation by both V2+-TiO2 and TiO2 were limited by the trapping efficiency of the conduction band electrons by molecular oxygen.

Nonradiative and radiative deactivation of singlet molecular oxygen (O2(a1deltag)) in micellar media and microemulsions.

The effects of microheterogeneous media (micelles and microemulsions) on the lifetime and, to our knowledge for the first time, on the emission of singlet molecular oxygen (O2 (a1Ag), denoted as 1O2) were investigated. Micellar media and various types of microemulsions based on anionic (sodiumdodecyl sulfate), cationic (cetyltrimethylammonium chloride) or nonionic (Triton X-100) surfactants were formulated for this purpose. The nonradiative and radiative deactivation rate constants (k(d) and k(e), respectively) were determined in selected microheterogeneous media and in the pure solvents used for their formulation, by combining steady-state and time-resolved 1O2, luminescence detection techniques. We have shown that a simple additive model, as used in homogeneous mixtures of solvents, was inadequate for predicting values of k(d) and k(e) in organized media. In contrast, both 1O2 lifetimes (taudelta = 1/k(d)) and k(e) in the microheterogeneous systems investigated could be predicted with good precision from the composition of the media and the taudelta and k(e) values in the pure solvents, using a two-pseudophase kinetic model for the 1O2 distribution. Such a model takes into account the average times spent by 1O2 in the aqueous and lipophilic pseudo-phases of the organized media, the corresponding equilibrium constant (Keq) depending on the nature of the system.

Effect of the microenvironment on the efficiency of singlet oxygen (O2(1 delta g)) production by photosensitizing anti-inflammatory drugs.

The influence of the medium on the quantum yields of singlet oxygen (O2(1 delta g)) production (phi delta) by a series of photosensitizing non-steroidal anti-inflammatory drugs (NSAID) derived from 2-arylpropionic acid (APA) has been investigated. Four-component oil-in-water and water-in-oil microemulsions, based on anionic and cationic surfactants, have been employed as the simplest models to mimic more complex biological environments. phi delta values have been determined by monitoring the singlet oxygen (1O2) luminescence at 1270 nm upon continuous excitation of the drugs under air-equilibrated conditions. Results indicate that phi delta values are highly affected by the medium, being higher in microheterogeneous systems than in (homogeneous) solution. Some of the anti-inflammatory derivatives are very efficient 1O2 sensitizers: e.g., values of apparent phi delta as high as 0.86 (+/- 0.04) and 0.70 (+/- 0.03) have been found for tiaprofenic acid and suprofen, respectively. The location of the drugs in the interfacial region of the microemulsions combined with their high phi delta values suggest that type II reactions may play a significant role in the overall photodynamic process in more complex organized media, such as biological membranes.

Effect of radiation and age on immunoglobulin levels in rhesus monkeys (Macaca mulatta).

We report the results of a study on the immunoglobulin levels of rhesus monkeys (Macaca mulatta) in a colony consisting of the survivors of monkeys that received a single whole-body exposure to protons, electrons or X rays between 1964 and 1969. This colony has been maintained to assess the long-term effects of ionizing radiation on astronauts and high-flying pilots. Of the original 358 monkeys that were retained for lifetime studies, 129 (97 irradiated and 32 controls) were available for our study. We found no significant difference between the irradiated and control monkeys in mean levels of IgA, IgG and IgM, irrespective of the radiation treatment. The availability of these aged monkeys provided a unique opportunity to compare their immunoglobulin levels to those of other monkeys of various ages, and thus assess the effect of age on immunoglobulin levels. We found that only the IgA levels increase with age.

Antioxidant activity of flavonoids: efficiency of singlet oxygen (1 delta g) quenching.

Flavonoids, polyphenolic pigments widely present in plants, have been reported to act as scavengers of various oxidizing species. However, most often an overall antioxidant effect was measured. In this paper we report the results of a systematic study of the reactivity of 13 selected flavonoids (from the flavonol, flavone, flavanone and flavane families) with singlet oxygen (1O2(1 delta g)) in order to establish a structure-activity relationship. The rate constants of the chemical reaction of these flavonoids with 1O2(k r) and their rate constants of 1O2 physical quenching (kq) have been determined by kinetic measurements and near-IR singlet oxygen luminescence. The efficiency of the physical quenching is mainly controlled by the presence of a catechol moiety on ring B, whereas the structure of ring C (particularly the presence of a hydroxyl group activating the double bond) is the main factor determining the efficiency of the chemical reactivity of these compounds with 1O2. The total reactivity factor determining the efficiency of the chemical reactivity of these compounds with 1O2. The total reactivity scale is dominated by kq, which is in general higher than kr. (+)-Catechin is the most efficient quencher of the series.

Primary effects of singlet oxygen sensitizers on eggs and embryos of sea urchins.

Photodynamic effects of rose bengal, a well-known singlet oxygen sensitizer, and of haematoporphyrin derivative, the most widely used sensitizer in photodynamic therapy of tumours, could be visualized using sea urchin eggs and embryos. This biological material is a valuable model for the analysis of mechanisms and/or sites of the photodynamic action occurring in any living tissue. Depending on the sensitizer used, singlet oxygen may be identified as the main mediator of the cytotoxic effects observed. Besides observations made on the living, in particular within the context of fertilization ability of the egg cell, gross damages of the cells are morphologically analysed by scanning electron microscopy. The results support the working hypothesis explaining the different susceptibility of healthy and tumour cells for photosensitization as a cell cycle phenomenon.

Changes in muscle proteins following different neural lesions.

The influence of various nerve lesions on the relative concentrations of proteins in the extensor digitorum longus (EDL), plantaris (PLN), and soleus (SOL) muscles from adult female rats was examined by electrophoresis on polyacrylamide gels. After cordotomy, levels of myosin light chains Lcs1 and -2 decreased with concomitant increases in Lcf1, -2, and -3 in SOL but not in EDL and PLN. The relative levels of several other proteins in all three muscle types were changed also. Following section of the sciatic nerve, corticospinal tract and removal of the motor cortex, the relative levels of distinct sets of protein bands in all three muscle types were altered. Only a 14,000-dalton protein band appeared to be affected by all four types of lesions. This experimental evidence supports the view that neural influences upon muscle properties are exceedingly complex. Some of these influences may be exerted via separate, central pathways to the motor neurons.

Analysis of rat hindlimb muscle proteins by two-dimensional gels following spinal cord injury.

Proteins from extensor digitorum longus (EDL), plantaris (PLN), and soleus (SOL) muscles of adult, female rats were examined by high resolution two-dimensional gel electrophoresis up to 4 weeks following spinal cord transection. The electrophoretograms were analyzed by computer imaging and densitometry. Reproducible and significant changes in the relative concentrations of several proteins in each muscle type were detected. Whereas changes involving the largest number of proteins were observed in SOL, changes in EDL and PLN were also detected. In SOL, approximately 50% of the altered proteins increased in concentration and the remaining decreased: Actin and myosin light chains LCF-1 and LCF-2 were among those proteins whose concentrations increased, whereas myosin light chains LCS-1 and LCS-2 were among those proteins whose concentrations decreased. The present findings regarding the reversal in myosin light chain composition provide biochemical support for previously published data on changes in contractile properties of muscles following spinalization. In EDL, the relative concentration of only one protein was elevated in a time-dependent manner. The concentrations of two protein species in PLN were increased following cord transection. These findings provide new biochemical markers on the effects of spinal cord on gene expression in specific hindlimb skeletal muscles.