Synergistischer photoinduzierter Schadstoffabbau mittels eines Porphyrazin-Titandioxid-Hybrids

Die zunehmende Luftverschmutzung aufgrund des steigenden Energiebedarfs und Mobilitätsanspruchs der Bevölkerung, insbesondere in urbanen Gebieten, erhöht das Gefährdungspotential für die Gesundheit und verschlechtert so die Lebensqualität. Neben der Vermeidung von Emissionen toxischer Gase als mittel- und langfristig optimale Maßnahme zur Verbesserung der Luftqualität, stellt der Abbau emittierter Luftschadstoffe ein geeignetes und kurzfristig wirksames Mittel dar. Ein solcher Abbau kann durch Photokatalyse erzielt werden, allerdings nutzen Photokatalysatoren, die auf dem Halbleiter Titandioxid (TiO2) basieren, das solare Emissionsspektrum nur geringfüfig aus und sind in Innenräumen und anderen UV-schwachen Bereichen nicht wirksam. Um diese Nachteile zu überwinden, wurde ein Photokatalysator entwickelt und hergestellt, der aus TiO2 (P25) als UV-aktiver Photokatalysator und als Trägermaterial sowie einem seinerseits im Vis-Bereich photoaktiven Porphyrazin-Farbstoff als Beschichtung besteht. Die sterisch anspruchsvollen und in der Peripherie mit acht Bindungsmotiven für TiO2 versehenen Farbstoffmoleküle wurden zu diesem Zweck auf der Halbleiteroberfläche immobilisiert. Die so gebildeten Porphyrazin-Titandioxid-Hybride wurde ausführlich charakterisiert. Dabei wurden unter anderem die Bindung der Farbstoffe auf der Titandioxidoberfläche mittels Adsorptionsisothermen und die UV/Vis-spektroskopischen Eigenschaften des Hybridmaterials untersucht. Zur Bestimmung der photokatalytischen Aktivitäten der Einzelkomponenten und des Hybridmaterials wurden diese auf die Fähigkeit zur Bildung von Singulett-Sauerstoff, Wasserstoffperoxid und Hydroxylradikalen hin sowie in einem an die ISO-22197-1 angelehnten Verfahren auf die Fähigkeit zum Abbau von NO hin jeweils bei Bestrahlung in drei Wellenlängenbereichen (UV-Strahlung, blaues Licht und rotes Licht) geprüft. Darüber hinaus konnte die Aktivität des Hybridmaterials bei der Photodynamischen Inaktivierung (PDI) von Bakterien unter UV- und Rotlichtbestrahlung im Vergleich zum reinen Ttandioxid bestimmt werden. Die Charakterisierung des Hybridmaterials ergab, dass die Farbstoffmoleküle in einer neutralen Suspension nahezu irreversibel in einer monomolekularen Schicht mit einer Bindungsenergie von -41.43 kJ/mol an die Oberfläche gebunden sind und das Hybridmaterial mit hohen Extinktionskoeffizienten von bis zu 105 M-1cm-1 in großen Bereichen des UV/Vis-Spektrums Photonen absorbiert. Das Spektrum des Hybridmaterials setzt sich dabei additiv aus den beiden Einzelspektren zusammen. Die Auswirkungen der Charakterisierungsergebnisse auf die Bildung reaktiver Sauerstoffspezies wurden ausführlich diskutiert. Der Vergleich der Aktivitäten in Bezug auf die Bildung der reaktiven Sauerstoffspezies zeigte, dass die Aktivität des Hybridmaterials bis auf die bei der Bildung von Hydroxylradikalen unter UV-Bestrahlung in allen Versuchen deutlich höher war als die Aktivität des reinen Titandioxids. Im Gegensatz zu reinem Titandioxid erzeugte das Hybridmaterial in allen untersuchten Wellenlängenbereichen Mengen an Singulett-Sauerstoff, die photophysikalisch eindeutig detektierbar waren. Zur Erklärung und Deutung dieser Beobachtungen wurde eine differenzierte Diskussion geführt, die die Ergebnisse der Hybridpartikelcharakterisierung aufgreift und implementiert. Der Vergleich der NO-Abbaueffizienzen ergab bei allen Experimenten durchgängig deutlich höhere Werte für das Hybridmaterial. Zudem wurden durch das Hybridmaterial nachgewiesenermaßen wesentlich geringere Mengen des unerwünschten Nebenprodukts des Abbaus (NO2) gebildet. Im Zuge der Diskussion wurden verschiedene mögliche Mechanismen der „sauberen“ Oxidation zu Nitrat durch das Hybridmaterial vorgestellt. Untersuchungen zur Photodynamischen Inaktivierung verschiedener Bakterien ergaben, dass das Hybridmaterial neben einer zu P25 ähnlichen Aktivität unter UV-Bestrahlung, anders als P25, auch eine PDI verschiedener Bakterien unter Rotlichtbestrahlung erreicht.

Ultrasound-assisted electrochemical treatment of wastewaters containing organic pollutants by using novel Ti/Ta2O5-SnO2 electrodes

Advanced oxidation processes (AOPs) are modern methods using reactive hydroxyl radicals for the mineralization of organic pollutants into simple inorganic compounds, such as CO2 and H2O. Among AOPs electrochemical oxidation (EO) is a method suitable for coloured and turbid wastewaters. The degradation of pollutants occurs on electrocatalytic electrodes. The majority of electrodes contain in their structure either expensive materials (diamond and Pt-group metals) or are toxic for the environment compounds (Sb or Pb). One of the main disadvantages of electrochemical method is the polarization and contamination of electrodes due to the deposition of reaction products on their surface, which results in diminishing of the process efficiency. Ultrasound combined with the electrochemical degradation process eliminates electrode contamination because of the continuous mechanical cleaning effect produced by the formation and collapse of acoustic cavitation bubbles near to the electrode surface. Moreover, high frequency ultrasound generates hydroxyl radicals at water sonolysis. Ultrasound-assisted EO is a non-selective method for oxidation of different organic compounds with high degradation efficiencies. The aim of this research was to develop novel sustainable and cost-effective electrodes working as electrocatalysts and test their activity in electrocatalytic oxidation of organic compounds such as dyes and organic acids. Moreover, the goal of the research was to enhance the efficiency of electrocatalytic degradation processes by assisting it with ultrasound in order to eliminate the main drawbacks of a single electrochemical oxidation such as electrodes polarization and passivation. Novel Ti/Ta2O5-SnO2 electrodes were developed and found to be electrocatalytically active towards water (with 5% Ta content, 10 oxide film layers) and organic compounds oxidation (with 7.5% Ta content, 8 oxide film layers) and therefore these electrodes can be applicable in both environmental and energy fields. The synergetic effect of combined electrolysis and sonication was shown while conducting sonoelectrochemical (EO/US) degradation of methylene blue (MB) and formic acid (FA). Complete degradation of MB and FA was achieved after 45 and 120 min of EO/US process respectively in neutral media. Mineralization efficiency of FA over 95% was obtained after 2 h of degradation using high frequency ultrasound (381, 863, 1176 kHz) combined with 9.1 mA/cm2 current density. EO/US degradation of MB provided over 75% mineralization in 8 h. High degradation kinetic rates and mineralization efficiencies of model pollutants obtained in EO/US experiments provide the preconditions for further extrapolation of this treatment method to pilot scale studies with industrial wastewaters.

Analysis of radiation induced DNA damage by LC-MS/MS in isolated and cellular DNA

Abstract: It is well established that ionizing radiation induces a variety of damage in DNA by direct effects that are mediated by one-electron oxidation and indirect effects that are mediated by the reaction of water radiolysis products, e.g., hydroxyl radicals (•OH). In cellular DNA, direct and indirect effects appear to have about an equal effect toward DNA damage. We have shown that ϒ-(gamma) ray irradiation of aqueous solutions of DNA, during which •OH is the major damaging ROS can lead to the formation several lesions. On the other hand, the methylation and oxidative demethylation of cytosine in CpG dinucleotides plays a critical role in the gene regulation. The C5 position of cytosine in CG dinucleotides is frequently methylated by DNA methyl transferees (DNMTs) and constitutes 4-5% of the total cytosine. Here, my PhD research work focuses on the analysis of oxidative base modifications of model compounds of methylated and non methylated oligonucleotides, isolated DNA (calf-thymus DNA) and F98 cultured cell by gamma radiation. In addition, we identified a series of modifications of the 2-deoxyribose moiety of DNA arising from the exposure of isolated and cellular DNA to ionizing radiation. We also studied one electron oxidation of cellular DNA in cultured human HeLa cells initiated by intense nanosecond 266 nm laser pulse irradiation, which produces cross-links between guanine and thymine bases (G*-T*). To achieve these goals, we developed several methods based on mass spectrometry to analyze base modifications in isolated DNA and cellular DNA.

Atividade antioxidante de fucanas e galactanas extraídas de algas marinhas

Studies made with polysaccharides of seaweed have demonstrated that these present important biological and pharmacological activities. These composites had presented "scavenging" activity of free radicals, which is important in the mediation of the inflammatory process and in the pathology of diverse disease. Recently, this "scavenging" property has taken some researches to evaluate the antioxidant capacity from various polysaccharides. Considering the limited research with polysaccharides and knowing its largely employed by the pharmaceutical and foodstuffs industries, we have objective to verify the actions from fucans and galactans as antioxidants. The fucans are found in brown seaweed and the galactans (carrageenans) in red seaweed. The fucans were obtained from seaweed Padina gymnospora (F0.5 e F1.1 fractions), common to our coastline and one another fucan, fucoidan, was of origin commercial and extracted from seaweed Fucus vesiculosus. The λ, κ e ι carrageenans were also of origin commercial. The antioxidant activities were tested in superoxide and hydroxyl systems to generated free radicals and for the inhibition of the lipid peroxidation. The results obtained to inhibition of formation the superoxide radicals demonstrated that all polysaccharides presented scavenging activity of superoxide radicals. The fucoidan, F0.5 and F1.1 fractions presented IC50 of 0.058; 0.243 and 0.243 mg/mL, respectively, while IC50 of the λ, κ and ι carrageenans were 0.046; 0.112 and 0.332 mg/mL, respectively. The results to inhibition of formation the hydroxyl radicals demonstrated that all sample had low effect in the inhibition of the formation of these radicals, except the F0.5. For these radicals the IC50 were 0.157 and 0.353 mg/mL to the fucoidan and F1.1, respectively and 0.357; 0.335 and 0.281 mg/mL to λ, κ and ι carrageenans, respectively. All the samples were capacity to inhibition the peroxidation, it present the IC50 of 1.250; 2.753 and 2.341 mg/mL to fucoidan, F0.5 and F1.1, respectively. Already the λ, κ and ι carrageenans presented the IC50 of 2.697; 0.323 and 0.830 mg/mL, respectively. With these findings, we conclude that polysaccharides used in this study presented activity antioxidant, and that fucoidan and the λ carrageenan show a significant "scavenging" activity for the radicals superoxide and the κ carrageenan a significant inhibitory activity for the lipid peroxidation

Role of nitrogen doping on the performance of carbon nanotube catalysts: a catalytic wet peroxide oxidation application

Four magnetic carbon nanotube samples (CNTs: undoped, completely N-doped and two selectively N-doped) have been synthesized by chemical vapor deposition. The materials were tested in the catalytic wet peroxide oxidation (CWPO) of highly concentrated 4 nitrophenol solutions (4-NP, 5 g L-1). Relatively mild operating conditions were considered (atmospheric pressure, T = 50 ºC, pH = 3), using a catalyst load of 2.5 g L-1 and the stoichiometric amount of H2O2 needed for the complete mineralization of 4-NP. N doping was identified to influence considerably the CWPO performance of the materials. In particular, undoped CNTs, with a moderate hydrophobicity, favor the controllable and efficient decomposition of H2O2 into highly reactive hydroxyl radicals (HO•), thus showing high catalytic activity for 4-NP degradation. On the other hand, the completely N-doped catalyst, fully hydrophilic, favors a quick decomposition of H2O2 into non-reactive O2 and H2O species. The selectively N-doped amphiphilic catalysts, i.e. hybrid structures containing undoped sections followed by N-doped ones, provided intermediate results, namely: a higher N content favored H2O2 decomposition towards non-reactive H2O and O2 species, whilst a lower N content resulted in the formation of HO•, increasing 4-NP mineralization. Catalyst stability and reusability were also investigated by consecutive CWPO runs.

Indigofera tinctoria Linn (Fabaceae) attenuates cognitive and behavioral deficits in scopolamine-induced amnesic mice

Purpose: To investigate the cognition-enhancing effects of aqueous extract of Indigofera tinctoria Linn (ITE, Fabaceae) in experimental amnesic mice. Methods: Scopolamine (2 mg/kg, i.p.) was used to induce amnesia in mice. The cognitive-enhancing activity of the ITE (5, 10 and 20 μg/mL) was studied by passive avoidance response, elevated plus maze and Y-maze behavioral paradigm in normal and scopolamine-induced amnesic mice. Antioxidant activities were also determined based on the ability of ITE to inhibit lipid peroxide, superoxide and hydroxyl radicals. Results: Scopolamine-induced cognitive deficits were significantly reversed by ITE (p < 0.001 at 20 mg/kg) in a dose-dependent fashion in all the behavioral paradigms tested. Furthermore, ITE dosedependently scavenged lipid peroxide, superoxide and hydroxyl free radicals with 50 % inhibition concentration (IC50) of 7.28 ± 0.37, 5.25 ± 0.28 and 7.62 ± 0.43 μg/mL, respectively. Conclusion: ITE possesses cognitive-enhancing properties in amnesic mice due to its potent antioxidant action.

UV absorption spectra of methyl-substituted hydroxy-cyclohexadienyl radicals in the gas phase

UV absorption spectra of five methyl-substituted hydroxy-cyclohexadienyl radicals, formed by the addition of the hydroxyl radical (OH) to toluene (methyl benzene), o-, m- and p-xylene (1,2-, 1,3- and 1,4-dimethyl benzene, respectively) and mesitylene (1,3,5-trimethylbenzene), have been determined at 298 K, 1 atm pressure (N-2 + O-2), and the corresponding absolute absorption cross-sections measured, using laser flash photolysis and time-resolved UV absorption detection. As observed for other cyclohexadienyl-type radicals, a strong absorption band is present in the 260-340 nm spectral region, with maximum cross-sections in the range (0.9-2.2) x 10(-17) cm(2) molecule(-1). The shape of the band varies significantly from one radical to the next for the series of aromatic precursors investigated. The nature and yields of hydroxylated ring-retaining oxidation products, identified in previous studies of the OH-initiated oxidation of aromatic hydrocarbons, and the results of theoretical density functional theory (DFT) calculations indicate that one or more possible isomers of the various OH-adducts may contribute to the observed spectra. Isomers where the OH-group is ortho- (or both ortho- and ipso-) to a substituent methyl-group are likely to be the most abundant but other isomers may also be formed to a significant extent. Nonetheless, the present study provides absorption spectra of the adduct radicals formed from the gas phase addition of OH to the aromatic hydrocarbons considered, near room temperature and I atm pressure. (c) 2005 Elsevier B.V. All rights reserved.

The reactivity of oytho-methoxy-substituted catechol radicals with sulfhydryl groups: Contribution for the comprehension of the mechanism of inhibition of NADPH oxidase by apocynin

Redox processes are involved in the mechanism of action of NADPH oxidase inhibitors such as diphenyleneiodonium and apocynin. Here, we studied the structure-activity relationship for apocynin and analogous ortho-methoxy-substituted catechols as inhibitors of the NADPH oxidase in neutrophils and their reactivity with peroxidase. Aiming to alter the reduction potential, the ortho-methoxy-catechol moiety was kept constant and the substituents at para position related to the hydroxyl group were varied. Two series of compounds were employed: methoxy-catechols bearing electron-withdrawing groups (MC-W) such as apocynin, vanillin, 4-nitroguaiacol, 4-cyanoguaiacol, and methoxy-catechol bearing electron-donating groups (MC-D) such as 4-methylguaiacol and 4-ethylguaiacol. We found that MC-D were weaker inhibitors compared to MD-W. Furthermore, the radicals generated by oxidation of MC-W via MPO/H(2)O(2), but not for MC-D, were able to oxidize glutathione (GSH) as verified by the formation of thiyl radicals, depletion of GSH, and recycling of the ortho-methoxy-catechols during their oxidations. The capacity of oxidizing sulfhydryl (SH) groups was also verified when ovalbumin was incubated with MC-W, but not for MC-D. Since the effect of apocynin has been correlated with inactivation of the cytosolic fractions of the NADPH oxidase complex and its oxidation during the inhibitory process develops a special role in this process, we suggest that the close relationship between the reactivity of the radicals of MC-W compounds with thiol groups and their efficacy as NADPH oxidase inhibitor could be the chemical pathway behind the mechanism of action of apocynin and should be taken into account in the design of new and specific NADPH oxidase inhibitors. (c) 2007 Elsevier B.V. All rights reserved.

Ethanol-induced gastric damage in the rat: Lack of a correlation with oxygen-derived free radicals

The present study investigated the role of oxygen-derived free radicals as mediators of acute damage to rat gastric mucosae exposed to topically applied absolute ethanol. Although a hydroxyl radical scavenger, Dimethylthiourea, was noted to exhibit profound gastroprotective properties, other pretreatment regimens employing a host of known free radical scavengers, and enzyme inhibitors failed to confirm this hypothesis. Furthermore, no change in mucosal malondialdehyde, an indicator of free radical attack to cell membranes, could be detected in ethanol exposed tissues. Taken together, the present study fails to confirm that oxygen-derived free radicals mediate the gastric damaging effects of topically applied absolute ethanol. ^

Iron accumulation in Alzheimer disease is a source of redox-generated free radicals

Damage from free radicals has been demonstrated in susceptible neuronal populations in cases of Alzheimer disease. In this study, we investigated whether iron, a potent source of the highly reactive hydroxyl radical that is generated by the Fenton reaction with H2O2, might contribute to the source of radicals in Alzheimer disease. We found, using a modified histochemical technique that relies on the formation of mixed valence iron complexes, that redox-active iron is associated with the senile plaques and neurofibrillary tangles—the pathological hallmark lesions of this disease. This lesion-associated iron is able to participate in in situ oxidation and readily catalyzes an H2O2-dependent oxidation. Furthermore, removal of iron was completely effected using deferoxamine, after which iron could be rebound to the lesions. Characterization of the iron-binding site suggests that binding is dependent on available histidine residues and on protein conformation. Taken together, these findings indicate that iron accumulation could be an important contributor toward the oxidative damage of Alzheimer disease.

DNA damage by sulfite autoxidation catalyzed by cobalt complexes

DNA damage was investigated in the presence of sulfite, dissolved oxygen and cobalt(II) complexes with glycylglycylhistidine, glycylhistidyllysine, glycylglycyltyrosylarginine and tetraglycine. These studies indicated that only Co(II) complexed with glycylglycylhistidine (GGH) induced DNA strand breaks at low sulfite concentrations (1-80 mu M) via strong oxidants formed in the reaction. In the presence of the other complexes, some damage occurred only in the presence of high sulfite concentrations (0.1-2.0 mM) after incubation for 4 h. In the presence of GGH, Co(II) and dissolved O(2), DNA damage must involve a reactive high-valent cobalt complex. The damaging effect was increased by adding S(IV), due to the oxysulfur radicals formed as intermediates in S(IV) autoxidation catalyzed by the complex. SO(3)(center dot)-S-, HO(center dot) and H(center dot) radicals were detected by EPR-spin trapping experiments with DMPO (5,5-dimethyl-1-pyrroline N-oxide). The results indicate that Co(II) binds O2 in the presence of GGH, and leads to the formation of a DMPO-HO(center dot) adduct without first forming free superoxide or hydroxyl radical, supporting the participation of a reactive high-valent cobalt complex.

Single reaction interface flow system for chemiluminescent monitoring of mannitol based on its hydroxyl radical scavenger activity

A single reaction interface flow analysis (SIFA) system for the monitoring of mannitol in pharmaceutical formulations and human urine is presented. The developed approach takes advantage of the mannitol scavenger aptitude to inhibit the chemiluminescent reaction between luminol and myoglobin in the absence of H(2)O(2). The SIFA system facilitated the fully automation of the developed methodology, allowing the in-line reproducible handling of chemical species with a very short lifetime as is the case of the hydroxyl radical generated in the abovementioned luminol/myoglobin reaction. The proposed methodology allowed the determination of mannitol concentrations between 25 mmol L(-1) and 1 mol L(-1), with good precision (R.S.D. < 4.7%, n = 3) and a sampling frequency of about 60 h(-1). The procedure was applied to the determination of mannitol in pharmaceuticals and in human urine samples Without any pretreatment process. The results obtained for pharmaceutical formulations were statistically comparable to those provided by the reference method (R.D. < 4.6%); recoveries values obtained in the analysis of spiked urine samples (between 94.9 and 105.3% of the added amount) were also satisfactory. (C) 2008 Elsevier B.V. All rights reserved.

Lignocellulosic polysaccharides and lignin degradation by wood decay fungi: the relevance of nonenzymatic Fenton-based reactions

The brown rot fungus Wolfiporia cocos and the selective white rot fungus Perenniporia medulla-panis produce peptides and phenolate-derivative compounds as low molecular weight Fe(3+)-reductants. Phenolates were the major compounds with Fe(3+)-reducing activity in both fungi and displayed Fe(3+)-reducing activity at pH 2.0 and 4.5 in the absence and presence of oxalic acid. The chemical structures of these compounds were identified. Together with Fe(3+) and H(2)O(2) (mediated Fenton reaction) they produced oxygen radicals that oxidized lignocellulosic polysaccharides and lignin extensively in vitro under conditions similar to those found in vivo. These results indicate that, in addition to the extensively studied Gloeophyllum trabeum-a model brown rot fungus-other brown rot fungi as well as selective white rot fungi, possess the means to promote Fenton chemistry to degrade cellulose and hemicellulose, and to modify lignin. Moreover, new information is provided, particularly regarding how lignin is attacked, and either repolymerized or solubilized depending on the type of fungal attack, and suggests a new pathway for selective white rot degradation of wood. The importance of Fenton reactions mediated by phenolates operating separately or synergistically with carbohydrate-degrading enzymes in brown rot fungi, and lignin-modifying enzymes in white rot fungi is discussed. This research improves our understanding of natural processes in carbon cycling in the environment, which may enable the exploration of novel methods for bioconversion of lignocellulose in the production of biofuels or polymers, in addition to the development of new and better ways to protect wood from degradation by microorganisms.

LEACHATE TREATMENT PROCESS AT A MUNICIPAL STABILIZED LANDFILL BY CATALYTIC OZONATION: AN EXPLORATORY STUDY FROM TAGUCHI ORTHOGONAL ARRAY

Catalytic ozonation has been recognized in the scientific community as an efficient technique, reaching elevated rates of recalcitrant organic material mineralization, even at the presence of scavenger species of hydroxyl free radicals. This study presents the most significant factors involving the leachate treatment stabilized by the municipal landfill of the city of Guaratingueta, State of Sao Paulo, Brazil, by using a catalytic ozonation activated by metallic ions Fe(3+), Zn(2+), Mn(2+), Ni(2+) and Cr(3+). The Taguchi L(16) orthogonal array and its associated statistical methods were also used in this study. Among the researched ions, the most notable catalysis was obtained with ferric ion, statistically significant in the reduction of COD with a confidence level of 99.5%.

Electrochemical oxidation of acid black 210 dye on the boron-doped diamond electrode in the presence of phosphate ions: Effect of current density, pH, and chloride ions

The electrochemical oxidation of acid black 210 dye (AB-210) on the boron-doped diamond (BDD) was investigated under different pH conditions. The best performance for the AB-210 oxidation occurred in alkaline phosphate solution. This is probably due to oxidizing agents such as phosphate radicals and peroxodiphosphate ions, which can be electrochemically produced with good yields on the BDD anode, mainly in alkaline solution. Under this condition, the COD (chemical oxygen demand) removal was higher than that obtained from the model proposed by Comninellis. Electrolyses performed in phosphate buffer and in the presence of chloride ions resulted in faster COD and color removals in acid and neutral solutions, but in alkaline phosphate solution, a better performance in terms of TOC removal was obtained in the absence of chloride. Moreover, organochloride compounds were detected in all electrolyses performed in the presence of chloride. The AB-210 electrooxidation on BDD using phosphate as supporting electrolyte proved to be interesting since oxidizing species generated from phosphate ions were able to completely degrade the dye without producing organochloride compounds. (C) 2009 Elsevier Ltd. All rights reserved.